METHOD OF PROCESSING POLYETHYLENE

Abstract: Melt processed linear polyethylenes are shown to exhibit improved processability through the addition of certain surfactants. Among the melt processing parameters improved are reduced head pressure, reduced torque, reduced motor load, reduced or eliminated melt fracture, or combinations of these parameters. The surfactants can be chosen from a non-aromatic alkyl sulfonate or sulfate salt wherein a cation of the salt is selected from the group consisting of Na, K, Li, and other alkali cations and a quaternary ammonium cations, said surfactant being essentially free of halogens.

Description: METHOD OF PROCESSING POLYETHYLENE BACKGROUND Linear polyolefins, in particular, linear polyethylenes, may be difficult to melt process. Specifically, due to a low shear sensitivity when compared to highly branched polyethylenes, the linear polyethylenes can require more extruder power to pump an equivalent amount of polymer melt. As a result, higher extruder head pressures, higher torque, greater motor loads, and the like can develop, as compared to the highly branched materials. Increases such as higher motor load, head pressure and/or torque can place undesirable, unacceptable, or unattainable requirements on specific machinery. As for instance, a specific extruder having a specific motor power and gearing, will reach a maximum of motor load, or head pressure, under certain melt temperature conditions for a given polymer being processed. If a polymer is introduced to such an extruder which has such a higher requirement for power, such as a polymer having higher molecular weight and/or narrower molecular weight distribution and/or lower shear sensitivity, the extruder will reach a maximum of one or several of these parameters, and be therefore limited in its ability to pump/perform at a similar level to the performance expected/demonstrated with a highly branched or broader molecular weight distribution polymer such as traditional high pressure low density polyethylenes. In the alternative, if melt processing machinery is to be used for certain production/extrusion, and it is not so limited, the prospect of using more power or increasing head pressure for a more difficult to extrude material, while achievable, the user of the machinery would prefer to conserve power. Additionally, linear polyethylenes may exhibit other imperfections during extrusion, specifically blown film extrusion, that may be undesirable, such as melt fracture. These imperfections are undesirable from a quality standpoint. For instance, melt fracture, also known as "shark skin" or "orange peel", can lead to poorer optical properties and/or diminished film physical properties, that are generally unacceptable. The introduction of linear Ziegler-Natta catalyzed polyethylenes in the late '70s and early '80s and extruder owner's attempts to use these polyethylenes in machines that had been previously used to extrude free radical initiated, highly branched, high pressure produced low density polyethylenes provided the early manifestations of these problems. The advent of metallocene catalyzed linear polyethylenes in the '90s, has continued the trend towards polymers that when fabricated into films for instance, offer better physical properties and/or manufacturing economics, but have higher power requirements and/or greater tendency to exhibit melt fracture in the blown film process. Linear polyethylenes therefore have been the subject of a good deal of effort to eliminate or reduce such problems. Some of the attempts included regearing extruders, designing new and more efficient screws and dies, increasing the power train, addition of expensive fiuoroelastomeric processing aids and the like. In nearly every instance, the cost involved has not been inconsequential, as well as the inconvenience. But such costs have been born, due to the desirability of physical properties and/or downgaging possible with the linear polyethylenes. GB 1,104,662 suggests addition of the salt of alkyl benzene sulfonic acids to polyolefins that purportedly gives a beneficial effect on melt extrusion behavior of the polyolefin. The purported effect is the reduction of the occurrence of "shark skin" or "orange peel". Both alkali and alkaline earth metal salts of alkyl benzene sulfonic acids are purported to be effective. The document is devoid of any identification of the polyethylene, such as molecular weight distribution (MWD), or composition distribution breadth index (CDBI). GB 1,078,738 suggests that addition of an "external lubricant" to high molecular weight polyolefins can, purportedly, reduce occurrence of melt fracture. Suggested as external lubricants are salts of monovalent to tetravalent metals, and saturated or unsaturated carboxylic acids containing 10 to 50 carbon atoms. Sulfonates corresponding to the fatty acid salts are also said to be suitable. However, stearates, palmitates and oleates are exemplified. This document indicates an equivalence of metal salts of mono to tetra-valent metals. JP A 59-176339 suggests that when polyolefins are narrowed in MWD or given higher molecular weight, poor fluidity results which in turn gives