AU6974098A - Compositions containing slip and antiblock agents - Google Patents

Compositions containing slip and antiblock agents Download PDF

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AU6974098A
AU6974098A AU69740/98A AU6974098A AU6974098A AU 6974098 A AU6974098 A AU 6974098A AU 69740/98 A AU69740/98 A AU 69740/98A AU 6974098 A AU6974098 A AU 6974098A AU 6974098 A AU6974098 A AU 6974098A
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Bernard Fehr
Laura K Mergenhagen
Brian E. Simmons
William R. Van Volkenburgh
Ronald Wevers
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Dow Chemical Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/01Use of inorganic substances as compounding ingredients characterized by their specific function
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/16Nitrogen-containing compounds
    • C08K5/20Carboxylic acid amides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised 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
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0838Copolymers of ethene with aromatic monomers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2314/00Polymer mixtures characterised by way of preparation
    • C08L2314/06Metallocene or single site catalysts

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Description

WO 98/46672 PCT/US98/07650 COMPOSITIONS CONTAINING SLIP AND ANTIBLOCK AGENTS 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 5 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/a-olefin interpolymers or blend compositions therefrom. The subject invention is also directed to compositions which comprise a saturated fatty acid amide or saturated 10 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 a substantially random interpolymer of one or more a-olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers or blend 15 compositions therefrom. The subject invention is also directed to compositions which comprise at least one homogeneous ethylene/a-olefin interpolymer or substantially random interpolymer of one or more c-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 20 propylene homopolymers, propylene/a-olefin copolymers, nucleating agents, and mixtures thereof. Ethylene homopolymers and ethylene/a-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 25 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. 1 WO 98/46672 PCT/US98/07650 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). A low slip tendency (or high coefficient of friction) is detrimental in automated high speed packaging operations. A low slip tendency often 5 causes equipment fouling, considerable down time, and imperfect products. 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. Typically as the density of a polyolefin composition is decreased, the tackiness of the film generally increases and the coefficient of friction 10 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 15 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 20 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. These problems have led to the development of a number of additives or agents 25 which, when included in a polymer composition, can improve the slip properties and lower the tendency to block of polymer films manufactured therefrom. The use of such slip and antiblock agents have been the subject of many publications, in part because of the numerous types of such additives, but also because the types and combinations of such additives (and their absolute and relative amounts) vary according to the nature of 30 the polymer with which they are to be mixed. For example, when low pressure gas 2 WO 98/46672 PCT/US98/07650 phase or solution phase linear low density polyethylene (LLDPE), produced using Ziegler catalysts, was commercialized in the 1970's and 1980's, new additive packages were required for maintaining slip and antiblock properties relative to those used for free radical polymerized polyolefins which had been widely used prior to the LLDPE 5 introduction. For instance, U.S. Pat. No 4,394,474 (McKinney et al.) describes a process for reducing block and increasing slip in extrusion cast films of LLDPE by incorporating into the polymer, a secondary fatty acid amide and a finely divided natural mineral composition. U.S. Pat. No 4,430,289 (McKinney et al.) describes a process for reducing block and increasing slip in blown films of LLDPE by 10 incorporating into the polymer, a secondary fatty acid amide having a saturated alkyl group and an unsaturated alkyl group and a finely divided natural mineral composition. U.S. Pat. No 4,454,272 (McKinney et al.) describes compositions comprising a blend of high molecular weight LLDPE. a secondary fatty acid amide. and a finely-divided naturally-occurring mineral. U.S. Pat. No 4,529,764 (McKinney et al.) describes an 15 extrusion blown film consisting essentially of a blend of high molecular weight 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 20 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. U.S. Pat. No 5,393,814 (Chen et al.) describes a composition of matter comprising a polyolefin, and an alkenyl monoamide of a dicarboxylic acid. Finally, J610119644-A describes a linear low density polyethylene 25 resin containing LLDPE, a fatty acid amide and/or silica gel particles. The relatively recent introduction of metallocene-based catalysts for ethylene/a 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, 30 terpolymers, etc.). These metallocene catalysts include the bis(cyclopentadienyl) 3 WO 98/46672 PCT/US98/07650 catalyst systems and the mono(cyclopentadienyl)- or Constrained Geometry catalyst systems. Such constrained geometry metal complexes and methods for their preparation are disclosed in U.S. Application Serial No. 545,403, filed July 3, 1990 (EP-A 5 416,815), European Patent Application EP-A-468,65 1; European Patent Application EP-A-514,828; U.S. Application Serial No. 876,268, filed May 1, 1992, (EP-A 520,732) as well as, US-A-5,374,696, US-A-5;470,993; US-A-5,055,438, US-A 5,057,475, US-A-5,096,867, US-A-5,064,802, and US-A-5,132,380. In addition, certain cationic derivatives of the foregoing constrained geometry catalysts that are 10 highly useful as olefin polymerization catalysts are disclosed and claimed in US-A 5,132,380. In US-A 5,453,410 combinations of cationic constrained geometry catalysts with an alumoxane were disclosed as suitable olefin polymerization catalysts. For the teachings contained therein, the aforementioned pending United States Patent applications, issued United States Patents and published European Patent Applications 15 are herein incorporated in their entirety by reference thereto. The use of 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, 20 traditional Ziegler catalyzed heterogeneous polyolefin polymers. Although not wishing to be bound by any theory, 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 25 block levels while maintaining other important properties such as optics. Attempts to combine the improved strength properties associated with homogeneous interpolymers with the inherent processing advantages of heterogeneous interpolymers has also led to the development of compositions comprising blends of homogeneous interpolymers produced by metallocene catalysts 30 and heterogeneous interpolymers produced using traditional Ziegler catalysts. 4 WO 98/46672 PCT/US98/07650 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 5 achieve targeted slip and block levels. In addition to ethylene/aliphatic c-olefin interpolymers, the new constrained geometry catalysts can also be used to prepare the generic class of a-olefin/hindered vinylidene monomer substantially random interpolymers, including materials such as c-olefin/vinyl aromatic monomer interpolymers. These materials, such as 10 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. Thus it would be advantageous to provide homogeneous interpolymer 15 compositions or substantially random u-olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers compositions exhibiting good antiblock properties and low COF while maintaining good physical properties including sealability and abuse resistance while maintaining good optical properties. 20 It would be further advantageous to provide compositions which are blends comprising homogeneous interpolymers or substantially random interpolymers of x 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 25 sealability and abuse resistance while maintaining good optical properties. These and other advantages are accomplished by the embodiments of the present invention described hereinafter. The present invention pertains to compositions comprising; 5 WO 98/46672 PCTIUS98/07650 (A) a homogeneous ethylene/c-olefin interpolymer having a narrow composition distribution; and (B) a saturated fatty acid amide or saturated ethylenebis(amide); and (C) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); 5 and (D) a finely divided inorganic compound; and wherein the sum of the concentrations of Components B and C is greater than 1500 ppm, based on the combined weights of Components A, B, C, and D and, when the resin composition is fabricated into a blown film having a thickness of 2 mils, said film is 10 characterized as having a block of less than 49 g and a COF of less than 0.31. The present invention also pertains to compositions comprising; (A) an interpolymer blend composition comprising; (1) a homogeneous ethylene/a-olefin interpolymer having a narrow composition distribution; and 15 (2) a second interpolymer comprising; (a) a heterogeneous ethylene/ac-olefin interpolymer having a broad composition distribution; or (b) the interpolymer (1) having a different 12, or density, or M., or MJM,; or 20 (c) any combination of (a) or (b); and (B) a saturated fatty acid amide or saturated ethylenebis(amide); and (C) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); and (D) a finely divided inorganic compound; and wherein 25 the sum of the concentrations of Components B and C is greater than 1,500 ppm based on the combined weights of Components A, B. C, and D, and when the resin composition is fabricated into a blown film having a thickness of 2 mils, said film is characterized as having a block of less than 49 g and a COF of less than 0.31. We have surprisingly found that a three component blend of a saturated fatty 30 acid amide or saturated ethylenebis(amide), an unsaturated fatty acid aide or 6 WO 98/46672 PCT/US98/07650 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/a-olefin interpolymers or blend compositions therefrom. Additionally these advantages can be realized, generally without loss of other important 5 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 thermoform fill/ seal. 10 The present invention also pertains to compositions comprising; (A) at least one substantially random interpolymer; wherein said interpolymer comprises; (1) from 0.5 to 65 mole percent of polymer units derived from; (a) at least one vinylidene aromatic monomer, or 15 (b) at least one hindered aliphatic vinylidene monomer, or (c) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic vinylidene monomer; and (2) from 35 to 99.5 mole percent of polymer units derived from at least one aliphatic c-olefin having from 2 to 20 carbon atoms; and 20 (B) a saturated fatty acid amide or saturated ethylenebis(amide); or (C) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); or (D) a finely divided inorganic compound; or (E) a combination of at least one of (B), (C), and (D). 25 The present invention also pertains to a composition comprising; (A) a resin composition comprising; (1) a homogeneous ethylene/a-olefin interpolymer having a narrow composition distribution; or (2) at least one substantially random interpolymer; wherein said 30 interpolymer comprises; 7 WO 98/46672 PCT/US98/07650 (a) from 0.5 to 65 mole percent of polymer units derived from; (i) at least one vinylidene aromatic monomer, or (ii) at least one hindered aliphatic vinylidene monomer, or 5 (iii) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic vinylidene monomer; and (b) from 35 to 99.5 mole percent of polymer units derived from at least one aliphatic a-olefin having from 2 to 20 carbon atoms; 10 and, optionally 3) a homopolymer of propylene or a copolymer of propylene and one or more C 2 - C, ax-olefins; and (B) one or more of; (1) a saturated fatty acid amide or saturated ethylenebis(amide) or 15 (2) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); or (3) a combination of B(1) and B(2); and, optionally, (C) a nucleating agent. 20 These and other features of the of the present invention will become better understood with reference to the following descriptions and appended claims. All references herein to elements or metals belonging to a certain Group refer to the Periodic Table of the Elements published and copyrighted by CRC Press, Inc., 25 1989. Also any reference to the Group or Groups shall be to the Group or Groups as reflected in this Periodic Table of the Elements using the IUPAC system for numbering groups. 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 30 units between any lower value and any higher value. As an example, if it is stated that 8 WO 98/46672 PCT/US98/07650 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. For values which are 5 less than one, one unit is considered to be 0.0001, 0.001, 0.01 or 0.1 as appropriate. These are only examples of what is specifically intended and all possible combinations of numerical values between the lowest value and the highest value enumerated are to be considered to be expressly stated in this application in a similar manner. The term "hydrocarbyl" as employed herein means any aliphatic, cycloaliphatic, 10 aromatic, aryl substituted aliphatic, aryl substituted cycloaliphatic, aliphatic substituted aromatic, or aliphatic substituted cycloaliphatic groups. The term "hydrocarbyloxy" means a hydrocarbyl group having an oxygen linkage between it and the carbon atom to which it is attached. The term "silyl" means a group having a silicon linkage between it and the 15 carbon atom to which it is attached. The term "germyl" means a group having a germanium linkage between it and the carbon atom to which it is attached. The term "substituted cyclopentadienyl" is intended to include ring-substituted or polynuclear derivatives of the cyclopentadienyl moiety wherein the substituent is 20 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. Specific examples of substituted cyclopentadienyls include indenyl, tetrahydroindenyl, fluorenyl, and octahydrofluorenyl groups. 25 The term "Bronsted Acid cation" means a cation which acts as a proton donor. The term "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. For the compositions of the present invention the COF values were measured 30 after 24 hr. in accordance with ASTM D-1894 (utilizing a TMI Direct Drive Monitor 9 WO 98/46672 PCTIUS98/07650 Slip and friction Tester). For the purposes of the present invention "good" slip characteristics are associated with COF values of less than 0.31. For the compositions of the present invention the block values were measured off line in accordance with ASTM D-3354-89 (utilizing a Kayeness Block Tester). For 5 the purposes of the present invention "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 10 invention was conveniently indicated using a melt index measurement according to ASTM D-1238, Condition 190'C/2.16 kg (formally known as "Condition (E)" and also known as 12). Melt index is inversely proportional to the molecular weight of the polymer. Thus, the higher the molecular weight, the lower the melt index, although the relationship is not linear 15 Other useful physical property determinations made on the novel interpolymer compositions described herein include the melt flow ratio (MFR): measured by determining "110" (according to ASTM D-1238, Condition 190*C/10 kg (formerly known as "Condition (N)") and dividing the obtained I10 by the 12. The ratio of these two melt index terms is the melt flow ratio and is designated as 110/12 20 The molecular weight (M,.) and distribution (M/Me) of the interpolymer component(s) of the present invention were determined by gel permeation chromatography (GPC) on a Waters 150C high temperature chromatographic unit equipped with mixed porosity columns, operating at a system temperature of 140'C. The solvent is 1,2,4-trichlorobenzene, from which 0.3 percent by weight solutions of 25 the samples were prepared for injection. The flow rate was 1.0 milliliters/minute and the injection size was 100 microliters. 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 30 determined by using appropriate Mark-Houwink coefficients for polyethylene and 10 WO 98/46672 PCT/US98/07650 polystyrene (as described by Williams and Ward in Journal of Polymer Science, Polymer Letters, Vol. 6, (621) 1968) to derive the following equation: Mpolyethylene = a * (Mpolystyrene)b. In this equation, a = 0.4316 and b = 1.0. Weight average molecular weight, Mw, and 5 number average molecular weight, M., was calculated in the usual manner according to the following formula: Mj= (I wj(M/)); where wi is the weight fraction of the molecules with molecular weight M, eluting from the GPC column in fraction i and j = I when calculating M, and j = -1 when calculating Mn. 10 The 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 15 RaC(O)NHRb where R' is a saturated alkyl group having of from 10 carbon atoms to 26 carbon atoms and R' 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 20 stearamide, palmityl pamitamide. stearyl arachidamide and mixtures thereof. The saturated ethylenebis(amides) useful in the present invention conform essentially to the empirical formula RaC(O)NHCHCH 2 NHC(O)Ra where R' is as defined previously. Compounds which conform to the above empirical 25 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 RcC(O)NHRd 11 WO 98/46672 PCT/US98/07650 where R* is an unsaturated alkyl group having of from 10 carbon atoms to 26 carbon atoms and Rd 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. 5 The unsaturated ethylenebis(amides) useful in the present invention conform essentially to the empirical formula
R*C(O)NHCH
2
CH
2 NHC(O)R* where R' 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* is unsaturated. 10 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 15 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 20 absorption value of 21 to 175 parts oil per 100 parts organic. The 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 25 interpolymer molecule and wherein substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer. Such interpolymers are distinct from the typical Ziegler catalyzed interpolymers which are known as heterogeneous interpolymers and are those in which the interpolymer molecules do not have the same ethylene/comonomer ratio. The homogeneous polymers are also distinct 30 from LDPE produced by high pressure free radical catalyzed ethylene polymerization 12 WO 98/46672 PCT/US98/07650 which results in highly branched polyethylene which is known to those skilled in the art to have numerous long chain branches. The term "narrow composition distribution" used herein describes the comonomer distribution for homogeneous interpolymers and means that the 5 homogeneous interpolymers 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 interpolymers can also be characterized by their SCBDI (Short Chain Branch Distribution Index) or CDBI 10 (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. 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 15 et al, Journal of Polymer Science, Polv. Phys. Ed., Vol. 20, p. 441 (1982), in U.S. Patent 4,798,081 (Hazlitt et al.), or as is described in USP 5,008,204 (Stehling), the disclosure of which is incorporated 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 20 incorporated herein by reference. The SCBDI or CDBI for the homogeneous narrow composition ethvlene/x-olefin interpolymers 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 interpolymers used in this 25 invention essentially lack a measurable "high density" (or homopolymer) fraction as measured by the TREF technique. The homogeneous interpolymers 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). 13 WO 98/46672 PCT/US98/07650 Also included as components in the current invention are the substantially linear ethylene/x-olefin interpolymers. The substantially linear ethylene/a-olefin interpolymers of the present invention are herein defined as in US Pat. Nos. 5,272,236 and 5,278,272 both of which are incorporated herein by reference. The substantially 5 linear ethylene/a-olefin interpolymers are also homogeneous interpolymers as the comonomer is randomly distributed within a given interpolymer molecule and substantially all of the interpolymer molecules have the same ethylene/comonomer ratio within that interpolymer. However the term "substantially linear" ethylene/a-olefin interpolymer means 10 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, for example. 