rise to melt fracture. The solution suggested is addition of fluorinated compounds including potassium salts of fluoroalkylsulfonic acids. These potassium salts are said to exhibit preferable temperature dependence when compared to other cations such as sodium, calcium, lithium and ammonium. The polyolefin/salt combination is said to be effective at 230° C or higher. DE 2823507 suggests molding or calendered objects of ethylene polymers and propylene polymers containing alkalai or alkaline earth mono sulfonates from the group alkyl sulfonates, alkenyl sulfonates, alkylaryl sulfonates and succinic acid dialkyl ester sulfonates. Sodium or calcium mono sulfonates are preferred. A suggested benefit is purported to be outstanding separation of the polymer from calendering rolls. JP 58-212429 (60-106846) suggests polyethylene compositions consisting of 70-95 weight parts of ethylene homopolymer or ethylene alpha-olefin copolymer with a density of at least 0.94 g/cm 3 ; 5-30 weight parts of at least one of low density polyethylene (high pressure), ethylene vinyl acetate, ionomer, and ethylene alpha-olefin copolymer (density not exceeding 0.935 g/cm 3 ); 0.01-5 weight parts of magnesium salt or calcium salt of alkylsulfonic acid or alkylbenzenesulfonic acid; and 0.05-0.5 weight parts of at least one substance selected from the group which includes dibenzylidene sorbitol or its nuclear substituted derivative. The combination is said to be especially useful in air-cooled inflation film. US 4,829,116 suggests polyolefin molding compositions purportedly having no surface defects that includes a fluorine-containing polymer together with a wax, preferred polyolefins are said to be ethylene copolymers with 1-olefins which contains 3-10 carbon atoms. The fluorine containing compounds are preferably copolymers of vinylidene fluoride and hexafluoropropylene or terpolymers of these monomers with tetra fluoroethylene. Among the suitable waxes enumerated are alkylsulfates or alkyl sulfonates containing straight chain or branched Cg to C 26 alkyl radicals and an alkalai metal ion, preferably a sodium ion. There is a need therefore for a relatively inexpensive, easily implemented solution to the processing problems outlined above. Such a solution should also include a material that when included in blown film extrusion of linear polyethylenes, will readily melt or incorporate into the melted polyethylene, and not adversely affect physical properties, be extractable, or negatively impact organoleptics of the film. Specifically, there is a commercial need for a material that may be easily incorporated into polyethylenes, that will reduce or eliminate the increased power requirement (e.g. motor load and or torque), increased head pressure, and melt fracture. SUMMARY The present invention is directed to such a material, a certain group of surfactants, and methods of their use which when incorporated into a linear polyethylene, can reduce or eliminate processing problems such as melt fracture, increased motor load, increased torque, and combinations thereof and may thereby increase potential production rates. In certain embodiments of the present invention a method of processing polyethylenes comprising selecting a linear polyethylene, from a group such as linear low density polyethylene (LLDPE), metallocene LLDPE (m-LLDPE), high density polyethylene (HDPE), plastomers, ultra high molecular weight high density polyethylene (UHMW-HDPE), medium density polyethylenes (MDPE), or combinations thereof, adding a surfactant having a melting point that does not exceed the processing temperature of the polyethylene by more than approximately 30°C. The surfactant being a non-aromatic alkyl sulfonate or sulfate salt having a cation of either an alkali metal or a quaternary ammonium salt, that is free of halogens. An amount of the surfactant should be added that will be sufficient to improve the melt processability of the polyethylene or polyethylene/elastomer blend. The combination of polyethylenes and surfactant or surfactants is then used to melt process the combination into a useful article, such as a film, blow molded part, and the like. The polyethylenes may be conventional Ziegler-Natta (Z-N) catalyzed materials that generally have a molecular weight distribution characterized by the ratio of weight average molecular weight to the number average molecular weight QΛv Mn) above 4, or the polyethylenes may be metallocene catalyzed, and will then have an approximate M- M„ of less than 3, preferably less than 2.5, and a z- average molecular weight (M z ) divided by M w (M z /M w ) not exceeding 2. Also contemplated are compositions of a polyethylene having an Mw/Mn less than 3, and an alkali metal alkyl sulfonate or sulfate wherein the alkyl group has 6-30 carbon atoms, where the surfactant is present in the polyolefin in a range of from 0.005 to 5 weight percent based on the total weight of the polyethylene. The surfactant should ideally be substantially non-extractable from the final fabricated article. These and other features, aspects, and advantages of the present invention will become better understood with reference to the following description and