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 15 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 13 C nuclear magnetic resonance (NMR) spectroscopy and is quantified using the method of Randall (Rev Macromol. Chem. Phys., C29 (2&3), p. 285-297), the disclosure of which is incorporated herein by reference. Long chain branching, of course, is to be 20 distinguished from short chain branches which result solely from incorporation 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. More specifically, the polymer is characterized as having 0.0 1 long chain 25 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/ax-olefin interpolymers useful in this invention 30 surprisingly have excellent processability, even though they have relatively narrow 14 WO 98/46672 PCT/US98/07650 molecular weight distributions. The substantially linear ethylene/ax-olefin interpolymers have a molecular weight distribution. Mw/Mn, defined by the equation: Mw/Mn -< (110/12) - 4.63. Even more surprising, the melt flow ratio (I10/12) of the substantially linear 5 olefin polymers can be varied essentially independently of the polydispersity index (that is, molecular weight distribution (Mw/Mn)). This is contrasted with conventional heterogeneously branched linear polyethylene resins having rheological properties such that as the polydispersity index increases, the Il 1/I, value also increases. For the substantially linear ethylene/x-olefin polymers used in the compositions of the 10 invention, the I10/12) ratio indicates the degree of long chain branching, that is, the higher the I10/12 ratio, the more long chain branching in the polymer. The "rheological processing index" (PI) is the apparent viscosity (in kpoise) of a polymer measured by a gas extrusion rheometer (GER). The gas extrusion rheometer is described by M. Shida, R.N. Shroff and L.V. Cancio in Polymer Engineering Science, 15 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 incorporated by reference herein in their entirety. All GER experiments are performed at a temperature of 190'C. at nitrogen pressures between 5250 to 500 psig using a 0.0296 inch diameter, 20:1 L/D die with an entrance angle of 1800. For the 20 substantially linear ethylene/a-olefin polymers described herein, the PI is the apparent viscosity (in kpoise) of a material measured by GER at an apparent shear stress of 2.15 x 106 dyne/cm 2 . The substantially linear ethylene/a-olefin interpolymers 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/a-olefin polymers described herein 25 have a PI less than or equal to 70 percent of the PI of a comparative linear ethylene/a olefin polymer which does not contain long chain branching but of the same 12 and Mw/Mn. An apparent shear stress vs. apparent shear rate plot is used to identify the melt fracture phenomena. According to Ramamurthy in Journal of Rheology, 30(2), 337 15 WO 98/46672 PCT/US98/07650 357, 1986, above a certain critical flow rate, the observed extrudate irregularities may be broadly classified into two main types: surface melt fracture and gross melt fracture. Surface melt fracture occurs under apparently steady flow conditions and ranges in detail from loss of specular gloss to the more severe form of "sharkskin". In this 5 disclosure, the onset of surface melt fracture (OSMF) is characterized at the beginning of losing extrudate gloss at which the surface roughness of extrudate can only be detected by 40X magnification. The critical shear rate at onset of surface melt fracture for the substantially linear ethylene/ax-olefin interpolymers is at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene/a 10 olefin polymer which does not contain long chain branching but of the same I2 and Mw/Mn. wherein " the same" as used herein means that each value is within 10 percent of the comparative value of the comparative linear ethylene polymer. Gross melt fracture occurs at unsteady flow conditions and ranges in detail from regular (alternating rough and smooth, helical. etc.) to random distortions. For 15 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 20 composition distribution ethylene/a-olefin interpolymer component of the present invention comprises: a) a metal complex corresponding to the formula: LMX X'q, that has been or subsequently is rendered catalytically active by combination with an 25 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 ii bonding mode to one or more L groups; L independently each occurrence is a cyclopentadienyl-, indenyl-, tetrahydroindenyl-, fluorenyl-,. tetrahydrofluorenyl-, or octahydrofluorenyl 30 group optionally substituted with from 1 to 8 substituents independently selected from 16 WO 98/46672 PCT/US98/07650 the group consisting of hydrocarbyl, halo, halohydrocarbyl, aminohydrocarbyl, hydrocarbyloxy, dihydrocarbylamino. dihydrocarbylphosphino, silyl, aminosilyl, hydrocarbyloxysilyl, and halosilyl groups containing up to 20 non-hydrogen atoms,. or further optionally two such L groups may be joined together by a divalent substituent 5 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 c-bonded ligand group, a divalent anionic a-bonded ligand group having both valences bonded to M, or 10 a divalent anionic a-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; 15 p is 0. 1 or 2, and is 1 less than the formal oxidation state of M when X is an monovalent anionic a-bonded ligand group or a divalent anionic a-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 a-bonded ligand group having both valencies bonded to M; and 20 q is 0, 1 or 2. The catalysts used to prepare the homogeneous narrow composition distribution ethylene/u-olefin interpolymer 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 25 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 incorporated in their entirety by reference thereto. The cationic complexes are believed to correspond to the formula: 17 WO 98/46672 PCT/US98/07650 LIM~X-, 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 5 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 10 substituted derivative thereof. having both valencies bonded to M) by the use of a Lewis acid activating cocatalyst, especially tris(perfluoro-aryl)boranes. These zwitterionic complexes are believed to correspond to the formula:
L,M~X-X**-A
wherein: 15 M is a Group 4 metal in the +4 formal oxidation state; L, X. I 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; and A- is a noncoordinating, compatible anion derived from the activating 20 cocatalyst. As used herein, the recitation "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 a olefin. A non-coordinating anion specifically refers to an anion which when 25 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 18 WO 98/46672 PCT/US98/07650 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(1,2-dimethylphosphino)ethane;
P(OR)
3 , 5 (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. 10 Examples of coordination complexes a) used for the present invention include the foregoing species: R RR R3 MX" (R* 2
E)
7 R3 MX" R, R3 R, R R or Ra wherein: M is titanium, zirconium or hafnium, preferably zirconium or hafnium, in the +2 15 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, siladiyl or germadiyl group) thereby forming a fused ring system, X" independently each occurrence is an anionic ligand 20 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 7n-complex with M, whereupon M is in the +2 formal oxidation state, R* independently each occurrence is C, alkyl or 19 WO 98/46672 PCTIUS98/07650 phenyl, E independently each occurrence is carbon or silicon, and x is an integer from 1 to 8. Additional examples of metal complexes a) include those corresponding to the formula: LMXpX'q (III) 5 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:
R
3 Z-Y 3 M X"n R 3 R 3 wherein: M is titanium, zirconium or hafnium in the +2, +3 or +4 formal oxidation state; 10 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, siladiyl or germadiyl group) thereby forming a fused ring system, each X" is a halo, hydrocarbyl, hydrocarbyloxy, hydrocarbylamino, 15 or silyl group, said group having up to 20 non-hydrogen atoms, or two X" groups together form a neutral C 5
-
3 0 conjugated diene or a divalent derivative thereof; Y is -0-, -S-, -NR*-, -PR*-; Z is SiR* 2 , CR* 2 , SiR*,SiR* 2 , CR* 2
CR*
2 , CR*=CR*, CR*,SiR* 2 , or GeR* 2 , wherein R* is as previously defined, and n is an integer from 1 to 3. 20 Most preferred coordination complexes a) used for the present invention are complexes corresponding to the formula: 20 WO 98/46672 PCT/US98/07650 Ra
R
3 z
R
3
R
3 z-Y
R
3 R3 R R ~~~~ Z Y o M \- XP RMR3 R3 V \Xq R 3
R
3 wherein:
R
3 independently each occurrence is a group selected from hydrogen, hydrocarbyl, halohydrocarbyl, silyl, germyl and mixtures thereof, said group containing 5 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; 10 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-, di(hydrocarbyl)amino-, hydrocarbyloxy- and 15 di(hydrocarbyl)phosphino-substituted derivatives thereof, said 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 20 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 21 WO 98/46672 PCT/US98/07650 hydrocarbyl groups, said X' having up to 40 carbon atoms and forming a 7t-complex with M. More preferred coordination complexes a) used according to the present invention are complexes corresponding to the formula:
R
3
R
3
R
3 3 Z*-Y R3 RR SZ y M - XP
R
3 or
R
3 M X' q 5 X q wherein: R3 independently each occurrence is hydrogen or C,.
6 alkyl; M is titanium; Y is -0-, -S-, -NR*-, -PR*-; 10 Z* is SiR* 9 , CR* 2 , SiR* 2 SiR* 2 , CR* 2
CR*
2 , CR*=CR*, CR*SiR* 2 , or GeR* 2 ; 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* 15 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-1,4 20 diyl, and when p is 0, q is 1, M is in the +2 formal oxidation state, and X' is 1,4-diphenyl 1,3-butadiene or 1,3-pentadiene. The latter diene is illustrative of unsymetrical diene 22 WO 98/46672 PCTIUS98/07650 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, 5 the teachings of which are hereby incorporated 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. Examples of suitable reducing agents are alkali metals, alkaline 10 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 15 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 1 20 dialkyl ethers, C 1 4 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 25 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, and 30 ferrocenium salts of compatible, noncoordinating anions. Suitable activating 23 WO 98/46672 PCT/US98/07650 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 5 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 incorporated by reference. More particularly, suitable ion forming compounds useful as cocatalysts comprise a cation which is a Bronsted acid capable of donating a proton. and a 10 compatible, noncoordinating anion, A-. As used herein, the term "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 15 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 20 components are combined. Also, 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 25 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. Preferably such cocatalysts may be represented by the following general formula: 24 WO 98/46672 PCTIUS98/07650 (L*-H)~d (A)d wherein: L* is a neutral Lewis base; (L*-H)^ is a Bronsted acid; 5 Ad- is a noncoordinating, compatible anion having a charge of d-. and d is an integer from I to 3. More preferably Ad~ corresponds to the formula: [M'Q 4 ]-; wherein: M' is boron or aluminum in the +3 formal oxidation state; and 10 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 15 more than one occurrence is Q halide. Examples of suitable hydrocarbyloxide Q groups are disclosed in U. S. Patent 5,296,433, the teachings of which are herein incorporated by reference. In a more preferred example. d is one, that is, the counter ion has a single negative charge and is A-. Activating cocatalysts comprising boron which are 20 particularly useful in the preparation of catalysts of this invention may be represented by the following general formula: (L*-H)*(BQ4)-; wherein: L* is as previously defined; 25 B is boron in a formal oxidation state of 3; and 25 WO 98/46672 PCTIUS98/07650 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. Most preferably, Q is each occurrence a fluorinated aryl group, especially, a 5 pentafluorophenyl group. Illustrative, but not limiting, examples of boron compounds which may be used as an activating cocatalyst for the present invention are tri-substituted ammonium salts such as: trimethylammonium tetrakis(pentafluorophenyl) borate, 10 triethylammonium tetrakis(pentafluorophenyl) borate, tripropylammonium tetrakis(pentafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(pentafluorophenyl) borate, tri(sec-butyl)ammonium tetrakis(pentafluorophenyl) borate, N.N-dimethyl-N-dodecylammonium tetrakis(pentafluorophenyl) borate, 15 N,N-dimethyl-N-octadecylammonium tetrakis(pentafluorophenyl) borate, N-methyl-NN-didodecylammonium tetrakis(pentafluorophenyl) borate, N-methyl-N.N-dioctadecylammonium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethylanilinium n-butyltris(pentafluorophenyl) borate, 20 NN-dimethylanilinium benzyltris(pentafluorophenyl) borate, N,N-dimethylanilinium tetrakis(4-(t-butyldimethylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis(4-(triisopropylsilyl)-2, 3, 5, 6-tetrafluorophenyl) borate, 25 N,N-dimethylanilinium pentafluorophenoxytris(pentafluorophenyl) borate, N,N-diethylanilinium tetrakis(pentafluorophenyl) borate, N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(pentafluorophenyl) borate, trimethylammonium tetrakis(2,3,4,6-tetrafluorophenyl)borate, triethylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, 26 WO 98/46672 PCT/US98/07650 tripropylammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, tri(n-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, dimethyl(t-butyl)ammonium tetrakis(2,3,4,6-tetrafluorophenyl) borate, N,N-dimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, 5 NN-diethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate, and N,N-dimethyl-2,4,6-trimethylanilinium tetrakis(2,3,4,6-tetrafluorophenyl) borate; disubstituted ammonium salts such as: di-(i-propyl)ammonium tetrakis(pentafluorophenyl) borate, and dicyclohexylammonium tetrakis(pentafluorophenyl) borate; 10 trisubstituted phosphonium salts such as: triphenylphosphonium tetrakis(pentafluorophenyl) borate, tri(o-tolyl)phosphonium tetrakis(pentafluorophenyl) borate, and tri(2,6-dimethylphenyl)phosphonium tetrakis(pentafluorophenyl) borate; disubstituted oxonium salts such as: 15 diphenyloxonium tetrakis(pentafluorophenyl) borate, di(o-tolyl)oxonium tetrakis(pentafluorophenyl) borate, and di(2,6-dimethylphenyl)oxonium tetrakis(pentafluorophenyl) borate; disubstituted sulfonium salts such as: diphenylsulfonium tetrakis(pentafluorophenyl) borate, 20 di(o-tolyl)sulfonium tetrakis(pentafluorophenyl) borate, and bis(2,6-dimethylphenyl)sulfonium tetrakis(pentafluorophenyl) borate. Preferred (L*-H)* cations are NN-dimethylanilinium, tributylammonium, N methyl-N,N-didodecylammonium, N-methyl-NN-dioctadecylammonium, and mixtures thereof 25 Another suitable ion forming, activating cocatalyst comprises a salt of a cationic oxidizing agent and a noncoordinating, compatible anion represented by the formula: (Oxe+)(Ad-). 27 WO 98/46672 PCT/US98/07650 wherein: Ox*" is a cationic oxidizing agent having a charge of e+; e is an integer from 1 to 3; and Ad- and d are as previously defined. 5 Examples of cationic oxidizing agents include: ferrocenium, hydrocarbyl substituted ferrocenium, Ag' or Pb 2 . Preferred embodiments of Ad 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 10 which is a salt of a carbenium ion and a noncoordinating. compatible anion represented by the formula: 0' A wherein: 0* is a C- 2 0 carbenium ion; and 15 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: 20 R'Si*A wherein: R'is C- 1 0 hydrocarbyl, and A- are as previously defined. Preferred silylium salt activating cocatalysts are trimethylsilylium tetrakispentafluorophenylborate, triethylsilylium tetrakispentafluorophenylborate and 25 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 28 WO 98/46672 PCT/US98/07650 activating cocatalysts for addition polymerization catalysts is claimed in USSN 08/304,314, filed September 12, 1994. Certain complexes of alcohols, mercaptans, silanols, and oximes with tris(pentafluorophenyl)borane are also effective catalyst activators and may be used for 5 the present invention. Such cocatalysts are disclosed in USP 5,296,433, the teachings of which are herein incorporated by reference. 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 10 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. 15 The metallocene catalyst can contain either no aluminum-containing cocatalyst or only a small amount (that is, from 3:1 Al:Transition metal ratio to 100:1 Al:Transition metal ratio) of aluminum cocatalyst. For example, 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 20 methylaluminoxane, propylaluminoxane, isobutylaluminoxane, and combinations thereof . So-called modified methylaluminoxane (MMAO) 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 incorporated herein by reference. Aluminoxanes can also be made as disclosed in U.S. patents Nos. 4,544,762 25 (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 incorporated herein by reference. In general, the polymerization may be accomplished at conditions well known in the prior art for Ziegler-Natta or Kaminsky-Sinn type polymerization reactions, that 29 WO 98/46672 PCT/US98/07650 is, temperatures from 0-250 *C, preferably 30 to 200 'C and pressures from atmospheric (1 x 10' 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 5 (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. 10 In most polymerization reactions the molar ratio of catalyst:polymerizable compounds employed is from 101:1 to 10-':1. more preferably from 10-: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 cvclohexane, 15 cycloheptane. methylcyclohexane, methylcycloheptane, and mixtures thereof; perfluorinated hydrocarbons such as perfluorinated C 410 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, 20 butene. butadiene, cyclopentene. 1 -hexene, 4-vinylcyclohexene, 3-methyl-i -pentene, 4 methyl-i -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. Also included as components in the resin compositions of the present invention 25 are blends of the homogeneous narrow composition distribution ethylene/a-olefin interpolymers 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 ethylene/x-olefin interpolymer, and most preferably with a 30 WO 98/46672 PCTIUS98/07650 second homogeneous narrow composition distribution ethylene/c--olefin interpolymer of different molecular weight and/or density. The heterogeneous component is differentiated from the homogeneous component in that in the latter, substantially all of the interpolymer molecules have the 5 same ethylene/comonomer ratio within that interpolymer, whereas heterogeneous interpolymers are those in which the interpolymer molecules do not have the same ethylene/comonomer ratio. The term "broad composition distribution" used herein describes the comonomer distribution for heterogeneous interpolymers and means that the heterogeneous interpolymers have a "high density" fraction and that the 10 heterogeneous interpolymers have multiple melting peaks (that is, exhibit at least two distinct melting peaks) by DSC. The heterogeneous interpolymers 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 interpolymers also have a degree of 15 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 interpolymer component of the blend can be an ethylene homopolymer or, preferably, interpolymers of ethylene with at least one C3-C20 a 20 olefin and/or C4-C 18 diolefins. Heterogeneous interpolymers of ethylene and propylene, butene- 1, hexene- 1, 4-methyl-i -pentene and octene- 1 are preferred and copolymers of ethylene and 1-octene are especially preferred. For the heterogeneous interpolymers described herein, the term "broad molecular weight distribution" means that the Mw/Mn of the interpolymer (or fraction) 25 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 30 or aluminum halides or hydrogen chloride, and a transition metal compound. Examples 31 WO 98/46672 PCT/US98/07650 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 incorporated herein by reference. Suitable catalyst materials may also be derived from a inert oxide supports and 5 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 incorporated herein by reference. If blends with a second ethylene c-olefin interpolymer are to be used then each component described herein can each be made separately in different reactors, and 10 subsequently blended together to make the interpolymer blend composition components of the present invention. Preferably. though. 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 incorporated 15 herein by reference. In the multiple reactor scheme, at least one of the reactors makes the homogeneous ethylene interpolymer using a metallocene catalyst and at least one of the reactors makes the second polymer, either a different homogeneous ethylene interpolymer using a single site catalyst or a heterogeneous ethylene interpolymer using a Ziegler catalyst. In a preferred mode of operation, the reactors are operated in a series 20 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/a-olefin reactants and if required, a second catalyst and solvent. Mixing of the individual components comprising the resin compositions of the 25 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 interpolymer of ethylene. This masterbatch is then blended or let down with additional 30 quantities of the homogeneous interpolymers or a blend comprising the homogeneous 32 WO 98/46672 PCT/US98/07650 interpolymers to achieve the desired concentrations of each component in articles fabricated from the resulting composition. Alternatively concentrates of each of the saturated fatty acid amide or ethylenebis(amide), the unsaturated fatty acid amide or ethylenebis(amide) and the 5 finely divided inorganic compound could be prepared in a polyethylene matrix and blended with additional quantities of the homogeneous interpolymers or a blend comprising the homogeneous interpolymer, to achieve the desired concentrations of each component. These desired concentrations will vary primarily with the polymer components density, but the correct amounts can be readily determined without undue 10 experimentation by one skilled in the art using the mixing methods and test procedures described herein. Thus in a typical preparation, 94.7 kgs of a homogeneous ethylene octene interpolymer AFFINITY® PL1880 (melt index, I = 1.0 g/10 min, density = 0.9020 g/cm 3 ), available from the Dow Chemical Company and made utilizing a metallocene 15 catalyst was blended with 3.0 kg of a 5 wt % concentrate of erucamide in a matrix of an ethylene octene interpolymer (melt index, I, = 6.0 g/10 min, density = 0.9110 g/cm 3 ) and 1.0 kgs of a 5 wt % concentrate of stearamide in a matrix of an ethylene octene interpolymer (melt index, I, = 6.0 g/10 min, density = 0.9110 g/cm 3 ) and 1.25 kgs of of a 20 wt% concentrate of SiOG in a matrix of an ethylene octene interpolymer (melt 20 index, 1 = 6.0 g/1l0 min, density = 0.9110 g/cm 3 ) to give a final resin composition containing 1500 ppm erucamide. 