appended claims. DESCRIPTION In certain embodiments of the present invention, methods of and compositions for reducing or eliminating; a) melt fracture; b) increased torque; c) increased head pressure; d) increased motor load, e) combinations thereof, and the like, during the melt processing of polyethylenes, and other polyolefins are contemplated. These embodiments include both conventional Z-N and metallocene catalyzed polyethylenes(the latter hereinafter "m-polyethylenes), and their combination with certain surfactants that when so combined achieve the stated melt processing improvements. The combination of polyethylenes and surfactants are particularly well suited to melt processing and fabrication into films, especially blown film, blow molded articles, and the like, while reducing or eliminating one or more of the processability problems discussed above and generally without being extractable from the final fabricated article. Following is a detailed description of certain preferred combinations of polyethylenes and surfactants and methods of using the combinations in melt processing into useful articles. Those skilled in the art will appreciate that numerous modifications to these preferred embodiments can be made without departing from the scope of the invention. For example: Although methods of improving melt processing of m-polyethylenes into films are exemplified, they will have numerous other uses and the films may be formed from other polyolefins or combinations of polyethylenes. To the extent this description is specific, it is solely for the purpose of illustrating preferred embodiments of the invention and should not be taken as limiting the present invention to these specific embodiments. DEFINITIONS Torque: horse power/rpm Motor Load: amps Head Pressure: Kpa (psi) Melt Fracture: The Encyclopedia of Polymer Science and Technology, Vol. 8, John Wiley & Sons, (1968) pp. 573-575 indicates that for a given polymer, processed at a constant melt temperature, there exists a critical shear rate in the melt fabrication process. Melt processing of the polymer below this critical shear rate will result in a smooth extrudate surface while processing the polymer above it will result in a rough extrudate surface. The observed roughness is commonly referred to as "melt fracture" but may also be described by other terms such as "sharkskin" or "orange peel". For a given polymer, the critical shear rate increases as the melt processing temperature of the polymer increases. The extent of extrudate roughness will vary depending upon the shear rate at which the polymer is processed. At shear rates just above the critical value, the extrudate roughness normally results in a loss of surface gloss and is typically called "sharkskin". At higher shear rates, the extrudate exhibits periodic areas of roughness followed by areas of smoothness in a more or less regular pattern. This phenomenon is normally described as "cyclic melt fracture". At very high shear rates, the extrudate may become grossly distorted resulting in a what is commonly called "continuous melt fracture". In general, linear polyethylenes, particularly those with high average molecular weights and/or narrow molecular weight distributions, tend to be more prone to the formation of melt fracture than highly branched polyethylenes, such as conventional LDPE made by high pressure polymerization. The presence of melt fracture in a fabricated article can lead to poorer optical properties and is generally aesthetically unacceptable. Attempts to eliminate melt fracture in articles fabricated from linear polyethylenes by either reducing the processing shear rate (reduced production rate) or by increasing the processing temperature (increased melt temperature) are generally not commercially viable. In addition, changes in die design to reduce the shear rate (e.g., use of wider die gaps) can result in other problems such as excessive orientation leading to unbalanced article properties. Although fluoroelastomeric processing additives have been used to eliminate sharkskin in linear polyethylenes under certain processing conditions, their use is expensive due to the high cost of the fluoroelastomer. POLYETHYLENES The polyethylenes contemplated in certain embodiments of the present invention, include ethylene alpha-olefin copolymers. By copolymers we intend combinations of ethylene and one or more alpha-olefins. In general the alpha-olefin comonomers can be selected from those having 3 to 20 carbon atoms. Specifically the combinations may include ethylene 1-butene; ethylene 1-pentene; ethylene 4- methyl-1-pentene; ethylene 1-hexene; ethylene -octene; ethylene decene; ethylene dodecene; ethylene, 1-butene, 1-hexene; ethylene, 1-butene, 1-pentene; ethylene, 1- butene, 4-methyl- 1-pentene; ethylene, 1-butene, 1-octene; ethylene, 1-hexene, 1- pentene; ethylene, 1-hexene, 4-methyl- 1-pentene; ethylene, 1-hexene, 1-octene, ethylene, 1-hexene, decene; ethylene, 1-hexene, dodecene; ethylene, 1-octene, 1- butene; ethylene, 1-octene, 1- pentene; ethylene, 1-octene, 4-methyl- 1-pentene; ethylene, 1-octene, 1-hexene; ethylene, 1-octene, decene; ethylene, 1-octene, dodecene; combinations thereof and the like permutations. The comonomer or comonomers will be present in the copolymers in the range of from 0.1 to 40 mole percent. The actual amount of comonomers will generally define the density range. Density ranges contemplated to be useful include 0.86-0.97 g/cc and all portions and constituents of the range. Specifically included are the 0.86 -0.915 g cc (plasto ers) 0.916-0.925 (LLDPE), 0.926-0.940 (MDPE), and 0.941-0.970 (HDPE). Melt indices contemplated include 0.001-30, preferably 0.5 to 5.0 for blown films, and 0.3-10 for blow molding, and all members of these ranges (melt index in dg/min or g/10 minutes). Polyethylenes that are produced using metallocene catalysts include ionizing activators as well as alumoxanes. Included in the embodiments contemplated are those where either m- polyethylenes and Z-N polyethylenes may be blended with each other and/or with other components such as LDPE, (highly branched, high pressure free radical polymerized) and other ethylene copolymers such as ethylene vinyl acetate (EVA), ethylene n-butyl acrylate (EnBA), ethylene methyl acrylate (EMA), ethylene ethyl acrylate (EEA), ethylene acrylic acid (EAA), ethylene methacrylic acid (EMAA), and ionomers of the acids, terpolymers such as ethylene, vinyl acetate, methyl acrylate; ethylene, methyl acylate, acrylic acid; ethylene, ethyl acrylate, acrylic acid; ethylene, methyl acrylate, methacrylic acid; ethylene, methylacrylate, methacrylic acid; and the like. Also contemplated are multi-layer blown film extrusions where one or more of the layers can include a polyethylene/surfactant combination. Such extrusion may include a linear polyethylene layer, a heat seal layer, a barrier (gas and/or vapor) layer, recycle or regrind layer or combinations thereof. Some of these blend components may affect processing variables in a positive manner, in which case the invention contemplated will include some portion of the below discussed surfactants, possibly less than with an unblended material. Most polyethylenes will contain various additives well known to those of ordinary skill in the art, including, but not limited to slip, anti-block, anti-oxidants, anti-fogs, acid neutralizers, UV inhibitors, anti-static agents, pigments, dyes, release agents, fungicidal, algecidal, bactericidal, and the like. As used in this application, the processing temperature of polyethylene in the blown film process will generally be in the range of 300 - 450° F (149-232° C), preferably 350 - 410° C (177-210° C), a point generally above the melting point of the polyethylene and below its degradation or decomposition temperature. This is generally the temperature of the melt exiting the die, but may be measured at any point downstream of the screw elements. The processing temperature will be understood by those of ordinary skill to vary generally by the melt fabrication technique, and within a fabrication technique, processing temperature can vary by the type of processing equipment, or by specific requirements of a particular manufacturer. SURFACTANTS The surfactants contemplated include non-aromatic alkyl sulfate or sulfonate salts where the cation is one of an alkali metal, e.g. Li, Na, K, and other alkali cations, or a quaternary ammonium salt. Sodium salts being preferred. The surfactants may also be described as alkali metal alkyl sulfates or sulfonates where the alkyl group is a C6 to C30 alkyl group, preferably C8 to C20, more preferably C12 to C18. The alkyl group may be chosen from the group consisting of branched or straight chain alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl and combinations thereof. Preferred are combinations of branched or straight chain alkenyl and branched or straight chain hydroxyl substituted alkyl alkalai metal surfates or sulfonates,of these the sodium combination is most preferred. One class of surfactants that are preferred in this application are α-olefin sulfonates. As stated in the Kirk-Oth er Encyclopedia of Chemical Technology, Vol. 22, John Wiley & Sons, (1983) pg. 352, -olefin sulfonates are produced by reaction of α-olefin with SO3 in air followed by neutralization with a base to produce the corresponding salt. The sodium salts are the most preferred. Commercial α-olefin sulfonates are a mixture of alkene sulfonates and hydroxy alkane sulfonates. The position of the double bond in alkene sulfonates as well as the hydroxyl group in hydroxy alkane sulfonates varies along the carbon chain of the alkyl group. More detailed description of the surfactants follows. The surfactant includes those, of the general formulae: I.) [R, SO * ] M, where x = 3 or 4 Mj is selected from the group consisting of: Li, Na, K, and other alkali cations, and M ] optionally includes NH4 " or quaternary ammonium salts of the structure: Rj,is selected from the group consisting of: branched or straight chain mono or di unsaturated alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl and combinations thereof; wherein said R\, R2, 3 and R4 are essentially free of halogens; and wherein said R2, R3 and R4 are sleeted from the group consisting of: branched or straight chain alkyl branched or straight chain alkenyl, branched or