500 ppm stearamide, and 2,500 ppm SiO 2 . While effective amounts and preferred concentrations of the individual components vary somewhat with the density of the homogeneous interpolymer or blend component, the temperature of fabrication and the smoothness of the film surface, for 25 the purposes of the invention, generally preferred concentrations of ; (i) 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, (ii) 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 and 30 (iii) the finely divided inorganic compound are in the range of from 500 to 15,000, 33 WO 98/46672 PCTIUS98/07650 preferably of from 1.000 to 10,000, more preferably of from 1,250 to 7.500 ppm and and the generally preferred weight ratio of the unsaturated fatty acid amide or ethylene bis(amides) to the saturated fatty acid amide or ethylene-bis(amide) is in the range of from 10:1 to 1:10 Finally the sum of the concentrations of the saturated fatty acid 5 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/a olefin interpolymer incorporated 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 10 to 0.910 g/cm 3 . The melt index,I 2 , for said homogeneous narrow composition distribution ethylene/u-olefin interpolymer is of from 0.2 to 100, preferably from 0.4 to 50. more preferably from 0.5 to 20 g/10 min. The 110/12 ratio of said homogeneous narrow composition distribution 15 ethylene/a-olefin interpolymer is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11. The Mw/Mn ratio of said homogeneous narrow composition distribution ethylene/a-olefin interpolymer is preferably of from 1.8 to 6.0. The amount of the first homogeneous narrow composition distribution 20 ethylene/a-olefin interpolymer incorporated into the blend component of the resin compositions of the present invention comprising two homogeneous interpolymers, 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. 25 In such blends, the density of said first homogeneous narrow composition distribution ethylene/a-olefin interpolymer 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 indexI 2 , of said first homogeneous narrow composition distribution ethylene/a-olefin interpolymer is generally from 0.05 to 100 preferably from 0.2 to 50, 30 more preferably from 0.2 to 20 grams/10 minutes (g/10 min). 34 WO 98/46672 PCT/US98/07650 The 110/12 ratio of said first homogeneous narrow composition distribution ethylene/a-olefin interpolymer is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11. The Mw/Mn ratio of said first homogeneous narrow composition distribution 5 ethylene/a-olefin interpolymer is preferably from 1.8 to 6.0. The amount of the second homogeneous narrow composition distribution ethylene/a-olefin interpolymer incorporated 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 10 the individual components of the final resin composition. The melt index, density, MJMn and I1/I of the said second homogeneous narrow composition distribution ethylene/a-olefin interpolymer is selected to give the required properties of the final blend composition. The amount of the homogeneous narrow composition distribution ethylene/a 15 olefin interpolymer incorporated into the blended composition of the present invention comprising a homogeneous and a heterogeneous interpolymer 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. In such blends, the density of said homogeneous narrow composition 20 distribution ethylene/a-olefin interpolymer is of 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, I2, of said homogeneous narrow composition distribution ethylene/u-olefin interpolymer is of from 0.05 to 100 preferably from 0.2 to 50, more preferably from 0.2 to 20 grams/10 minutes (g/1 0 min). 25 The I 10/1,2 ratio of said homogeneous narrow composition distribution ethylene/u-olefin interpolymer is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11. The Mw/Mn ratio of said homogeneous narrow composition distribution ethylene/a-olefin interpolymer is preferably of from 1.8 to 6.0. 35 WO 98/46672 PCT/US98/07650 The amount of the heterogeneous narrow composition distribution ethylene/aX olefin interpolymer incorporated 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. 5 The melt index, density, M,/Mn and 10/12 of the said heterogeneous broad composition distribution ethylene/a-olefin interpolymer 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 interpolymers or a homogeneous and a heterogeneous 10 ethylene/ax-olefin interpolymer 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, L of the final blended ethylene/a-olefin interpolymer 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). 15 The 110/12 ratio of the blended ethylene/a-olefin interpolymer of the present invention is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11. The Mw/Mn ratio of the blended ethylene/a-olefin interpolymer of the present invention is preferably from 1.8 to 6.0. 20 The compositions of the present invention can also comprise one or more substantially random interpolymers. The term "substantially random" in the substantially random interpolymer comprising an a-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 interpolymer can be described by 25 the Bernoulli statistical model or by a first or second order Markovian statistical model, as described by J. C. Randall in POLYMER SEQUENCE DETERMINATION, Carbon-13 NMR Method, Academic Press New York, 1977, pp. 71-78. Preferably, the substantially random interpolymer comprising an ax-olefin and a vinylidene aromatic monomer does not contain more than 15 percent of the total amount of vinylidene 30 aromatic monomer in blocks of vinylidene aromatic monomer of more than 3 units. 36 WO 98/46672 PCT/US98/07650 More preferably, the interpolymer was not characterized by a high degree of either isotacticity or syndiotacticity. This means that in the carbon-13 NMR spectrum of the substantially random interpolymer the peak areas corresponding to the main chain methylene and methine carbons representing either meso diad sequences or racemic 5 diad sequences should not exceed 75 percent of the total peak area of the main chain methylene and methine carbons. The substantially random ax-olefin/vinylidene aromatic interpolymers blend components of the present invention include. but are not limited to interpolymers prepared by polymerizing one or more a-olefins with one or more vinylidene aromatic 10 monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers, and optionally other polymerizable monomers. Suitable a-olefins include for example. a-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-i -pentene, hexene- 1 and octene- 1. 15 These a-olefins do not contain an aromatic moiety. Preferred are ethylene in combination with a C-C 8 x-olefin, more preferred is ethylene. Suitable vinylidene aromatic monomers which can be employed to prepare the interpolymers include, for example, those represented by the following formula: Ar (CH,), RI - C = CR2)2 20 wherein 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 I to 5 substituents selected from 25 the group consisting of halo, C 1 4 -alkyl, and C 1 4 -haloalkyl; and n has a value from zero to 4, preferably from zero to 2, most preferably zero. Exemplary monovinylidene aromatic monomers include styrene, vinyl toluene, a-methylstyrene, t-butyl styrene, chlorostyrene, including all isomers of these compounds, . Particularly suitable such 37 WO 98/46672 PCT/US98/07650 monomers include styrene and lower alkyl- or halogen-substituted derivatives thereof. Preferred monomers include styrene, x-methyl styrene, the lower alkyl- (C, - C 4 ) or phenyl-ring substituted derivatives of styrene, such as for example, ortho-, meta-, and para-methylstyrene, the ring halogenated styrenes, para-vinyl toluene or mixtures 5 thereof, . A more preferred aromatic monovinylidene monomer is styrene. By the term "hindered aliphatic or cycloaliphatic vinylidene compounds", it is meant addition polymerizable vinylidene monomers corresponding to the formula: A' RI - C = CR2)2 wherein A' is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 10 carbons, 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; or alternatively R' and A' together form a ring system. By the term "sterically bulky" is 15 meant that the monomer bearing this substituent is normally incapable of addition polymerization by standard Ziegler-Natta polymerization catalysts at a rate comparable with ethylene polymerizations. Preferred hindered aliphatic or cycloaliphatic vinylidene compounds are monomers in which one of the carbon atoms bearing ethylenic unsaturation is tertiary or quaternary substituted. Examples of such 20 substituents include cyclic aliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or ring alkyl or aryl substituted derivatives thereof, including tert-butyl, and norbornyl. Most preferred 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 25 1-, 3-, and 4-vinylcyclohexene. Other optional polymerizable ethylenically unsaturated monomer(s) include strained ring olefins such as norbornene and C,.
10 alkyl or C 6 .,, aryl substituted norbornenes, with an exemplary interpolymer being ethylene/styrene/norbornene. 38 WO 98/46672 PCT/US98/07650 The substantially random interpolymers 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. 5 One method of preparation of the substantially random interpolymers 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 interpolymers can be prepared as described in EP-A 0,416,815 and US Patent No. 5,703,187 by Francis Timmers incorporated herein by 10 reference in their entirety. Preferred operating conditions for such polymerization reactions are pressures from atmospheric (1 x 105 Pa) up to 3000 atmospheres (3 x 108 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 15 products, for example the production of atactic polystyrene. Examples of suitable catalysts and methods for preparing the substantially random interpolymers are disclosed in U.S. Application Serial No. 545,403, filed July 3. 1990 (EP-A-416,815); U.S. Application Serial No. 702,475, filed May 20, 1991 (EP-A 514,828); U.S. Application Serial No. 876,268, filed May 1, 1992, (EP-A-520,732); U.S. 20 Application Serial No. 241,523, filed May 12, 1994; as well as U.S. 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 incorporated herein by reference. The substantially random a-olefin/vinylidene aromatic interpolymers can also 25 be prepared by the methods described in JP 07/278230 employing compounds shown by the general formula /CP R 1 R M Cp 2 R2 39 WO 98/46672 PCTIUS98/07650 where Cp' and Cp 2 are cyclopentadienyl groups, indenyl groups, fluorenyl groups, or substituents of these, independently of each other; R' 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 5 Hf, most preferably Zr; and R' is an alkylene group or silanediyl group used to cross link Cp' and Cp 2 . The substantially random c-olefin/vinylidene aromatic interpolymers 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; 10 and in Plastics Technology, p. 25 (September 1992), all of which are incorporated herein by reference in their entirety. Also suitable are the substantially random interpolymers which comprise at least one c-olefin/vinyl aromatic/vinyl aromatic/a-olefin tetrad disclosed in U. S. Application No. 08/708,809 filed September 4, 1996 by Francis J. Timmers et al. 15 These interpolymers 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 20 signals in the region 38.0 - 38.5 ppm are methylene carbons. It is believed that these new signals are due to sequences involving two head-to tail vinyl aromatic monomer insertions preceded and followed by at least one a-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. It is 25 understood by one skilled in the art that for such tetrads involving a vinyl aromatic monomer other than styrene and an a-olefin other than ethylene that the ethylene/vinyl aromatic monomer/vinyl aromatic monomer/ethylene tetrad will give rise to similar carbon-13 NMR peaks but with slightly different chemical shifts. These interpolymers are prepared by polymerizing at temperatures of from 30 30 0 C to 250 0 C in the presence of such catalysts as those represented by the formula 40 WO 98/46672 PCTIUS98/07650 Cp
(ER
2 )m MR'2 wherein: each Cp is independently, each occurrence, a substituted cyclopentadienyl group n-bound to M; E is C or Si; M is a group IV metal, preferably Zr or Hf, most preferably Zr; each R is independently, each occurrence, H, hydrocarbyl, 5 silahydrocarbyl, or hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from 1 to 10 carbon or silicon atoms; each R' is independently, each occurrence, H, 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, hydrocarbyl substituted 1,3 10 butadiene; m is 1 or 2; and optionally, but preferably in the presence of an activating cocatalyst. Particularly, suitable substituted cyclopentadienyl groups include those illustrated by the formula:
(R)
3 wherein each R is independently, each occurrence, H, hydrocarbyl, silahydrocarbyl, or 15 hydrocarbylsilyl, containing up to 30 preferably from 1 to 20 more preferably from I to 10 carbon or silicon atoms or two R groups together form a divalent derivative of such group. Preferably, 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 20 such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl. Particularly preferred catalysts include, for example, racemic (dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium dichloride, racemic (dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium 1,4-diphenyl-1,3 25 butadiene, racemic-(dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium di 41 WO 98/46672 PCT/US98/07650 C1 -4 alkyl, racemic-(dimethylsilanediyl-bis-(2-methyl-4-phenylindenyl))zirconium di C1 -4 alkoxide. Also included are the titanium-based Constarined Geometry catalysts, [N-( 1,1 dimethylethyl)-1,1 -dimethyl- 1-[( 1
,
2
,
3
,
4
,
5 -a )- 1,5,6,7-tetrahydro-s-indacen- 1 5 yl]silanaminato(2-)-N]titanium dimethyl; (1 -indenyl)(tert-butylamido)dimethyl- silane titanium dimethyl; ((3-tert-butyl)(1, 2 ,3,4,5-ri)-1-indenyl)(tert-butylamido) dimethylsilane titanium dimethyl; and ((3 -iso-propyl)( 1
,
2
,
3 ,4,5-i )-1-indenyl)(tert butyl amido) dimethylsilane titanium dimethyl, or any combination thereof . Further preparative methods for the interpolymers used in the present invention 10 have been described in the literature. Longo and Grassi (Makromol. Chem.. Volume 191, pages 2387 to 2396 [1990]) and D'Anniello et al. (Journal of Applied Polymer Science, Volume 58, pages 1701-1706 [1995]) reported the use of a catalytic system based on methylalumoxane (MAO) and cyclopentadienyltitanium trichloride (CpTiCl 3 ) to prepare an ethylene-styrene copolymer. Xu and Lin (Polymer Preprints, Am. Chem. 15 Soc., Div. Polym. Chem.) Volume 35, pages 686,687 [1994]) have reported copolymerization using a MgCl 2 /TiCl 4 /NdCl 3 / Al(iBu) 3 catalyst to give random copolymers of styrene and propylene. Lu et al (Journal of Applied Polymer Science, Volume 53, pages 1453 to 1460 [1994]) have described the copolymerization of ethylene and styrene using a TiCl 4 /NdCI3/ MgCl, /Al(Et) 3 catalyst. Sernetz and 20 Mulhaupt, (Macromol. Chem. Phys., v. 197, pp. 1071-1083, 1997) have described the influence of polymerization conditions on the copolymerization of styrene with ethylene using Me 2 Si(Me 4 Cp)(N-tert-butyl)TiCl/methylaluminoxane Ziegler-Natta catalysts. Copolymers of ethylene and styrene produced by bridged metallocene catalysts have been described by Arai, Toshiaki and Suzuki (Polymer Preprints, Am. 25 Chem. Soc., Div. Polym. Chem.) Volume 38, pages 349, 350 [1997]). The manufacture of c-olefin/vinyl aromatic monomer interpolymers 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 42 WO 98/46672 PCT/US98/07650 DE 197 11 339 Al to Denki KAGAKU Kogyo KK. All the above methods disclosed for preparing the interpolymer component are incorporated herein by reference. The interpolymers of one or more ac-olefins and one or more monovinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene 5 monomers employed in the present invention are substantially random polymers. These interpolymers 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 10 aliphatic a-olefin having from 2 to 20 carbon atoms. The number average molecular weight (M,) of these interpolymers is usually greater than 1,000, preferably from 5,000 to 1.000,00. more preferably from 10.000 to 500,000. The interpolymer(s) applicable to the present invention can have a melt index 15 (12) 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,/Mn of the interpolymer(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. 20 While preparing the substantially random interpolymer, 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 purposes of the present invention and can be tolerated. The vinylidene aromatic homopolymer may be 25 separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the interpolymer or the vinylidene aromatic homopolymer. For the purpose 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 interpolymers of atactic vinylidene aromatic 30 homopolymer is present. 43 WO 98/46672 PCT/US98/07650 The properties of the saturated and unsaturated amides and the finely divided inorganic compound for use in compositions comprising the substantially random interpolymers are as described previously. While effective amounts and preferred concentrations of the individual 5 components vary somewhat with the composition of the substantially random interpolymers component, the temperature of fabrication and the smoothness of the film surface, for the purposes of the invention, generally preferred concentrations of ; (i) 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, (ii) the 10 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 and (iii) 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. Also included in the present invention are compositions comprising the 15 homogeneous or substantially random interpolymers and a modifying agent. The modifying agent comprises either a propylene homopolymer or propylene/aX-olefin copolymer and/or a nucleating agent. We have found that homogeneous interpolymers with a density of between 0.885 and 0.905 g/cm 3 have a refractive index which is similar to that of a propylene homopolymer or propylene/a-olefin copolymer. This 20 allows such homo- and interpolymers of propylene to be dispersed within said homogeneous interpolymers without deterioration of the optical properties while acting as an antiblocking agent. We have also found that when adding nucleating agents to improve the optical qualities of said homogeneous interpolymers, a surprising reduction in blocking tendency of the films fabricated therefrom was also observed. 25 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 a-olefins including, but not limited to, impact copolymers (for example, those wherein a secondary copolymerization step reacting ethylene with the propylene 30 is employed) and random copolymers (also reactor modified and usually containing 1.5 44 WO 98/46672 PCT/US98/07650 to 7 weight percent ethylene copolymerized with the propylene), however, can alternatively be used. A complete discussion of various polypropylene polymers is contained in Modem Plastics Encyclopedia/89, mid October 1988 Issue, Volume 65, Number 11, pp. 86-92, the entire disclosure of which is incorporated herein by 5 reference. 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 12). 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 10 is not linear. Good clarity is achieved when the homogeneous linear or substantially linear ethylene/u-olefin 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. Generally, polypropylene has a 15 refractive index from 1.470 to 1.515, for example, 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 20 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). Chum, Silvis, and Kao, in the presentation entitled "INSITE Technology Based 25 Polyolefiin Elastomers for Impact Modification", SPO '93, presented a plot of refractive index versus density for substantially linear ethylene polymers. From this, they derived the equation: RI = 0.69694 (density) + 0.87884 30 45 WO 98/46672 PCT/US98/07650 where RI is the refractive index of the polymer. Accordingly, when it is desirable to use a clarified polypropylene random copolymer having a refractive index of 1.5044, preferred homogeneous linear and substantially linear ethylene polymers will have a density of 0.898 g/cm 3 . 5 To promote clarity, 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 10 polypropylene melt flow rate is to divide the polypropylene melt flow rate by 4. Thus a polypropylene having a melt flow rate of 12 g/10 min. is somewhat like a polyethylene having a melt index of 3 g/l10 min., in terms of its viscosity or flow behavior. Accordingly, 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 15 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. In contrast, using a polypropylene having a melt flow rate of 12 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 lower viscosity component constitutes the lower viscosity component of the blend, 20 leading to improved dispersion of the minor component in the dominant homogeneous linear or substantially linear ethylene polymer phase, and thus providing excellent optical properties. The term "nucleating agent", is defined to mean a material useful to control the particle size and process by which crystals are formed from liquids, supersaturated 25 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 30 nucleating site for the homogeneous polymer and wax. 46 WO 98/46672 PCTIUS98/07650 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, 5 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)
18
.(CO
3
)
17
H
2 0 (see W.T. Reichle, J. Catal., Vol. 94, p. 547 10 (1985), which have positively charged layers and exchangeable anions in the interlayer spaces. Other multi-layered particles having little or no charge on the layers may be useful in this invention. Such materials include chlorides such as ReCl 3 and FeOCI; chalcogenides such as TiS 2 , MoS2, and MoS 3 ; cyanides such as Ni(CN) 2 ; and oxides such as H 2 Si 2 0 5 , V 5 0 1 3 , HTiNbO 5 , Cro 5
V
0 .5S2, Wo.