straight chain alkoxy; where said R 3 and R« may optionally contain hydroxyl groups; and wherein the carbon number of said Ri, ranges from 6 to 30; and wherein the carbon number of said R 2 , R 3 , R_ι ranges from 2 to 8; wherein said surfactant is present in said combination in a range of 0.005 to 5.0 weight percent, preferably 0.01 to 0.5, more preferably 0.03 to 0.35 weight percent based on the total weight of the combination. or a surfactant represented by one of the formulae: where x = 3 or 4 M] is selected from the group consisting of: Li, Na, K, and other cations. Mj optionally includes NH4 " or quaternary ammonium salts of the structure, K\, is selected from the group consisting of: branched or straight chain mono or di unsaturated alkenyl, branched or straight chain alkoxy branched or straight chain hydroxyl substituted alkyl and combinations thereof, R2, R3, R4 are selected from the group consisting of: branched or straight chain alkyl, branched or straight chain alkenyl, branched or straight chain alkoxy, wherein said R2, 3 and R4 may contain hydroxyl groups; and wherein the carbon number of said Ri ranges from 6 to 30; and wherein the carbon number of said R 2 , R , and R_4 ranges from 2 to 8. wherein said surfactant is present in said combination in a range of 0.005 to 5.0 weight percent, preferably 0.01 to 0.5, more preferably 0.03 to 0.35 weight percent based on the total weight of the combination. The surfactant or surfactants should be substantially or essentially free of halogens. By substantially free of halogens we intend that the surfactant molecules will have preferably no halogen. The surfactants contemplated, whether a mixture of surfactants or a single species, should have a melting point less than 240° C, preferably 230° C, more preferably 220° C, most preferably 210° C. The surfactants may be present in the polyethylene combination in the range of from 0.005-5.0 weight percent, preferably 0.01-0.5, more preferably 0.03- 0.35 weight percent (including all elements in these ranges) based on the total weight of the combination. The amount and type of surfactant present will determine the effect on the melt processing characteristics, for instance as shown below, smaller amounts at 0.35 wt% or below preferably 0.25%, more preferably 0.10 wt%, or below, will primarily function to reduce melt fracture, while amounts above that level, up to the indicated higher levels will begin to also reduce head pressures, torque, motor load or combinations thereof. While greater amounts than the 0.5 levels may be used, adverse extrusion effects may result, such as screw slippage. Those of ordinary skill will appreciate that at higher levels, generally above 0.1 weight percent, the surfactant or a combination of surfactants will be effective in reducing not only melt fracture, but motor load, torque, head pressure and the like by at least 5% for one or more of these variables. Generally at lower levels than 0.1 weight percent the reductions of these motor load, torque and head pressure parameters will be less, but the surfactants will be effective in reducing melt fracture. The mechanism of melt fracture reduction is believed to involve the formation of a layer of surfactant on the internal metal surfaces of key components of the melt processing equipment. This layer effectively increases the velocity of molten polymer at the metal interface thereby minimizing the polymer flow distortions that occur as the molten polymer exits the melt processing equipment which typically results in melt fracture. The use of a relatively high concentration of surfactant, e.g. 0.5 weight percent, will generally result in a faster rate of metal surface coating and, therefore, a more rapid rate of reduction in melt fracture of the final fabricated article. At lower surfactant levels, the metal surface coating rate, and the corresponding melt fracture reduction rate, will be slower. It should be noted that when discussing the weight percent of surfactant, we intend that this be based on the total weight of the surfactant and polyethylene (or polyethylene blend). If other constituents are included the amount of surfactant should be then calculated on a parts per hundred parts of polyethylene basis. Likewise if a blend constituent (with the linear m-polyethylene) assists in improving processability, then the contemplated amount of surfactant will be that level sufficient to achieve the intended effect, e.g. reduction of one or more of melt fracture,, motor load, torque, or head pressure. For example, blends of one or more of the above surfactants may be used to achieve the desired results, as well as combinations of polyolefin waxes and/or fluoroelastomers and/or fluoropolymers with one or more surfactants. For instance one or more of the surfactants listed above may be combined with a polyethylene wax in ratios from 10-90 and 90-10 and all elements in and between these ranges, and a similar combination with fluoroelastomers and/or fluoropolymers is also contemplated, as well as surfactant polyethylene wax/fluoroelastomer combinations. FILM PROPERTIES Other final product variables or parameters that are included are discussed below. The addition of sufficient levels of surfactant to a polyethylene should generally be "property neutral" that is, the surfactant addition should not substantially diminish any important finished product property such as haze, impact resistance, gloss, tear resistance, modulus, and the like. The surfactant should have a melting point not generally greater than 30° C, preferably 25° C, more preferably 20° C, most preferably 15° C above the processing temperature of the linear polyethylene. The surfactant is generally and preferably molten at the processing temperature of the polyethylene. The processing temperature will be well understood by those of ordinary skill in the art and will differ by melt fabrication technique, e.g. blown film and blow molding temperatures will vary. Also melt processing temperature can be characterized by the melt temperature itself rather than the extruder zone temperatures. EXTRACT ABILITY Extractability of the surfactant from the polyethylene-surfactant matrix should be no more than 7% (wt) of the total surfactant in either water (at 100° C for 3 hrs.) or 95%/5% ethanol/water (at 55° C for 4 hrs.), preferably not more than 5% (wt.), more preferably not more than 4% (wt.), all based on not more than 3 wt. % of surfactant in the polyethylene. EXAMPLES EXAMPLE 1 An antioxidant stabilized metallocene catalyzed linear low density polyethylene resin (m-LLDPE), Exceed™ ECD102 of the following nominal properties (a 1 melt index, 0.917 gm/cc density, ethylene 1-hexene copolymer available from Exxon Chemical Co., Houston, TX, USA), is used in this example. To the granular m-LLDPE resin (Example 1) is added 0.25 wt% BioTerge® AS- 90B Beads (a sodium C14-C16 alpha olefin sulfonate available from Stepan Co., Northfield, IL, USA). A control sample (Comparative example Cl) is prepared by adding 0.08 wt% Dynamar™ FX-9613 (a fluoroelastomeric processing aid available from 3M Co., St. Paul, MN, USA) to a separate portion of the granular m-LLDPE resin. Both portions are compounded and pelletized on a Werner Pfleiderer twin screw extruder. The two pelletized formulations are extruded into film on a 2.5 inch (6.35 cm) Egan tubular blown film extruder. The extruder has a 24/1 length/diameter ratio, Sterlex ® barrier LLDPE screw and is equipped with a 6 inch (15.25 cm) diameter annular die with a 0.030 inch (0.076 cm) die gap. The temperature profile used ranged from 325 to 410°F (162-210° C). Observed melt temperatures ranged from 432 to 438°F (222-225° C). Extruder screw rpm is set to achieve approximately 120 lbs (54.5 kg)/hr of polymer output. Under these conditions, the estimated shear rate is approximately 430 sec"* . The extruded film gauge was nominally 0.0015 inch (38 microns) with a layflat of approximately 24 inches (61 cm). The extrusion sequence for each formulation is as follows. The film line is purged with an LDPE masterbatch containing approximately 4 wt% diatomaceous earth antiblock (Al product from Exxon Chemical Co., Houston, TX, USA). Next, a portion of the m-LLDPE resin, to which no BioTerge® AS-90B or Dynamar™ FX-9613 is added, is extruded into film. Samples of the film are inspected to ensure complete melt fracture. Finally, the test formulation is extruded into film. Periodic samples of the film are taken and the portions which display visible melt fracture, characterized by patterns of irregular flow known as sharkskin, are measured in the transverse direction of the film. The % melt fracture is calculated based upon the total layflat width of the film. The data in Table 1 demonstrates that 0.25 wt% BioTerge® AS-90B used in Example 1 substantially eliminates melt fracture in the m-LLDPE film. The elapsed time for this substantial elimination of melt fracture is nearly the same amount of time needed for 0.08 wt% Dynamar™ FX-9613 (Comparative example Cl) to eliminate melt fracture. At the end of each run, the extruder rpm is increased until the motor load limit is reached (93 rpm) and melt fracture-free film is maintained for each formulation (680 sec-1). A sample with neither FX-9613 nor AS-90B never achieves melt fracture free performances. This is as expected since extrusion shear under these conditions results in a rate above the critical shear rate for this m-LLDPE. In the absence of the surfactant or fluoroelastomer, this will cause melt fracture in the resulting film. Table 1 Table 1A Example Output AS-90B FX-9613 Head Die Motor (lb./hr) Cone. Cone. Pressure Pressure Load (wt%) (wt%) (psig) (psig) (amps) 1 120 None None 5670. 4340. 57.7 1 120 0.25% None 4794. 3670. 45.0 Cl 115 None None 4945. 4008. 54.2 Cl 115 None 0.08% 3701. 3098. 