2
V
2
.
8 0 7 , Cr 3 0 8 , MoO 3
(OH)
2 , VOPO 4 15 2HO, CaPO 4
CH
3 -HO, MnHAsO 4
-H
2 0, and Ag 6 Mo 10
O
3 3 . 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. Representative examples of exchangeable 20 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 polyvinyl pyrrolidone. 25 Representative examples of the quaternary ammonium salts (cationic surface active agents) which can be employed in this invention include the quaternary ammonium salts having octadecyl, hexadecyl, tetradecyl, or dodecyl groups; with preferred quaternary ammonium salts including dimethyl dihydrogenated tallow ammonium salt, octadecyl trimethyl ammonium salt, dioctadecyl dimethyl ammonium 47 WO 98/46672 PCT/US98/07650 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 5 layered material is a montmorillonite clay treated with a quaternary ammonium salt, most preferably dimethyl dihydrogenated tallow ammonium salt, commercially sold as Claytone T M HY (a trademark of Southern Clay Products). The organophilic multi-layered particles may also be prepared by the exchange of the sodium, potassium, or calcium cations with an inorganic material, a polymeric 10 substance obtained by hydrolyzing a polymerizable metallic alcoholate such as Si(OR) 4 , Al(OR) 3 , Ge(OR) 4 , Si(OC 2
H)
4 , Si(OCH 3 ), Ge(OC 3 H,), or Ge(OCH 5
)
4 , either alone, or in any combination. Alternatively, the inorganic material can be a colloidal inorganic compound. Representative colloidal inorganic compounds which can be used include SiO 2 , Sb,0 3 , Fe 2 0 3 , AL,0 3 , TiO 2 , ZrO,. and SnO,. alone, or in any combination. 15 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 incorporated herein by reference. Exemplary nucleating agents which are particles which are formed in situ in melt of the other components of the polymer composition include acetals such as 20 trinaphthylidene sorbitol, tri (4-methyl-i -naphthylidene) sorbitol, tri-(4-methyoxy- 1 naphtylidene)sorbitol, and dibenzylidene zylitol. 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 25 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, amino and halogen e.g fluorine, bromine and chlorine. Examples as described in US patent No's.4,419,473 and 5,001,176 (the 30 entire contents of which are incorporated herein by reference) include, but are not 48 WO 98/46672 PCTIUS98/07650 limited to, dibenzylidenesorbitol, 3,4.-dimethyl dibenzylidene-sorbitol. 1,3-benzylidene 2,4-p-methvlbenzylidenesorbitol, 1,3-benzvlidene-2,4-p-ethvlbenzylidenesorbitol, 1,3-p methylbenzvlidene-2,4-benzylidenesorbitol, 1,3-p-ethylbenzylidene-2,4 benzylidenesorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p 5 ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1,3,2,4-di-(p methylbenzylidene)sorbitol, 1,3,2,4-di-(p-ethylbenzylidene)sorbitol, 1,3,2,4-di-(p-n propylbenzylidene)sorbitol, 1,3 ,2,4-di-(p-i-propylbenzylidene)sorbitol, 1,3 ,2,4-di-(p-n butylbenzylidene)sorbitol, 1,3.2,4-di-(p-sec-butylbenzylidene)sorbitol, 1,3,2,4-di-(p-t butylbenzylidene)sorbitol, 1,3,2,4-di-(2',4'-dimethylbenzylidene)sorbitol, 1,3,2.4-di-(p 10 methoxybenzylidene)sorbitol, 1,3,2.,4-di-(p-ethoxybenzylidene)sorbitol, 1,3 benzylidene-2,4-p-chlorobenzylidenesorbitol, 1,3 -p-chlorobenzylidene-2,4 benzvlidenesorbitol. 1 , 3 -p-chlorobenzvlidene-2.4-p-methylbenzylidenesorbitol. 1.3-p chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol. 1,3-p-methylbenzylidene-2,4-p chlorobenzylidenesorbitol, 1,3-p-ethylbenzvlidene-2.4-p-chlorobenzylidenesorbitol. and 15 1,3,2,4-di-(p-chlorobenzylidene)sorbitol. Most preferred materials are 3.4,-dimethyl dibenzylidene sorbitol, which is available from Milliken Chemical, Inc. as Millad TM 3988, which is further available as a 10 weight percent mixture in 90 weight percent low density polyethylene as Millad T M 5L71-10. as well as Millad TM 3905P dibenzylidene sorbitol. 20 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 (12, 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 25 g/10min. 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 30 500 to 2500, and more preferably of from 1,000 to 2000 ppm in the final composition. 49 WO 98/46672 PCT/US98/07650 The density of the homogeneous narrow composition distribution ethylene/c olefin interpolymer incorporated 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 . 5 The melt index for said homogeneous narrow composition distribution ethylene/a.-olefin interpolymer 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/i 0 minutes (g/10 min). The I10/12 ratio of said homogeneous narrow composition distribution 10 ethylene/a-olefin interpolymer is greater than 5.6, preferably of from 5.6 to 13, more preferably of from 5.6 to 11. The Mw/Mn ratio of said homogeneous narrow composition distribution ethylene/u-olefin interpolymer is preferably of from 1.8 to 6.0. The interpolymers of one or more c-olefins and one or more monovinylidene 15 aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers employed in the present invention are substantially random polymers. These interpolymers 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, 20 preferably from 45 to 99, more preferably from 50 to 98 mole percent of at least one aliphatic c-olefin having from 2 to 20 carbon atoms. The number average molecular weight (Me) of these interpolymers is usually greater than 1,000, preferably from 5,000 to 1,000,000, more preferably from 10,000 to 500,000. 25 The interpolymer(s) applicable to the present invention can have a melt index (12) 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,,/M, of the interpolymer(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 30 5. 50 WO 98/46672 PCTIUS98/07650 While preparing the substantially random interpolymer. 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 purposes of the present 5 invention and can be tolerated. The vinylidene aromatic homopolymer may be separated from the interpolymer, if desired, by extraction techniques such as selective precipitation from solution with a non solvent for either the interpolymer or the vinylidene aromatic homopolymer. For the purpose of the present invention it is preferred that no more than 20 weight percent, preferably less than 15 weight percent 10 based on the total weight of the interpolymers of atactic vinylidene aromatic homopolymer is present. While effective amounts and preferred concentrations of the individual components vary somewhat with the density of the homogeneous interpolymer or blend component or with the composition of the substantially random interpolymers 15 component, as well as the temperature of fabrication and the smoothness of the film surface, for the purposes of the invention, generally preferred concentrations of ; (i) 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, (ii) the unsaturated fatty acid amide or ethylene-bis(amide) are in the range of from 0 to 10,000, 20 preferably of from 500 to 7,500, more preferably of from 1000 to 3000 ppm. For all of the aforementioned compositions. additives such as antioxidants (for TM example, hindered phenolics (for example, Irganox 1010 or 1076), phosphites (for example, Irgafos TM 168 or PEP QTM, or tris nonyl-phenylphosphite), cling additives (for example, PIB), polymer processing aids, pigments, fillers, can also be included in the 25 formulations, to the extent that they do not interfere with the enhanced formulation properties discovered by Applicants. Both Irganox and IrgafosTM are made by and trademarks of Ciba Geigy Corporation. 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 51 WO 98/46672 PCT/US98/07650 Sandoz Chemical, the primary ingredient of which is believed to be tetrakis-(2,4-di tertbutyl-phenyl)-4,4'biphenylphosphonite. EXAMPLES 5 In the case of Examples 1 -14, the additives were provided in the form of concentrates, the base polymer for which was a substantially linear ethylene/1-octene interpolymer available from the Dow Chemical Company, prepared using a metallocene catalyst, and having melt index, I, = 6.0 g/10 min, a density 0.9110 g/cm 3 and containing 50 ppm Irganox T M 1076 and 800 ppm PEPQ TM 10 Example 1 A resin composition was prepared by dry blending the following ingredients: (a) a substantially linear ethylene/1-octene interpolymer available from the Dow Chemical Company, prepared using a metallocene catalyst, and having melt index, 1 = 1.0 g/10 min, a density = 0.902 g/cm 3 a an 110/12 of 9 and containing 500 ppm IrganoxTM 15 1076 and 800 ppm PEPQ
T
M (b) Erucamide by Witco, 5 wt% concentrate to give a final concentration in the resin of 1500 ppm. (c) Stearamide by Witco. 5 wt% concentrate to give a final concentration in the resin of 250 ppm 20 (d) SiO,-White Mist by Celite, 20 wt% concentrate to give a final concentration of 2,500 ppm in the resin. Blown film samples of 2 mil thickness were prepared from the resin composition using a 2 % inch extruder equipped with a 6 inch Gloucester die, and a 70 25 mil die pin. The extrusion parameters were: Output -- 120 lb/hr (1.51 x 10 2 kg/s) Target melt temperature -- 450'F (232'C) Blow up ratio -- 2.5:1 Frostline height -- 25 inches (63.5 cm) 30 52 WO 98/46672 PCTIUS98/07650 Example 2 As for Example 1 but having 1500 ppm erucamide. 500 ppm stearamide. Example 3 As for Example 1 but having 1500 ppm erucamide, 750 ppm stearamide. 5 Example 4 As for Example I but having 1250 ppm erucamide, 250 ppm stearamide. Example 5 As for Example 1 but having 1250 ppm erucamide, 500 ppm stearamide. Example 6 10 As for Example 1 but having 1250 ppm erucamide, 750 ppm stearamide. Example 7 As for Example 1 but having 500ppm erucamide. 1500 ppm stearamide. Example 8 As for Example 1 but having 1500ppm erucamide. 500 ppm stearamide. 15 Comparative Experiment 1 As for Example 1 but having 0 ppm erucamide, 0 ppm stearamide and 0 ppm SiO,. Comparative Experiment 2 As for Example 1 but having only 750 ppm erucamide, 0 ppm stearamide. 20 Comparative Experiment 3 As for Example 1 but having 750 ppm erucamide. 250 ppm stearamide. Comparative Experiment 4 As for Example 1 but having 750 ppm erucamide, 500 ppm stearamide. Comparative Experiment 5 25 As for Example I but having 750 ppm erucamide, 750 ppm stearamide. Comparative Experiment 6 As for Example 1 but having 250 ppm erucamide, 250 ppm stearamide. Comparative Experiment 7 As for Example I but having 250 ppm erucamide, 750 ppm stearamide. 30 53 WO 98/46672 PCT/US98/07650 Comparative Experiment 8 As for Example 1 having 500 ppm erucamide, 500 ppm stearamide. Comparative Experiment 9 As for Comparative Experiment 1 but having 2500 ppm SiO, 5 The values for COF and block for these examples are summarized in Table I. Example 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/i -octene interpolymer available from the Dow 10 Chemical Company, prepared using a metallocene catalyst, and having melt index, 1, 1.6 g/10 min, a density = 0.8965 g/cm'a an I1/1, of 10 and containing 500 ppm Irganox T M 1076 and 800 ppm PEPQ
T
I' (b) Erucamide by Witco, 5 wt% concentrate to give a final concentration in the resin of 2000 ppm. 15 (c) Stearamide by Witco. 5 wt% concentrate to give a final concentration in the resin of 1000 ppm. (d) SiO 2 -White Mist by Celite, 20 wt% concentrate to give a final concentration of 4,000 ppm in the resin. Example 10 20 As for Example 9 but having 1250 ppm erucamide, 500 ppm stearamide. Example 11 As for Example 9 but having 1500 ppm erucamide, 750 ppm stearamide. Example 12 As for Example 9 but having 1000 ppm erucamide, 1000 ppm stearamide. 25 Example 13 As for Example 9 but having 1000 ppm erucamide, 2000 ppm stearamide. Comparative Experiment 10 As for Example 9 but having 1500 ppm erucamide, 250 ppm stearamide. Comparative Experiment 11 30 As for Example 9 but having 1250 ppm erucamide, 250 ppm stearamide. 54 WO 98/46672 PCT/US98/07650 Comparative Experiment 12 As for Example 9 but having 0 ppm erucamide, 0 ppm stearamide and 0 ppm SiO 2 Comparative Experiment 13 5 As for Example 9 but having 1000 ppm erucamide, 0 ppm stearamide. Comparative Experiment 14 As for Example 9 but having 750 ppm erucamide, 0 ppm stearamide. Comparative Experiment 15 As for Example 9 but having 750 ppm erucamide. 250 ppm stearamide. 10 Comparative Experiment 16 As for Example 9 but having 750 ppm erucamide. 500 ppm stearamide. Comparative Experiment 17 As for Example 9 but having 750 ppm erucamide. 750 ppm stearamide. Comparative Experiment 18 15 As for Example 8 but having 500 ppm erucamide, 500 ppm stearamide. Comparative Experiment 19 As for Example 9 but having 500 ppm erucamide, 1000 ppm stearamide. The values for COF and block for these examples are summarized in Table 2. Example 14 20 Blown film samples of 2 mil thickness were prepared using the same conditions used in Example 1 from a resin prepared by dry blending the following (a) an ethylene butene interpolymer EXACT T M 3028 (melt index, 12 =1.2 g/10 min, density = 0.900 g/cm), available from the Exxon Chemical Company and made utilizing a metallocene-catalyst was used. 25 (b) Erucamide by Witco, 5 wt% concentrate supplied by Ampacet (Product no. 100329) to give a final concentration in the resin of 1500 ppm. (c) Stearamide by Witco. 5 wt% concentrate supplied by Bayshore to give a final concentration in the resin of 500 ppm. (d) SiO 2 -White Mist by Celite, 20 wt% concentrate by Ampacet (Product no.100342) 30 to give a final concentration of 3,000 ppm in the resin. 