46.8 In addition, the extruder head pressure, die pressure and motor load measured during the extrusion of Example 1 was reduced by approximately 15 to 22% when compared to the same m-LLDPE resin without BioTerge® AS-90B. Comparative example Cl showed reductions in the range of 14 to 25% when compared to the same m-LLDPE resin without Dynamar™ FX-9613. Based upon this example, 0.25 wt % of the BioTerge® AS-90B provides equivalent performance to 0.08 wt % Dynamar® FX-9613 in reduction of melt fracture, head pressure, die pressure and motor load in Exceed® ECD102 m- LLDPE. EXAMPLE 2 The m-LLDPE resin used is the same as that of Example 1. The granular m-LLDPE resin is split into two portions. The first portion, which contained no processing aid previously discussed (e.g. BioTerge ® AS-90B or FX-9613), is pelletized on a Werner Pfleiderer 57 mm twin screw extruder (Comparative example C2). To the second portion of m-LLDPE is added 0.06 wt% BioTerge® AS-90B beads followed by compounding pelletization on the same twin screw extruder (Example 2). The two formulations are extruded into film using the same extruder as in Example 1. The temperature profile used ranged from 325 to 400°F (162-204° C). Observed melt temperatures range from 432 to 439°F (222-226° C). Extruder screw m is held constant at 74 m to achieve approximately 140 lbs hr of polymer output. Under these conditions, the estimated shear rate is approximately 500 sec'l . The extrusion sequence is as follows: Al, Comparative example C2, Example 2. The elimination of melt fracture is measured using the same method as in Example 1. In addition, extruder measurements of head pressure, die pressure and motor load are taken periodically. The data in Table 2 demonstrates that 0.06 wt% BioTerge® AS-90B used in Example 2 reduces melt fracture in the m-LLDPE film to approximately 1% within an hour and completely eliminates it within 1.5 hours As expected, the rate of elimination of melt fracture is slower when a lower concentration of BioTerge® AS-90B is used. By contrast, the m-LLDPE resin which contains no BioTerge® AS-90B yielded film which was completely melt fractured. Even at this low concentration, the BioTerge® AS-90B reduced the extruder head pressure, die pressure and motor load by 6 - 7%. At the end of the run, the extruder φm was increased until the motor load limit was reached (96 φm) and the Example 2 formulation maintained melt fracture-free film (630 sec-1). Table 2 Example Elapsed AS-90B Head Die Motor Melt Time Cone. Pressure Pressure Load Fracture (min) (wt%) (psig) (psig) (amps) (%) C2 94 0 5709 4520 57.4 100 2 0 0.06 5771 4592 57.5 100 2 30 0.06 5601 4392 55.0 18 2 57 0.06 5462 4338 54.4 1 2 86 0.06 5314 4220 53.6 0 EXAMPLE 3 The antioxidant stabilized m-plastomer used in this example was an Exact™ 3128 (a 1.2 melt index, 0.900 gm/cc density, ethylene 1-butene copolymer available from Exxon Chemical Co., Houston, TX, USA). The pelletized metallocene plastomer resin was split into two portions. The first portion, which contained no processing aid, was tested directly (Comparative example C3). To the second portion of metallocene plastomer was added 0.06 wt% BioTerge® AS- 90B beads followed by compounding/pelletization on a Werner Pfleiderer 57 mm twin screw extruder (Example 3). The two formulations were extruded into film using the same extruder and test sequence as Example 2. The temperature profile used ranged from 300 to 395 °F (149-202° C). Observed melt temperatures ranged from 413 to 417°F (212- 214° C). Extruder screw φm was held constant at 52 φm to achieve approximately 120 lbs/hr of polymer output. Under these conditions, the estimated shear rate was approximately 430 sec'l . The data in Table 3 demonstrates that 0.06 wt% BioTerge® AS-90B used in Example 3 completely eliminates melt fracture within 33 minutes. By contrast, the metallocene plastomer resin which contained no BioTerge® AS-90B yielded films which was completely melt fractured. The observed reductions in extruder head pressure, die pressure and motor load ranged from 10 to 14%. At the end of the run, the extruder φm was increased until the motor load limit was reached (64 φm) and the Example 3 formulation maintained melt fracture-free films (520 sec- 1). Table 3 Example Elapsed AS-90B Head Die Motor Melt Time Cone. Pressure Pressure Load Fracture (min) (wt%) (psig) (psig) (amps) (%) C3 30 0 6047 4555 62.3 100 C3 56 0 6045 4543 63.0 100 3 0 0.06 5979 4521 60.7 100 3 33 0.06 5503 4131 57.4 0 3 59 0.06 5225 3920 55.9 0 EXAMPLE 4 An antioxidant stabilized Z-N catalyzed linear low density polyethylene resin (LLDPE), Escorene® LL1001 (a 1 melt index, 0.918 gm/cc density, ethylene 1-butene copolymer available from Exxon Chemical Co., Houston, TX, USA), is used in this example. The granular LLDPE resin is split into two portions. The first portion, which contains no processing aid, is pelletized on a Werner Pfleiderer 57mm twin screw extruder and then tested directly (Comparative example C4). To the second portion of LLDPE was added 0.06 wt% BioTerge® AS-90B beads followed by compounding/pelletization on a Werner Pfleiderer 57mm twin screw extruder (Example 4). The two formulations were extruded into film using the same extruder and test sequence as Example 2. The temperature profile used ranged from 233 to 411 °F (112-211°C). Observed melt temperatures ranged from 434 to 440°F (223- 227° C). Extruder screw φm was held constant at 69 φm to achieve approximately 147 lbs/hr of polymer output. Under these conditions, the estimated shear rate was approximately 525 sec " * . The data in Table 4 demonstrates that 0.06 wt% BioTerge® AS-90B used in Example 4 reduced melt fracture in the LLDPE film to approximately 24% within an hour. By contrast, the