55 WO 98/46672 PCTIUS98/07650 Comparative Experiment 20 As for Example 14 but having 750 ppm erucamide, 0 ppm stearamide and 2500 ppm SiO 2 Comparative Experiment 21 5 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. Table 1 Example Resin Erucamide Stearamide SiO. Erucamide+ Thickness E/S Block COF # (ppm) (ppm) (ppm) Stearamide (mils) ratio (g) (ppm) Ex I PL 1880 1500 250 2500 1750 2 6:1 45.4 0.25 Ex 2 PL 1880 1500 500 2500 2000 2 3:1 43.7 0.10 Ex 3 PL 1880 1500 750 2500 2250 2 2:1 47.7 0.20 Ex 4 PL 1880 1250 250 2500 1500 2 5:1 47.4 0.25 Ex 5 PL 1880 1250 500 2500 1750 2 2.5:1 44.1 0.20 Ex 6 PL 1880 1250 750 2500 2000 2 1.7:1 44.2 0.18 Ex 7 PL 1880 500 1500 2500 2000 2 1:3 47.8 0.19 Ex 8 PL 1880 1500 500 3000 2000 2 3:1 36.9 0.19 Comp. Ex I* PL 1880 0 0 0 0 2 99.3 >1 Comp. Ex 2* PL 1880 750 0 2500 750 2 92.0 0.10 Comp. Ex 3* PL 1880 750 250 2500 1000 2 3:1 84.1 0.10 Comp. Ex 4* PL 1880 750 500 2500 1250 2 1.5:1 58.2 1 Comp. Ex 5* PL 1880 750 750 2500 1500 2 1:1 70.8 1 Comp. Ex 6* PL 1880 250 250 2500 500 2 1:1 93.7 0.31 Comp. Ex 7* PL 1880 250 750 2500 1000 2 1:3 78.9 0.24 Comp Ex 8* PL 1880 500 500 2500 1000 2 1:1 80.7 0.13 Comp. Ex 9* PL 1880 0 0 2500 0 2 94 CNA 10 *Not an example of claimed invention (":good" block < 49g, "good" COF < 0.31) 56 WO 98/46672 PCT/US98/07650 Table 2 Example 4 Resin Erucamide Stearamide SiO, Erucamide4 Thickness E/S Block COF # (ppm) (ppm) (ppm) Stearamide milss) ratio (g) (ppm) Ex 9 PF 1140 2000 1000 4000 3000 2 2:1 33.4 0.16 Ex 10 PF 1140 1250 500 4000 1750 2 2.5:1 39.8 0.25 Ex II PF 1140 1500 750 4000 2250 2 2:1 29.5 0.20 Ex 12 PF 1140 1000 1000 4000 2000 2 1:1 36.4 0.18 Ex 13 PF 1140 1000 2000 4000 3000 2 1:2 37.3 0.24 Comp. Ex 10* PF 1140 1500 250 4000 1750 2 6:1 39.4 0.35 Comp. Ex 11* PF 1140 1250 250 4000 1500 2 5:1 50.7 0.35 Comp. Ex 12* PF 1140 0 0 0 0 2 112.6 >1 Comp. Ex 13* PF 1140 1000 0 4000 1000 2 63.8 0.15 Comp. Ex 14* PF 1140 750 0 4000 750 2 103.1 >I Comp. Ex 15* PF 1140 750 250 4000 1000 2 3:1 82.3 >I Comp. Ex 16* PF 1140 750 500 4000 1250 2 1.5:1 83.6 >I Comp. Ex 17* PF 1140 750 750 4000 1500 2 1:1 43.5 >1 Comp. Ex 18* PF 1140 500 500 4000 1000 2 1:1 75.7 0.34 Comp. Ex 19* PF 1140 500 1000 4000 1500 2 1:2 40.6 0.32 *Not an example of claimed invention (':good" block < 49g. "good" COF < 0.31) 5 Table 3 Example # Resin Erucamide Stearamide SiO, Erucamide+ Thickness E/S Block COF (ppm) (ppm) (ppm) Stearamide (mils) ratio (g) 1-I (ppm) Ex 14 EXACTTUI 1500 500 3000 2000 2 3:1 25.1 0.22 3028' 1 Comp. Ex 20* EXACTTI 750 - 0 2500 750 2 35.3 1.0 3028" Comp. Ex 21* EXACTI 2000 0 3000 2000 2 23.7 0.40 3028' *Not an example of claimed invention (":good" block < 49g, "good" COF < 0.31) # is a trademark of Exxon Chemical. 57 WO 98/46672 PCT/US98/07650 Examples 15 - 17 Examples 15 - 17 were formulated using the ethylene/styrene interpolymers ESI #1 - 3 respectively. 5 Preparation of ESI #1 Catalyst A Preparation - (Dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1,2,3,4,5 ri)-1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl]silanaminato(2-)-N]- titanium). 1) Preparation of 3.5.6.7-Tetrahydro-s-Hydrindacen- 1 (2H)-one. 10 Indan (94.00 g, 0.7954 moles) and 3-chloropropionyl chloride (100.99 g, 0.7954 moles) were stirred in CHCl, (300 mL) at 0 0 C as AlCl 3 (130.00 g, 0.9750 moles) was added slowly under a nitrogen flow. The mixture was then allowed to stir at room temperature for 2 hours. The volatiles were then removed. The mixture was then cooled to 0 0 C and concentrated H 2 S0 4 (500 mL) slowly added. The forming solid had 15 to be frequently broken up with a spatula as stirring was lost early in this step. The mixture was then left under nitrogen overnight at room temperature. The mixture was then heated until the temperature readings reached 90 0 C. These conditions were maintained for a 2 hour period of time during which a spatula was periodically used to stir the mixture. After the reaction period crushed ice was placed in the mixture and 20 moved around. The mixture was then transferred to a beaker and washed intermittently with H2O and diethylether and then the fractions filtered and combined. The mixture was washed with H 2 0 (2 x 200 mL). The organic layer was then separated and the volatiles removed. The desired product was then isolated via recrystallization from hexane at 0 0 C as pale yellow crystals (22.36 g, 16.3% yield). 25 H NMR (CDCl 3 ): d2.04-2.19 (in, 2 H), 2.65 (t, 3 HH=5.7 Hz, 2 H), 2.84-3.0 (in, 4 H), 3.03 (t, 3 HH=5.5 Hz, 2 H), 7.26 (s, 1 H), 7.53 (s, 1 H). 13 C NMR (CDC1 3 ): d25.71, 26.01, 32.19, 33.24, 36.93, 118.90, 122.16, 135.88, 144.06, 152.89. 154.36, 206.50. GC-MS: Calculated for C 12H 20 172.09, found 172.05. 30 58 WO 98/46672 PCTIUS98/07650 2) Preparation of 1.2,3,5-Tetrahydro-7-phenvl-s-indacen. 3,5,6,7-Tetrahydro-s-Hydrindacen-1(2H)-one (12.00 g, 0.06967 moles) was stirred in diethylether (200 mL) at 0 0 C as PhMgBr (0.105 moles, 35.00 mL of 3.0 M solution in diethylether) was added slowly. This mixture was then allowed to stir 5 overnight at room temperature. After the reaction period the mixture was quenched by pouring over ice. The mixture was then acidified (pH=1) with HCl and stirred vigorously for 2 hours. The organic layer was then separated and washed with H,0 (2 x 100 mL) and then dried over MgSO 4 . Filtration followed by the removal of the volatiles resulted in the isolation of the desired product as a dark oil (14.68 g, 90.3% 10 yield). H NMR (CDC): 52.0-2.2 (in. 2 H), 2.8-3.1 (m. 4 H), 6.54 (s, 1 H). 7.2-7.6 (in, 7 H). GC-MS: Calculated for C 18
H
16 232.13. found 232.05. 3) Preparation of 1.2.3.5-Tetrahydro-7-phenvl-s-indacene. dilithium salt. 15 1,2,3.5-Tetrahydro-7-phenyl-s-indacen (14.68 g. 0.06291 moles) was stirred in hexane (150 mL) as nBuLi (0.080 moles, 40.00 mL of 2.0 M solution in cyclohexane) was slowly added. This mixture was then allowed to stir overnight. After the reaction period the solid was collected via suction filtration as a yellow solid which was washed with hexane, dried under vacuum, and used without further purification or analysis 20 (12.2075 g, 81.1% yield). 4) Preparation of Chlorodimethyl(1.5.6.7-tetrahvdro-3-phenvl-s-indacen-1-vl)silane. 1,2,3,5-Tetrahydro-7-phenyl-s-indacene, dilithium salt (12.2075 g, 0.05102 moles) in THF (50 mL) was added dropwise to a solution of Me 2 SiCl, (19.5010 g, 25 0.1511 moles) in THF (100 mL) at 0 0 C. This mixture was then allowed to stir at room temperature overnight. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. The removal of the hexane resulted in the isolation of the desired product as a yellow oil (15.1492 g, 91.1% yield). H NMR (CDCl 3 ): dO.33 (s, 3 H), 0.38 (s, 3 H), 2.20 (p, 3 JHH=7.5 Hz, 2 H), 2.9-3.1 30 (in, 4 H), 3.84 (s, 1 H), 6.69 (d, JHH=2.8 Hz, 1 H), 7.3-7.6 (m, 7 H), 7.68 (d, JHH=7-4 Hz, 2 H). 59 WO 98/46672 PCTIUS98/07650 C NMR (CDCl,): dO.24, 0.38, 26.28, 33.05, 33.18, 46.13. 116.42, 119.71, 127.51, 128.33, 128.64, 129.56, 136.51, 141.31, 141.86, 142.17, 142.41, 144.62. GC-MS: Calculated for C 0 H ClSi 324.11, found 324.05. 5 5) Preparation of N-(1,1-Dimethylethyl)-.1-dimethyl-1-(1.5,6.7-tetrahydro-3-phenyl s-indacen- I -vl)silanamine. Chlorodimethyl(1,5,6,7-tetrahydro-3 -phenyl-s-indacen-1-yl)silane (10.8277 g, 0.03322 moles) was stirred in hexane (150 mL) as NEt 3 (3.5123 g, 0.03471 moles) and t-butylamine (2.6074 g, 0.03565 moles) were added. This mixture was allowed to stir 10 for 24 hours. After the reaction period the mixture was filtered and the volatiles removed resulting in the isolation of the desired product as a thick red-yellow oil (10.6551 g. 88.7% yield). H NMR (CDCl,): dO.02 (s. 3 H). 0.04 (s. 3 H). 1.27 (s. 9 H). 2.16 (p, 3 JHH=7.2 Hz. 2 H), 2.9-3.0 (in. 4 H), 3.68 (s, I H). 6.69 (s. I H), 7.3-7.5 (in. 4 H). 7.63 (d, 3 JHH=7-4 15 Hz,2 H). C NMR (CDCl,): d-0.32, -0.09, 26.28, 33.39, 34.11, 46.46, 47.54, 49.81, 115.80. 119.30, 126.92, 127.89, 128.46, 132.99, 137.30, 140.20, 140.81, 141.64, 142.08, 144.83. 20 6) Preparation of N-(1.1-Dimethvlethyl)-1.1-dimethvl-1-(1.5.6.7-tetrahydro-3-phenyl s-indacen- I -vl)silanamine. dilithium salt. N-(1,1-Dimethylethyl)- 1,1-dimethyl-1-(1,5.6,7-tetrahydro-3-phenyl-s-indacen 1-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 25 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). The dark red residue was then pumped dry and used without further purification or analysis (9.6517 g, 87.7% yield). 30 60 WO 98/46672 PCT/US98/07650 7) Preparation of Dichloro[N-(1.1-dimethvlethvl)-1.1-dimethyl-1-[(1.2.3.4.5-i) 1.5.6.7-tetrahvdro-3-phenyl-s-indacen- I -vllsilanaminato(2-)-Nltitanium. N-( 1,1 -Dimethylethyl)- 1,1 -dimethyl- 1 -(1.5,6,7-tetrahydro-3-phenyl-s-indacen 1-yl)silanamine, dilithium salt (4.5355 g, 0.01214 moles) in THF (50 mL) was added 5 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, (1.7136 g, 0.006162 moles) was then added and the mixture allowed to stir for an additional hour. After the reaction period the volatiles were removed and the residue extracted and filtered using toluene. Removal of the toluene resulted in the isolation of a dark residue. This residue was 10 then slurried in hexane and cooled to 0 0 C. The desired product was then isolated via filtration as a red-brown crystalline solid (2.5280 g. 43.5% yield). H NMR (CDClI: dO.71 (s. 3 H), 0.97 (s. 3 H). 1.37 (s, 9 H), 2.0-2.2 (m. 2 H), 2.9-3 .2 (m, 4 H), 6.62 (s, 1 H), 7.35-7.45 (m. 1 H). 7.50 (t, JHH=7.8 Hz, 2 H), 7.57 (s, I H), 7.70 (d, JHH=7.1 Hz, 2 H), 7.78 (s, 1 H). 15 H NMR (C 6
D
6 ): dO.44 (s, 3 H), 0.68 (s, 3 H), 1.35 (s, 9 H), 1.6-1.9 (in. 2 H), 2.5-3.9 (in, 4 H), 6.65 (s, I H), 7.1-7.2 (in, 1 H), 7.24 (t, JHH=7.1 Hz, 2 H), 7.61 (s, 1 H). 7.69 (s, 1 H), 7.77-7.8 (m, 2 H). C NMR (CDCl 3 ): dl.29, 3.89, 26.47. 32.62, 32.84, 32.92, 63.16, 98.25, 118.70, 121.75, 125.62, 128.46, 128.55, 128.79, 129.01, 134.11, 134.53, 136.04, 146.15, 20 148.93. 13 C NMR (C 6
D
6 ): dO.90, 3.57, 26.46, 32.56. 32.78, 62.88, 98.14, 119.19, 121.97, 125.84. 127.15, 128.83, 129.03, 129.55, 134.57. 135.04, 136.41, 136.51. 147.24, 148.96. 25 8) Preparation of Dimethyl[N-(1.1-dimethvlethvl)-.1-dimethvl-1-[(1.2.3.4.5-n) 1.5.6.7-tetrahvdro-3-phenvl-s-indacen-I -v11silanaminato(2-)-Nltitanium. Dichloro[N-(1,1 -dimethylethyl)-1,1 -dimethyl-1-[(1,2,3,4,5-ri)- 1,5.,6,7 tetrahydro-3-phenyl-s-indacen-1-yl]silanaminato(2-)-N]titanium (0.4970 g, 0.001039 moles) was stirred in diethylether (50 mL) as MeMgBr (0.0021 moles, 0.70 mL of 3.0 30 M solution in diethylether) was added slowly. This mixture was then stirred for 1 hour. After the reaction period the volatiles were removed and the residue extracted and filtered using hexane. Removal of the hexane resulted in the isolation of the desired product as a golden yellow solid (0.4546 g, 66.7% yield). 61 WO 98/46672 PCT/US98/07650 NMR (C D ): dO.071 (s, 3 H), 0.49 (s, 3 H), 0.70 (s. 3 H), 0.73 (s, 3 H), 1.49 (s, 9 H), 1.7-1.8 (in, 2 H), 2.5-2.8 (in, 4 H), 6.41 (s, 1 H), 7.29 (t, JHH=7.4 Hz, 2 H), 7.48 (s, 1 H), 7.72 (d, JHH=7.4 Hz, 2 H), 7.92 (s, 1 H). 13 C NMR (C 6
D
6 ): d2.19, 4.61, 27.12, 32.86, 33.00, 34.73, 58.68, 58.82, 118.62, 121.98, 5 124.26, 127.32, 128.63, 128.98, 131.23, 134.39, 136.38, 143.19, 144.85. Polymerization The interpolymers were prepared in a 6 gallon (22.7 L), oil jacketed, Autoclave continuously stirred tank reactor (CSTR). A magnetically coupled agitator with 10 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) 15 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. At the discharge of the solvent pump, a side stream was taken to provide flush flows for the catalyst injection line (1 lb/hr (0.45 20 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 25 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 30 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 62 WO 98/46672 PCT/US98/07650 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 5 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. Polymerization was stopped with the addition of catalyst kill (water mixed with 10 solvent) into the reactor product line after the micromotion flow meter measuring the solution density. Other polymer additives can be added with the catalyst kill. A static mixer in the line provided dispersion of the catalyst kill and additives in the reactor effluent stream. This stream next entered post reactor heaters that provide additional energy for the solvent removal flash. This flash occurred as the effluent exited the post 15 reactor heater and the pressure was dropped from 475 psig (3,275 kPa) down to ~250 mm of pressure absolute at the reactor pressure control valve. This flashed polymer entered a hot oil jacketed devolatilizer. Approximately 85 percent of the volatiles were removed from the polymer in the devolatilizer. The volatiles exited the top of the devolatilizer. The stream was condensed with a glycol jacketed exchanger and entered 20 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 25 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. The dry polymer exits the extruder as a single strand. This strand was cooled as it was pulled through a water bath. The excess water was blown from the strand with air and the strand was chopped into pellets with a strand chopper. 30 63 WO 98/46672 PCTIUS98/07650 Preparation of ESI #2 Catalyst B Preparation - (1 H-cyclopenta[l]phenanthrene-2-yl)dimethyl(t-butylamido) silanetitanium 1,4-diphenylbutadiene. 5 1) Preparation of lithium 1 H-cyclopentarllphenanthrene-2-yl To a 250 ml round bottom flask containing 1.42 g (0.00657 mole) of 1H cyclopenta[l]phenanthrene and 120 ml of benzene was added dropwise, 4.2 ml of a 1.60 M solution of n-BuLi in mixed hexanes. The solution was allowed to stir overnight. The lithium salt was isolated by filtration, washing twice with 25 ml benzene and 10 drying under vacuum. Isolated yield was 1.426 g (97.7 percent). IH NMR analysis indicated the predominant isomer was substituted at the 2 position. 2) Preparation of (1H-cvclopenta[llphenanthrene-2-yl)dimethvlchlorosilane To a 500 ml round bottom flask containing 4.16 g (0.0322 mole) of dimethyldichlorosilane (MeSiCl, ) and 250 ml of tetrahydrofuran (THF) was added 15 dropwise a solution of 1.45 g (0.0064 mole) of lithium 1 H-cyclopenta[l]phenanthrene 2-yl in THE. The solution was stirred for approximately 16 hours, after which the solvent was removed under reduced pressure, leaving an oily solid which was extracted with toluene, filtered through diatomaceous earth filter aid (CeliteTM), washed twice with toluene and dried under reduced pressure. Isolated yield was 1.98 g (99.5 20 percent). 3) Preparation of (1 H-cyclopenta[llphenanthrene-2-vl)dimethyl (t-butylamino)silane To a 500 ml round bottom flask containing 1.98 g (0.0064 mole) of (1H cyclopenta[1]phenanthrene-2-yl)dimethylchlorosilane and 250 ml of hexane was added 2.00 ml (0.0160 mole) of t-butylamine. The reaction mixture was allowed to stir for 25 several days, then filtered using diatomaceous earth filter aid (CeliteTM), washed twice with hexane. The product was isolated by removing residual solvent under reduced pressure. The isolated yield was 1.98 g (88.9 percent). 64 WO 98/46672 PCT/US98/07650 4) Preparation of dilithio (1 H-cyclopentafllphenanthrene-2-yl)dimethyl(t butylamido)silane To a 250 ml round bottom flask containing 1.03 g (0.0030 mole) of (1H cyclopenta[l]phenanthrene-2-yl)dimethyl(t-butylamino)silane) and 120 ml of benzene 5 was added dropwise 3.90 ml of a solution of 1.6 M n-BuLi in mixed hexanes. The reaction mixture was stirred for approximately 16 hours. The product was isolated by filtration, washed twice with benzene and dried under reduced pressure. Isolated yield was 1.08 g (100 percent). 5) Preparation of (1 H-cvclopentaFllphenanthrene-2-vl)dimethvl(t-butvlamido) 10 silanetitanium dichloride To a 250 ml round bottom flask containing 1.17 g (0.0030 mole) of TiCl 3 *3THF and 120 ml of THF was added at a fast drip rate about 50 ml of a THF solution of 1.08 g of dilithio (IH-cyclopenta[1]phenanthrene-2-yl)dimethyl(t butylamido)silane. The mixture was stirred at about 20 'C for 1.5 h at which time 0.55 15 gm (0.002 mole) of solid PbCl 2 was added. After stirring for an additional 1.5 h the THF was removed under vacuum and the reside was extracted with toluene, filtered and dried under reduced pressure to give an orange solid. Yield was 1.31 g (93.5 percent). 6) Preparation of (1 H-cyclopenta[llphenanthrene-2-yl)dimethvl(t-butvlamido) silanetitanium 1.4-diphenvlbutadiene 20 To a slurry of (1 H-cyclopenta[]phenanthrene-2-yl)dimethyl(t butylamido)silanetitanium dichloride (3.48 g, 0.0075 mole) and 1.551 gm (0.0075 mole) of 1,4-diphenyllbutadiene in about 80 ml of toluene at 70 'C was add 9.9 ml of a 1.6 M solution of n-BuLi (0.0150 mole). The solution immediately darkened. The temperature was increased to bring the mixture to reflux and the mixture was 25 maintained at that temperature for 2 hrs. The mixture was cooled to about -20 'C and the volatiles were removed under reduced pressure. The residue was slurried in 60 ml of mixed hexanes at about 20 'C for approximately 16 hours. The mixture was cooled 65 WO 98/46672 PCTIUS98/07650 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 5 -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. Polymerization 10 The polymerization was conducted as for ESI #1 apart from the use of Catalyst B under the co-catalyst and process conditions summarized in Table 4. Preparation of ESI #3 The catalyst and polymerization procedures used were as for ESI #1 15 under the co-catalyst and process conditions summarized in Table 4. Table 4 Preparation Conditions for the Ethylene/Styrene Interpolymers ESI #s 1 - 3'. ESI- Reactor Solvent Ethylene Hydrogen Styrene Ethylene Co- Catalyst MMAO # Temp Flow Flow Flow Flow Conversion Catalyst Ti 0 C lb/hr lb/hr lb/hr lb/hr % Ratio (kg/s) (kg/s) (kg/s) (kg/s) ESI # 1 92.7 34.8 3.1 16 5.4 95.3 Cc A' 7.0 (4.4 E- 3 ) (3.9 E 4 ) (2.0 E-) (6.8 E-) ESI # 2 68.9 30.0 1.3 0 10.0 87.1 CC Bb 5.0 (3.8 E 3 ) (1.6 E 4 ) (1.2 E 3 ) ESI # 3 71.6 30.0 1.3 0 15.6 96.6 C A 4.0 (3.8 E- 3 (1.6 E 4 ) (2.0 E- 3 ) a The catalyst was dimethyl[N-(1,1-dimethylethyl)-1,1-dimethyl-1-[(1.2,3.4.5-s)-l5.6.7-tetrahydro-3-phenyl-s-indacen-l 20 yllsilanaminato(2-)-N]- titanium. b The catalyst was (I H-cyclopenta[l]phenanthrene-2-yl)dimethyl(t-butylamido)silanetitanium 1,4-diphenylbutadiene c Cocatalyst C was tris(pentafluorophenyl)borane. d a modified methylaluminoxane commercially available from Akzo Nobel as MMAO-3A. e the B/Ti mole ratio in all cases was 3.0:1 66 WO 98/46672 PCT/US98/07650 Examples 15 - 17 In the case of Examples 15 - 17. the additives were provided in the form of concentrates, the base polymer for which was a substantially linear ethylene/styrene 5 interpolymer available from the Dow Chemical Company, prepared using a metallocene catalyst, and having melt index, I2 = 6.0 g/10 min. containing 70 wt.% (38.6 mol %) styrene. 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. 10 Example 15 A resin composition was prepared by dry blending the following ingredients: (a) the substantially linear ethylene/styrene interpolymer. ESI # 1. as described in Table 4, and having melt index, I, = 1.4 g/10 min, and an interpolymer styrene content 15 of 40.3 wt % (35.4 mol %) and having 5000 ppm talc, dry blended on the pellets. (b) Erucamide by Croda International, 5 wt% concentrate to give a final concentration in the resin of 2000 ppm. (c) Stearamide by Croda International, 5 wt% concentrate to give a final concentration in the resin of 1000 ppm. 20 Blown film samples of 3.5 mil thickness were prepared from the resin composition using a 1.25 inch (3.17 cm) extruder equipped with a 3 inch (7.6 cm) Killion die, and a 60 mil die gap. The extrusion parameters were: Screw Speed --50 rpm Target melt temperature -- 415'F (213'C) 25 Layflat width -- 9 inches (23 cm) Frostline height -- 20 inches (51 cm) Example 16 As for Example 15 but using the ethylene/styrene interpolymer, ESI # 2, 30 prepared as described in Table 4, and having a melt index, 12 = 0.9 g/10 min, and an 67 WO 98/46672 PCT/US98/07650 interpolymer styrene content of 70 wt % (38.6 mol %) and having 5000 ppm talc dry blended on the pellets. 5.5 mil thick samples were prepared. Example 17 As for Example 15 with the ethylene/styrene interpolymer, ESI # 3, prepared as 5 described in Table 4, and having a melt index, I2 = 1.3 g/10 min, and an interpolymer styrene content of 75 wt % (44.7 mol %) and having 5000 ppm talc dry blended on the pellets. 5 mil thick samples were prepared. The values for block for these examples are summarized in Table 5. It is significant in these samples that the samples were not destructively blocked, as is 10 normal with this type of material without the addition of additives. Also, the COF of at least one of the samples was measurable, while normally with this type of material the COF is not measurable. Table 5 15 Example Resin Erucamide Stearamide Talc Erucamide+ Thickness E/S Block COF # (ppm) (ppm) (ppm) Stearamide milss) ratio (g) I-I (ppm) Ex 15 ESI # 1 2000 1000 5000 3000 3.5 2:1 50 N.A. Ex 16 ES1 # 2 2000 1000 5000 3000 5 2:1 156 NA. Ex 17 ESl # 3 2000 1000 5000 3000 5 2:1 52 1.8 Examples 18 - 22 For Examples 18-22, Block was measured using ASTM D-3354, COF was measured using ASTM D-1894, Haze was measured using ASTM D-1003, Gloss was measured 20 using ASTM D-2457and Transparency or Clarity was measured using ASTM D- 1746. Identification of Ingredients Used in the Compositions of Examples 18 - 22. POP 1 was a substantially linear ethylene/ 1-octene copolymer having a density of 0.902 g/cm 3 , a melt index (12) at 190"C of 1 g/10 min, and an 110/12 of 9.0, which is available from The Dow Chemical Company under the Trade name Affinity PLI 880. 68 WO 98/46672 PCT/US98/07650 POP2 was a substantially linear ethylene/i -octene copolymer having a density of 0.902 g/cm 3 , a melt index (12) at 190'C of 3 g/10 min., and an I10/12 of 8.0, which is available from The Dow Chemical Company under the Trade name Affinity FW1650. POP3 was a substantially linear ethylene/i -octene copolymer having a density 5 of 0.896 g/cm 3 , a melt index (12) at 190 0 C of 1.6 g/10 min., and an I 10 /I, of 9.9, which is available from The Dow Chemical Company under the Trade name Affinity PF 1140. POP4 was a substantially linear ethylene/i -octene copolymer having a density of 0.903 g/cm3, a melt index (I2) at 190'C of 1.0 g/10 min., and an I~o/I, of 9.0, which has 750 ppm Erucamide, and 2500 ppm SiOG, and which is available from The Dow 10 Chemical Company under the Trade name Affinity PL 1881. PPl was an isotactic propylene homopolymer available from Amoco under the designation T100l, 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 Q3OP, which has a melt flow rate at 230 C of 0.7 g/10 min. 15 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 (12) 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 20 100371-E) prepared from a substantially linear ethylene/1-octene copolymer having a density of 0.910 g/cm 3 , and a melt index (12) at 190'C of 6 g/10 min (available from The Dow Chemical Company) and containing 20 weight percent SiO, antiblock. MB3 was a masterbatch available from Ampacet (Ampacet commercial code LR-87476) prepared from a substantially linear ethylene/1-octene copolymer having a 25 density of 0.910 g/cm3, and a melt index (12) at 190'C of 6 g/10 min (available from The Dow Chemical Company) and containing 5 weight percent Stearamide slip agent 69 WO 98/46672 PCT/US98/07650 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 (12) at 190'C of 6 g/10 min (available from The Dow Chemical Company) and containing 20 weight percent White Mist antiblock. 5 MB5 was a masterbatch prepared from an ethylene/I -octene copolymer having a density of 0.910 g/cm 3 , and a melt index (12) 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. 10 MB6 was a masterbatch prepared from an ethylene/i -octene copolymer having a density of 0.910 g/cm 3 . and a melt index (1) at 190'C of 6 g/10 min (available from The Dow Chemical Company) and containing 6% Erucamide and 15% tale. 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. 15 MB7 was a melt blend of 1200 grams POP2 and 800 grams POP 1, 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. 20 Examples 18 - 20 and Comparative Experiments 22 -24. This series of blown films were made on a Davo Blown film extruder with a 40 mm screw, equipped with a 90 mm diameter die with a 1.2 mm die gap. Settings used to make film were 50 rpm, 2.5 blow up ratio, 50 micron film thickness, at a melt temperature of 240'C at approximately 15 kg/hr. 25 Examples 18 - 20 and Comparative Experiments 22 - 24 were extruded as dry blend of the POPI with the appropriate masterbatch and/or nucleating agent after tumble blending of the ingredients. In the case of each example, the sum of the amount of POP1 and masterbatch was 100, with the various additives, for example, slip, 70 WO 98/46672 PCT/US98/07650 antiblock, and nucleating agent, being present in the indicated amount by virtue of their being present in the masterbatches. However, it is noted that in the case of Examples 18 - 19, nucleating agent above and beyond that present in the masterbatch is utilized; and, in the case of Example 20, all of the nucleating agent present is provided 5 separated, that is, rather than by means of masterbatch MB7. The compositions were evaluated for blocking, COF, gloss, haze, and clarity. The compositions, and the measured properties, are set forth in Table 6. Table 6 Example Comp. Comp. Comp. Expt. Ex. 18 Ex. 19 Ex. 20 Expt. 22 Expt. 23 24 base POPI POPI POPI POPI POPI POP1 MB1 (wt. %) 0 0 1.6 1.6 1.6 1.6 MB2 (wt. %) 0 0 1 0 0 0 MB5 (wt. %) 0 1.33 0 0 0 0 MB7 (wt. %) 0 0 0 5 2.5 0 Slip Level 0 800 800 800 800 800 (ppm) AB level 0 2000 2000 20000 10000 0 (ppm) AB type - CaCO 3 SiO 2 PP1 PPl 0 Nucleating 0 0 0 1100** 1050*** 1000 agent (ppm) Block (N)* n.m.* 0.47 0.55 0.26 0.35 0.27 COF n.m.* 1.14 0.35 0.18 0.83 n.m.* Gloss 112 120 110 70 107 119 Haze (%) 3.7 4.8 3.8 7 3.8 2.8 Clarity 70 63.5 49.7 65.4 62.4 72.5 * n.m = not measurable because too high ** 100ppm attributable to MB7 used 71 WO 98/46672 PCT/US98/07650 *** 50ppm attributable to MB7 used + Block in Newtons measured by ASTM 1893 (225mm film width) Comparative Experiment 22 represents the performance of the pure POP 1. 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 5 unmodified resin POP I. 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 10 is not as favorable as that of Example19. Example 21 and Comparative Experiments 25 - 27 The blown films of 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 POP 1 with the 15 appropriate master-batch after tumble blending. In the case of each example, 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 20 properties, are set forth in the following Table 7. 72 WO 98/46672 PCT/US98/07650 Table 7 Example Comp. Expt. Comp. Expt. Comp. Expt. Ex. 21 25 26 27 base POPI POPI POPI POPI MB1 (wt. %) 0 1.6 4 4 MB4 (wt. %) 0 1.25 1.5 0 MB7 (wt. %) 0 0 0 1.25 Slip Level 0 800 2000 2000 (ppm) AB level (ppm) 0 2500 3000 5000 AB type - White Mist' White Mist~ PPI Nucleating 0 0 0 25** agent (ppm) Block (N)-* 0.827 0.4 0.185 0.106 COF n.m.* 0.161 0.145 n.m.* Gloss 133 98.3 95.7 126.7 Haze (%) 2.44 3.85 4.2 2.47 Clarity 79.1 34.7 32.7 76.4 * n.m = not measurable because too high ** 25ppm attributable to MB7 used + White Mist- is a white flux-calcined diatomite available from Celite Corp. ++ Block in Newtons measured by ASTM 1893 (225mm film width) 5 Comparative Experiment 25 represents the performance of unmodified POP 1. 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 POP 1. Example 21 10 represents a film fabricated from a composition of the current invention. This film shows good clarity, haze, gloss, and anti block properties. 73 WO 98/46672 PCT/US98/07650 Example 22 and Comparative Experiments 28- 30 The films of Example 22 and Comparative Experiments 28- 30 were made on a blown coextrusion line. A low density polyethylene having a density of 0.924 and a melt index of 1.75, non stabilized and available from The Dow Chemical Company 5 (Commercial name LD320), was used as the outside layer. A heterogeneously branched linear low density ethylene/1-octene copolymer, having a density of 0.919 g/cm 3 , a melt index (12) of 1.05 g/10 min and available from The Dow Chemical Company (commercial name Dowlex NG 5056.01E), was used as the core layer. The indicated POPI or POP4 was used as the inner heat seal layer. Each of the 10 compositions was extruded as dry blend of the POP 1 layer with the appropriate master batch and or PPI by automatic feeding on the basis of weight. In the case of each example, the sum of the amount of POPI 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. 15 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. 74 WO 98/46672 PCT/US98/07650 Table 8 Example Comp. Expt. Comp. Expt. Comp. Expt. Ex. 22 28 29 30 base POP4 POPI POPI POP1 MB1 % 0 0 1.2 3 MB3 % 0 0 1 1 MB4 % 0 2.2 2.2 0 PP1 % 0 0 0 1 Slip Level ppm 750 990 2090 2000 (1590 Er+ 500 (1500 Er St) + 500 St) AB level ppm 3000 2750 2750 10000 AB type White Mist Talc Talc PP Nip roll set temp 0 C 35 43 42 42 comment wrinkles no wrinkles no wrinkles no wrinkles COF (initial in/in) 0.44 0.64 0.32 0.32 Gloss 20 89.94 81.62 95.6 91.92 Gloss 60 116.04 114.54 119.48 115.4 Haze (%) 5.54 5.62 5.66 5.9 Clarity 78.6 65.8 70.6 83.4 * n.m = not measurable because too high + White MistTM is a white flux-calcined diatomite available from Celite Corp. 5 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 75 WO 98/46672 PCT/US98/07650 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 5 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 10 to the films of Comparative Experiments 28 and 30. 76

Claims (35)

  1. . A composition comprising; (A) a homogeneous ethylene/α-olefin inteφolymer having a narrow composition distribution; and (B) a saturated fatty acid amide or saturated ethylenebis(amide); and (C) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); and (D) a finely divided inorganic compound; and wherein the sum of the concentrations of Components B and C is greater than 1500 ppm (based on the combined weights of Components A, B. C, and D) and, when the resin composition is fabricated into a blown film having a thickness of 2 mils, said film is characterized as having a block of less than 49 g and a COF of less than 0.31.
  2. 2. The composition of Claim 1 wherein; (A) Component A has a density of from 0.870 to 0.940 g/cm3, a melt index (L) of from 0.2 to 100 g/lOmin, an I10/I2 greater than 5.6; and (B) Component B conforms essentially to the empirical formula Ra-C(O)NHRb or Ra-C(O)NHCH2CH2NHC(O)-Ra where Ra is a saturated alkyl group having from 10 - 26 carbon atoms and Rb is independently hydrogen or a saturated alkyl group having from 10 - 26 carbon atoms and wherein said Component B is present in a concentration of from 10 ppm to 1,250 ppm based on the combined weights of Components A. B, C, and D (C) Component C conforms essentially to the empirical formula RcC(O)NHRd where Rc is an unsaturated alkyl group having from 10 - 26 carbon atoms and Rd is independently hydrogen or a unsaturated alkyl group having from 10 - 26 carbon atoms, or to the empirical formula ReC(O)NHCH2CH2NHC(O)Re where Re is either a saturated or unsaturated alkyl group having from 10 - 26 carbon atoms with the proviso that at least one of Re is an unsaturated alkyl group having from 10 -26 carbon atoms, and wherein said Component C is present in a concentration of from 250 ppm to 10,000 ppm based on the combined weights of Components A, B, C, and D; and (D) Component D comprises at least one of silica, alumina, talc, limestone, clay, celite, titanium dioxide or calcium carbonate and is present in a concentration of from 500 ppm to 15,000 ppm based on the combined weights of Components A, B, C, and D.
  3. 3. The composition of Claim 1 wherein; (A) Component A has a density of from 0.890 to 0.920 g/cm3, a melt index (I2) of from 0.4 to 50 g/lOmin, an I]0/I2 of from 5.6 to 13; and (B) Component B is stearamide, behenamide or arachidamide and is present in a concentration of from 100 ppm to 1000 ppm based on the combined weights of Components A, B, C, and D; and (C) Component C is erucamide, oleamide, erucamido ethylerucamide or oleamidoethylbisoleamide and is present in a concentration of from 500 ppm to 8,000 ppm based on the combined weights of Components A, B, C, and D; and (D) Component D is silica, and is present in a concentration of from 1 ,000 ppm to 10,000 ppm based on the combined weights of Components A, B, C, and D.
  4. 4. The composition of Claim 1 wherein; (A) Component A has a density of from 0.890 to 0.910 g/cm3, a melt index (I2) of from 0.5 to 20 g/1 Omin, an I]0/I2 ratio of from 5.6 to 11, and an MJMn ratio of from 1.8 to 6.0; and (B) Component B is stearamide, and is present in a concentration of from 250 ppm to 750 ppm based on the combined weights of Components A, B, C, and D; and (C) Component C is erucamide. and is present in a concentration of from 750 ppm to 5000 ppm based on the combined weights of Components A. B, C, and D; and (D) Component D is silica, and is present in a concentration of from 1250 ppm to 7500 ppm based on the combined weights of Components A, B, C, and D.
  5. 5. The composition of Claim 1 wherein Component A is a substantially linear ethylene/α-olefin inteφolymer. wherein said inteφolymer is characterized as having: A) a melt flow ratio, 1 \ QI\2, ≥ 5.63; and B) a molecular weight distribution. Mw/Mn. defined by the equation: Mw/Mn < (I10 I2) - 4.63; and C) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene/α-olefin polymer having the same 12 and Mw/Mn; and D) a processing index less than or equal to 70 percent of the PI of a linear ethylene/α-olefin polymer having the same 12 and Mw/Mn; and E) has from 0.01 to 3 long chain branches/1000 carbons.
  6. 6. A process for reducing block and increasing slip of films and thin sheets which process comprises fabricating said films and sheets from the composition of Claim 1.
  7. 7. A composition comprising; (A) an inteφolymer blend composition comprising; (1) a homogeneous ethylene/α-olefin inteφolymer having a narrow composition distribution; and (2) a second inteφolymer comprising; (a) a heterogeneous ethylene/α-olefin inteφolymer having a broad composition distribution; or (b) the inteφolymer (1) having a different L, or density, or Mw, or M /Mn; or (c) any combination of (a) or (b); and (B) a saturated fatty acid amide or saturated ethylenebis(amide); and (C) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); and (D) a finely divided inorganic compound; and wherein the sum of the concentrations of Components B and C is greater than 1.500 ppm based on the combined weights of Components A. B. C, and D. and. when the resin composition is fabricated into a blown film having a thickness of 2 mils, said film is characterized as having a block of less than 49 g and a COF of less than 0.31.
  8. 8. The composition of Claim 7 wherein Component A has a density of from 0.870 to 0.940 g/cm3, a melt index (L) of from 0.2 to 100 g/lOmin. and an I10/I2 greater than 5.6; and wherein A) Component (A)(1) is present in the inteφolymer composition in an amount of from 10 to 90 % by weight based on the combined weights of Components A. B, C. and D. and has a density of from 0.870 to 0.940 g/cm3, a melt index (I2) of from 0.05 to 100 g/lOmin, an I10/I2 greater than 5.6; and B) Component (A)(2) is present in the inteφolymer composition in an amount of from 10 to 90 % by weight based on the combined weights of Components A, B, C, and D; and wherein said Component (A)(2) has the correct density, I2, 1,0/,2, and M„/Mn , and is present in the correct concentration to yield the desired properties of the final blend Component (A). C) Component B conforms essentially to the empirical formula Ra-C(O)NHRb or Ra-C(O)NHCH2CH2NHC(O)-Ra where Ra is a saturated alkyl group having from 10 -26 carbon atoms and Rb is independently hydrogen or a saturated alkyl group having from 10 -26 carbon atoms and wherein said Component B is present in a concentration of from 10 ppm to 1 ,250 ppm based on the combined weights of Components A, B, C, and D; and D) Component C conforms essentially to the empirical formula RcC(0)NHRd where Rc is an unsaturated alkyl group having from 10 -26 carbon atoms and Rd is independently hydrogen or a unsaturated alkyl group having from 10 -26 carbon atoms, or to the empirical formula ReC(O)NHCH2CH2NHC(O)Re where Re is either a saturated or unsaturated alkyl group having from 10 -26 carbon atoms with the proviso that at least one of Re is an unsaturated alkyl group having from 10 -26 carbon atoms, and wherein said Component C is present in a concentration of from 250 ppm to 10,000 ppm based on the combined weights of Components A. B. C. and D; and E) Component D comprises at least one of silica, talc, limestone, clay, celite. titanium dioxide or calcium carbonate and is present in a concentration of from 500 ppm to 15000 ppm based on the combined weights of Components A, B, C, and D.
  9. composition of claim 7 wherein A) Component A has a density of from 0.890 g/cm3 to 0.920 g/cm3, a melt index (I2) of from 0.4 to 50 g/lOmin, and I,0/I2 of from 5.6 to 13; and B) Component (A)(1) is present in the inteφolymer composition in an amount of from 15 to 85 % by weight based on the combined weights of Components A, B, C. and D. and has a density of from 0.870 to 0.920 g/cm3, a melt index (I2) of from 0.2 to 50 g/10 min, an I10/I2 of from 5.6 to 13; and C) Component (A)(2) is present in the inteφolymer composition in an amount of from 15 to 85 % by weight based on the combined weights of Components A, B, C. and D; and D) Component B is at least one selected from the group of stearamide, behenamide or arachidamide and is present in a concentration of from 100 ppm to 1000 ppm based on the combined weights of Components A. B, C, and D; and E) Component C is at least one selected from the group of erucamide, oleamide or erucamidoethylerucamide or oleamidoethylbisoleamide and is present in a concentration of from 500 ppm to 8.000 ppm based on the combined weights of Components A, B, C. and D; and F) Component D comprises is silica, and is present in a concentration of from 1,000 ppm to 10.000 ppm based on the combined weights of Components A. B, C. and D.
  10. 10. The composition of claim 7 wherein : A) Component A has a density of from 0.890 g/cm3 to 0.910 g/cm3, a melt index (L) of from 0.5 to 20 g/lOmin. an I10/L of from 5.6 to 11. an MNJMn of from 1.8 to 6.0; and B) Component (A)(1) is present in the inteφolymer composition in an amount of from 20 to 80 % by weight based on the combined weights of Components A, B, C, and D, and has a density of from 0.870 to 0.905 g/cm3 and a melt index (I2) of from 0.2 to 20 g/10 min, an I10/I2 of from 5.6 to 11 , and an M„/Mn of from 1.8 to 6.0; and C) Component (A)(2) is present in the inteφolymer composition in an amount of from 20 to 80 % by weight based on the combined weights of Components A, B, C, and D; and D) Component B is stearamide, and is present in a concentration of from 250 ppm to 750 ppm based on the combined weights of Components A, B, C. and D; and E) Component C is erucamide. and is present in a concentration of from 750 ppm to 5000 ppm based on the combined weights of Components A, B, C, and D; and F) Component D is silica, and is present in a concentration of from 1.250 ppm to 7.500 ppm based on the combined weights of Components A. B, C, and D.
  11. 11. The composition of Claim 7 wherein the homogeneous inteφolymer having a narrow composition distribution is a substantially linear ethylene/α-olefin inteφolymer, wherein the substantially linear efhylene/α-olefin polymer is characterized as having: a) a melt flow ratio, ≥ 5.63; and b) a molecular weight distribution. Mw/Mn. defined by the equation: Mw/Mn < (I10/l2) - 4.63; and c) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene/α-olefin polymer having about the same 12 and M /Mn; and d) a processing index less than or equal to about 70 percent of the PI of a linear ethylene/α-olefin polymer having about the same 12 and M /Mn; and e) has from 0.01 to 3 long chain branches/ 1000 carbons.
  12. 12. A process for reducing block and increasing slip of films and thin sheets which process comprises fabricating said films and sheets from the composition of Claim 7.
  13. 13. The composition of Claim 1 in the form of a thin sheet having a thickness in the range of from 10 to 20 mils.
  14. 14. The composition of Claim 7 in the form of a thin sheet having a thickness in the range of from 10 to 20 mils.
  15. 15. The composition of Claim 1 in the form of a film having an average thickness in the range of from 0.3 to 8 mils.
  16. 16. The composition of Claim 7 in the form of a film having an average thickness in the range of from 0.3 to 8 mils.
  17. 17. The composition of Claim 1 in the form of a blown film, a cast film, a monolayer film, or a coextruded film.
  18. 18. The composition of Claim 7 in the form of a blown film, a cast film, a monolayer film, or a coextruded film.
  19. 19. A composition comprising; (A) at least one substantially random inteφolymer; wherein said inteφolymer comprises; (1) from 0.5 to 65 mole percent of polymer units derived from; (a) at least one vinylidene aromatic monomer, or (b) at least one hindered aliphatic vinylidene monomer, or (c) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic vinylidene monomer; and (2) from 35 to 99.5 mole percent of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and (B) a saturated fatty acid amide or saturated ethylenebis(amide); or (C) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); or (D) a finely divided inorganic compound; or (E) a combination of at least one of (B), (C). and (D).
  20. 20. The composition of Claim 19; wherein (1) said substantially random inteφolymer. Component A, comprises of from 1 to 55 mole percent of polymer units derived from; (a) at least one of said vinylidene aromatic monomers. Component A( 1 )(a). represented by the follo ing general formula;
    Ar I (CH2)n R1 - C = C(R2)2 wherein R1 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 R2 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,.4-alkyl, and C -haloalkyl; and n has a value from zero to 4; or b) at least one of said hindered aliphatic vinylidene monomers. Component A(l)(b), represented by the following general formula;
    A' I Rl ~ C = C(R2)2 wherein A1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons, R1 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 R2 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 R1 and A1 together form a ring system; or (2) said substantially random inteφolymer, Component A, contains of from 45 to 99 mole percent of polymer units derived from at least one of said aliphatic α-olefins selected from the group consisting of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene. butene- 1 , hexene- 1 or octene- 1 ; (3) said substantially random inteφolymer, Component A. has a melt index (I2) of from 0.01 to 1,000; (4) said substantially random inteφolymer, Component A, has a molecular weight distribution (M /Mn) of from 1.5 to 20; and (5) said saturated fatty acid amide or saturated ethylenebis(amide). Component B. respectively conforms essentially to the empirical formula Ra-C(0)NHRb or Ra-C(O)NHCH2CH2NHC(O)-Ra where Ra is a saturated alkyl group having from 10 -26 carbon atoms and Rb is independently hydrogen or a saturated alkyl group having from 10 -26 carbon atoms and wherein said Component B is present in a concentration of from 0 to 5000 ppm based on the combined weights of Components A. B. C. and D; (6) said unsaturated fatty acid amide or unsaturated ethylenebis(amide), Component C, respectively conforms essentially to the empirical formula RlG(O)NHRd where Rc is an unsaturated alkyl group having from 10 - 26 carbon atoms and Rd is independently hydrogen or a unsaturated alkyl group having from 10 -26 carbon atoms, or to the empirical formula ReC(0)NHCH2CH2NHC(O)Re where Re is either a saturated or unsaturated alkyl group having from 10 - 26 carbon atoms with the proviso that at least one of Re is an unsaturated alkyl group having from 10 - 26 carbon atoms, and wherein said Component C is present in a concentration of from 0 to 10.000 ppm based on the combined weights of Components A, B, C, and D; and (7) said finely divided inorganic compound. Component D, comprises at least one of silica, alumina, talc, limestone, clay, celite, titanium dioxide or calcium carbonate and is present in a concentration of from 0 to 20,000 ppm based on the combined weights of Components A, B, C, and D.
  21. 21. The composition of Claim 19; wherein (1) said substantially random inteφolymer, Component A. comprises of from 2 to 50 mole percent of polymer units derived from; (a) the group consisting of styrene, α-methyl styrene, ortho-, meta-, and para-methylstyrene, and the ring halogenated styrenes. or (b) the group consisting of 5-ethylidene-2-norbornene or 1- vinylcyclo-hexene, 3-vinylcyclohexene, and 4-vinylcyclohexene: or (c) a combination of at least one of a) and b); (2) said substantially random inteφolymer. Component A. comprises of from 50 to 98 mole percent of polymer units derived from ethylene: (3) said substantially random inteφolymer. Component A. has a melt index (I,) of from 0.1 to 100; (4) said substantially random inteφolymer, Component A. has a molecular weight distribution (Mw/Mn) of from 1.8 to 10; (5) said saturated fatty acid amide or saturated ethylenebis(amide), Component B. is stearamide. behenamide or arachidamide and is present in a concentration of from 250 to 2500 ppm based on the combined w eights of Components A, B, C, and D; and (6) said unsaturated fatty acid amide or unsaturated ethylenebis(amide), Component C. is erucamide. oleamide. erucamido ethylerucamide or oleamidoethvlbisoleamide and is present in a concentration of from 500 to 7500 ppm based on the combined weights of Components A, B, C, and D; and (7) said finely divided inorganic compound, Component D. is silica or talc and is present in a concentration of from 1.000 to 15.000 ppm based on the combined weights of Components A, B. C, and D.
  22. 22. The composition of Claim 21 ; wherein (1) said substantially random inteφolymer, Component A, has a melt index (I2) of from 0.5 to 30; (2) said substantially random inteφolymer, Component A, has a molecular weight distribution (Mw7Mn) of from 2 to 5; (3) said vinylidene aromatic monomer, Component A 1(a), is styrene; (4) said aliphatic α-olefin, Component A2, is ethylene; (5) said saturated fatty acid amide or saturated ethylenebis(amide), Component B, is stearamide, and is present in a concentration of from 500 to 1500 ppm based on the combined weights of Components A, B, C, and D; and (6) said unsaturated fatty acid amide or unsaturated ethylenebis(amide), Component C, is erucamide, and is present in a concentration of from 1000 ppm to 3000 ppm based on the combined weights of Components A, B, C, and D; and (7) said finely divided inorganic compound, Component D. is silica or talc present in a concentration of from 2.000 to 10,000 ppm based on the combined weights of Components A, B, C, and D.
  23. 23. A composition comprising; (A) a resin composition comprising; (1) a homogeneous ethylene/α-olefin inteφolymer having a narrow composition distribution; or (2) at least one substantially random inteφolymer; wherein said inteφolymer comprises; (a) from 0.5 to 65 mole percent of polymer units derived from; (i) at least one vinylidene aromatic monomer, or (ii) at least one hindered aliphatic vinylidene monomer, or (iii) a combination of at least one vinylidene aromatic monomer and at least one hindered aliphatic vinylidene monomer; and (b) from 35 to 99.5 mole percent of polymer units derived from at least one aliphatic α-olefin having from 2 to 20 carbon atoms; and, optionally 3) a homopolymer of propylene or copolymer of propylene and one or more C2 - C20 α-olefins; and (B) one or more of; (1) a saturated fatty acid amide or saturated ethylenebis(amide) or (2) an unsaturated fatty acid amide or unsaturated ethylenebis(amide); or (3) a combination of B(l) and B(2); and, optionally, (C) a nucleating agent.
  24. 24. The composition of Claim 23; wherein (1) said homogeneous ethylene/α-olefin inteφolymer, Component (A)(1), has a density of from 0.855 to 0.960 g/cm3, a melt index (I2) of from 0.02 to 100 g/lOmin, an I10/I2 greater than 5.6; and (2) said substantially random inteφolymer, Component (A)(2), contains of from 1 to 55 mole percent of polymer units derived from; (a) at least one of said vinylidene aromatic monomers, Component (A)(2)(a)(i), represented by the following general formula:
    Ar
    (CH2)n Ri - C = C(R2)2 wherein R1 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 R2 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 -a╬╣kyl, and C,.4-haloalkyl; and n has a value from zero to 4; or b) at least one of said hindered aliphatic vinylidene monomers, Component (A)(2)(a)(ii), represented by the following general formula;
    A1 R' - C = C(R2)2 wherein A1 is a sterically bulky, aliphatic or cycloaliphatic substituent of up to 20 carbons, R1 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 R2 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 R1 and A' together form a ring system; and (3) said substantially random inteφolymer, Component (A)(2), contains of from 45 to 99 mole percent of polymer units derived from at least one of said aliphatic α-olefins selected from the group consisting of ethylene or a combination of ethylene and at least one of propylene, 4-methyl pentene, butene-1, hexene-1 or octene- 1; (4) said substantially random inteφolymer, Component (A)(2), has a melt index (I2) of from 0.01 to 1,000; (5) said substantially random inteφolymer, Component (A)(2), has a molecular weight distribution (M /Mn) of from 1.5 to 20; (6) said homopolymer or copolymer of propylene, Component (A)(3), is present in an amount of from 0 to 5 wt %> (based on the combined weights of Components A, B, and C) and has a melt index (I,, 230°C) of from 0.2 to 10 g/lOm, and a density of from 0.880 to 0.920 g/cm3; and (7) said saturated fatty acid amide or saturated ethylenebis(amide), Component B(l), respectively conforms essentially to the empirical formula Ra- C(O)NHRb or Ra-C(O)NHCH2CH2NHC(O)-Ra where Ra is a saturated alkyl group having from 10 - 26 carbon atoms and Rb is independently hydrogen or a saturated alkyl group having from 10 - 26 carbon atoms and wherein said Component B(l) is present in a concentration of from 0 to 5000 ppm based on the combined weights of Components A, B, and C; and (8) said unsaturated fatty acid amide or unsaturated ethylenebis(amide), Component B(2), respectively conforms essentially to the empirical formula RcC(O)NHRd where Rc is an unsaturated alkyl group having from 10 - 26 carbon atoms and Rd is independently hydrogen or a unsaturated alkyl group having from 10 - 26 carbon atoms, or to the empirical formula ReC(O)NHCH2CH2NHC(O)Re where Re is either a saturated or unsaturated alkyl group having from 10 -26 carbon atoms with the proviso that at least one of Re is an unsaturated alkyl group having from 10 -26 carbon atoms, and wherein said Component B(2) is present in a concentration of from 0 to 10,000 ppm based on the combined weights of Components A, B. and C: and (9) said nucleating agent, Component C, comprises at least one of a smectite clay mineral, an illite mineral, a layered double hydroxide, a cyanide, and oxide, a chalcogenide, a metal chloride, or an acetal or a mixture thereof; and wherein said nucleating agent, Component C is present in a concentration of from 0 to 3,000 ppm based on the combined weights of Components A, B, and C.
  25. 25. The composition of Claim 23 wherein; (1) said homogeneous ethylene/α-olefin inteφolymer, Component (A)(1), has a density of from 0.870 to 0.915 g/cm3, a melt index (L) of from 0.2 to 50 g/lOmin, an I10/I2 of from 5.6 to 13; and (2) said substantially random inteφolymer, Component (A)(2), contains of from 2 to 50 mole percent of polymer units derived from; a) the group consisting of styrene, α-methyl styrene, ortho-, meta-. and para-methylstyrene, and the ring halogenated styrenes, or b) the group consisting of 5-ethylidene-2-norbornene or 1- vinylcyclo-hexene, 3-vinylcyclohexene, and 4-vinylcyclohexene; or c) a combination of at least one of a) and b); (3) said substantially random inteφolymer. Component (A)(2). contains of from 50 to 98 mole percent of polymer units derived from ethylene; (4) said substantially random inteφolymer. Component (A)(2), has a melt index (I2) of from 0.1 to 100; (5) said substantially random inteφolymer, Component (A)(2), has a molecular weight distribution (M Mn) of from 1.8 to 10; (6) said homopolymer or copolymer of propylene, Component (A)(3), is present in an amount of from 0.3 to 3 wt % (based on the combined weights of Components A, B, and C);and has a melt index (I2, 230°C) of from 0.3 to 5 g/lOm. and a density of from 0.890 to 0.910 g/cm3; and (7) said saturated fatty acid amide or saturated ethylenebis(amide). Component B(l), is stearamide, behenamide or arachidamide and is present in a concentration of from 250 to 2500 ppm based on the combined weights of Components A, B, and C; and (8) said unsaturated fatty acid amide or unsaturated ethylenebis(amide), Component B(2), is erucamide, oleamide, erucamido ethylerucamide or oleamidoethylbisoleamide and is present in a concentration of from 500 ppm to 7,500 ppm based on the combined weights of Components A, B. and C; and (9) said nucleating agent, Component C. montmorillonite, nontronite, beidellite. volkonskoite, hectorite, saponite, sauconite, magadiite, kenyaite, and vermiculite. ledikite and admixtures thereof. Mg6Al3 4(OH)18 8(CO3), 7H2O, ReCl3, FeOCl. TiS2, MoS2, and MoS3; Ni(CN)2, H2Si2O5, V5O13, HTiNbO5, Cr05V05S2, W02V2 8O7. Cr3O8, MoO3(OH)2, VOPO4-2H2O, CaPO4CH3-H2O, MnHAsO4-H2O,Ag6Mo10O33, sodium benzoate, lithium benzoate, sodium 2,2' methylene-bis-( 4,6-di-tert-butylphenyl) phosphate, di (benzylidene) sorbitol. methyl-di (benzylidene) sorbitol, trinaphthylidene sorbitol, tri (4-methyl-l-naphthylidene) sorbitol, tri-(4-methyoxy-l-naphtylidene)sorbitol, dibenzylidene zylitol, dibenzylidenesorbitol, 3,4,-dimethyl dibenzylidene-sorbitol, l,3-benzylidene-2,4-p- methylbenzylidenesorbitol, l,3-benzylidene-2,4-p-ethylbenzylidenesorbitol, 1,3-p- methylbenzylidene-2,4-benzylidenesorbitol, 1 ,3-p-ethylbenzylidene-2,4- benzylidenesorbitol, l,3-p-methylbenzylidene-2.4-p-ethylbenzylidenesorbitol, 1,3-p- ethylbenzylidene-2,4-p-methylbenzylidenesorbitol, 1 ,3,2,4-di-(p- methylbenzylidene)sorbitol, l,3,2,4-di-(p-ethylbenzylidene)sorbitol, l,3,2,4-di-(p-n- propylbenzylidene)sorbitol, l,3,2,4-di-(p-i-propylbenzylidene)sorbitol, l,3,2,4-di-(p-n- butylbenzylidene)sorbitol, 1 ,3 ,2,4-di-(p-sec-butylbenzylidene)sorbitol, 1 ,3 ,2,4-di-(p-t- butylbenzylidene)sorbitol, l,3,2,4-di-(2',4'-dimethylbenzylidene)sorbitol, l,3,2,4-di-(p- methoxybenzylidene)sorbitol, l,3,2,4-di-(p-ethoxybenzylidene)sorbitol, 1,3- benzylidene-2,4-p-chlorobenzylidenesorbitol, 1 ,3 -p-chlorobenzylidene-2,4- benzylidenesorbitol, l,3-p-chlorobenzylidene-2.4-p-methylbenzylidenesorbitol, 1,3-p- chlorobenzylidene-2,4-p-ethylbenzylidenesorbitol, 1 ,3-p-methylbenzylidene-2,4-p- chlorobenzylidenesorbitol, l,3-p-ethylbenzylidene-2,4-p-chlorobenzylidenesorbitol, or 1 ,3,2,4-di-(p-chlorobenzylidene)sorbitol. or mixtures thereof and is present in a concentration of from 500 to 2500 ppm based on the combined weights of Components A, B, and C.
  26. 26. The resin composition of Claim 25 wherein; (1) said homogeneous ethylene/α-olefin inteφolymer, has a density of from 0.885 to 0.905 g/cm3, a melt index (I2) of from 0.5 to 4 g/lOmin, an I10/I2 ratio of from 5.6 to 11, and an MJMn ratio of from 1.8 to 6.0; and (2) said vinylidene aromatic monomer is styrene; (3) said aliphatic α-olefin is ethylene; (4) said substantially random inteφolymer has a melt index (I2) of from 0.5 to 30; (5) said substantially random inteφolymer has a molecular weight distribution (MNV/Mn) of from 2 to 5 ; (6) said homopolymer or copolymer of propylene, is an isotactic propylene homopolymer or copolymer present in an amount of from 0.5 to 2 wt % (based on the combined weights of Components A, B, and C);and has a melt index (I2, 230°C) of from 0.5 to 2 g/lOm, and a density of from 0.895 to 0.905 g/cm3; and (7) said saturated fatty acid amide or saturated ethylenebis(amide), is stearamide, and is present in a concentration of from 500 to 1500 ppm based on the combined weights of Components A, B, and C; and (8) said unsaturated fatty acid amide or unsaturated ethylenebis(amide), is erucamide, and is present in a concentration of from 1,000 ppm to 3,000 ppm based on the combined weights of Components A, B, and C; and (9) said nucleating agent is Millad™ 3988, and is present in a concentration of from 1,000 to 2,000 ppm based on the combined weights of Components A, B, and C.
  27. 27. The resin composition of Claim 23 wherein said homogeneous ethylene/α- olefin inteφolymer, Component (A)(1), is a substantially linear ethylene/α-olefin inteφolymer, wherein said inteφolymer is characterized as having: (A) a melt flow ratio, I I Q I2, ≥ 5.63; (B) a molecular weight distribution, Mw/Mn, defined by the equation: Mw/Mn < (I10/I2) - 4.63; (C) a critical shear rate at onset of surface melt fracture of at least 50 percent greater than the critical shear rate at the onset of surface melt fracture of a linear ethylene/α-olefin polymer having the same 12 and Mw/Mn; (D) a processing index less than or equal to 70 percent of the PI of a linear ethylene/α-olefin polymer having the same 12 and Mw/Mn; and (E) has from 0.01 to 3 long chain branches/1000 carbons.
  28. 28. A process for reducing block and increasing slip of films and thin sheets which process comprises fabricating said films and sheets from the resin composition of Claim 19.
  29. 29. The resin composition of Claim 19 in the form of a thin sheet having a thickness in the range of from 10 to 20 mils.
  30. 30. The resin composition of Claim 19 in the form of a film having an average thickness in the range of from 0.3 to 8 mils.
  31. 31. The resin composition of Claim 19 in the form of a blown film, a cast film, a monolayer film, or a coextruded film.
  32. 32. A process for reducing block and increasing slip of films and thin sheets which process comprises fabricating said films and sheets from the composition of Claim 23.
  33. 33. The composition of Claim 23 in the form of a thin sheet having a thickness in the range of from 10 to 20 mils.
  34. 34. The composition of Claim 23 in the form of a film having an average thickness in the range of from 0.3 to 8 mils.
  35. 35. The composition of Claim 23 in the form of a blown film, a cast film, a monolayer film, or a coextruded film.
    Disclosed are resin compositions comprising; a homogeneous ethylene/α-olefin inteφolymer; and a saturated fatty acid amide or saturated ethylenebis(amide); and an unsaturated fatty acid amide or unsaturated ethylenebis(amide); and a finely divided inorganic compound. Also disclosed are compositions comprising a saturated fatty acid amide or saturated ethylenebis(amide), an unsaturated fatty acid amide or unsaturated ethylenebis(amide), and a finely divided inorganic compound and a substantially random inteφolymer of one or more α-olefins with one or more vinylidene aromatic monomers and/or one or more hindered aliphatic or cycloaliphatic vinylidene monomers or blend compositions therefrom. Also disclosed are compositions which comprise at least one homogeneous ethylene/α-olefin inteφolymer or substantially random inteφolymer of one or more α-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 copolymers, nucleating agents, and mixtures thereof.
AU69740/98A 1997-04-16 1998-04-15 Compositions containing slip and antiblock agents Abandoned AU6974098A (en)

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BRPI0713204A8 (en) 2006-06-29 2017-12-12 Dow Global Technologies Inc PROCESS FOR MAKING A CONFORMED ARTICLE, KIT FOR USE IN A PROCESS FOR MAKING A CONFORMED ARTICLE AND ARTICLE
US8709316B2 (en) 2008-03-14 2014-04-29 Dow Global Technologies Llc Process for shaping polymeric articles
GB0910781D0 (en) 2009-06-23 2009-08-05 Croda Int Plc Slip and antiblocking agent
JP6047964B2 (en) * 2011-07-12 2016-12-21 三菱化学株式会社 Resin composition for release film and release film
TWI519339B (en) 2012-12-28 2016-02-01 財團法人工業技術研究院 Filtering membrane
CA2996291C (en) * 2015-08-31 2023-08-22 Dow Global Technologies Llc Multilayer films and methods thereof
CN108136754B (en) * 2015-08-31 2020-11-06 陶氏环球技术有限责任公司 Multilayer film and method thereof
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EP3312007B1 (en) * 2016-10-18 2023-12-27 Dow Global Technologies LLC Multilayer stretch hood compositions and structures
WO2018223357A1 (en) * 2017-06-09 2018-12-13 Dow Global Technologies Llc Multilayer films and laminates containing slip agents

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AR012432A1 (en) 2000-10-18
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CN1252824A (en) 2000-05-10

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