LLDPE resin which contained no BioTerge® AS- 90B yielded film which was completely melt fractured. The observed reductions in extruder head pressure, die pressure and motor load ranged from 8 to 15%. Melt fracture was completely eliminated after 155 minutes. At the end of the run, the extruder φm was increased up to the limit of bubble stability (105 φm) and the Example 4 formulation maintained melt fracture-free film (700 sec-1). Table 4 Example Elapsed AS-90BB Head Die Motor Melt Time Cone. Pressure Pressure Load Fracture (min) (wt%) (psig) (psig) (amps) (%) C4 39 0 4877 3724 48.9 100 4 0 0.06 4733 3597 45.3 100 4 41 0.06 4451 3471 41.8 45 4 56 0.06 4419 3423 41.7 24 EXAMPLE 5 An antioxidant stabilized metallocene catalyst produced plastomer, Exact ® 4049 (a 4.5 melt index, 0.873 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co., Houston, Texas, USA) is used in this example. A pelletized form of the copolymer is introduced into a Brabender Plasti-corder melt mixer which was heated to 193° C. Typically, 50-60 g of material is introduced at a rotation speed of 40 RPM. Upon complete melting, the torque remains essentially invariant with time and is used as the base value. Subsequently, a measured amount of sodium alpha olefin sulfonate (Bio Terge ® AS-90B beads - product of Stepan Co., Northfield, Illinois, USA) is added. The torque is again measured at 40 RPM and compared with the base torque value. In this particular example, a torque reduction (12%) is observed at 0.5 wt% of the Bio Terge ® AS-90B beads. At higher levels of the Bio Terge ® AS-90B beads, further reductions are noted. For example, at a 3.0 wt% addition, the torque is reduced by >35%. To insure that complete mixing has occurred, the rotation speed is increased to 100 RPM for five minutes. The material is dumped from the Brabender, cut into small pieces, and allowed to cool to room temperature. The material is formed in sheets via conventional compression molding techniques (PHI Co.). 2" x 2" x 0.02" pads are formed using the following conditions: 2 minute preheat at 193° C, followed by a 3 minute press cycle at 29 tons (193° C) and finally a 4 minute cooling to room temperature again at 29 tons pressure. The tensile properties of all materials are measured on a computer controlled Instron tensile tester (Model 5565). In most instances, little to moderate improvement in tensile properties are measured. The films containing Bio Terge ® AS-90B beads are optically clear and homogeneous. EXAMPLE 6 Following the mixing procedure of Example 5 using again the Exact ® 4049 copolymer, a 3.0 wt% of a calcium alpha olefin sulfonate material (product of Stepan Co., Northfield, Illinois, USA) was introduced into the copolymer melt. In this particular instance, the torque was not reduced. Expanding the range of the calcium-based material from 1.0 to 5.0 wt%, again showed no reduction in torque. Compression-molded pads were produced (as in example 5). An examination of the films showed that the calcium alpha olefin sulfonate was not mixed and, in fact, a large number of specks, i.e. heterogeneous regions, were observed, illustrating poor dispersion and mixing. EXAMPLE 7 Example 5 is repeated using an antioxidant stabilized metallocene catalyst synthesized plastomer, Exact ® 3033 (a 1.2 melt index, 0.900 g/cc density, ethylene butene hexene teφolymer produced by Exxon Chemical Co., Houston, Texas, USA). Two concentrations (0.5 and 3.0 wt%) of the Bio Terge ® AS-90B beads are evaluated. The lower and higher concentrations produced a torque reduction of 28 and >35%, respectively. The compression-molded films were optically clear and homogeneous, indicating excellent dispersion and mixing. EXAMPLE 8 Example 7 is repeated substituting the sodium alpha olefin sulfonate with 3 0 wt% calcium alpha olefin sulfonate No torque reduction is measured The compression-molded films are heterogeneous with a large number of specks randomly distributed throughout the film, illustrating poor dispersion and mixing EXAMPLE 9 Example 5 is repeated using an antioxidant stabilized metallocene catalyst produced plastomer, Exact ® 3028 (a 1 2 melt index, 0 900 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co , Houston, Texas, USA Three concentrations (0 5, 1 0 and 3 0 wt%) of the Bio Terge ® AS-90B beads are evaluated The data in Table 5 demonstrates that as the concentration is increased the torque is reduced Table 5 Sodium Alpha Olefin Sulfonate Torque Reduction (wt%) (%) 0 5 21 1 0 27 3 0 35 EXAMPLE 10 Example 5 is repeated using an antioxidant stabilized metallocene catalyst produced plastomer, Exact ® 3025 (a 1 2 melt index, 0 910 g/cc density, ethylene butene copolymer produced by Exxon Chemical Co , Houston, Texas, USA) Two concentrations (0 5 and 3 0 wt%) of the Bio Terge ® AS-90B beads are evaluated The date in Table 6 demonstrates that as the concentration is increased the torque is reduced Table 6 Sodium Alpha Olefin Sulfonate Torque Reduction (wt%) %) 0 5 25 3 0 30 EXAMPLE I I Example 5 is repeated using a physical mixture of antioxidant stabilized metallocene catalyst produced plastomers. In this example, the Exact ® 4049 copolymer and Exact ® 3033 teφolymer are melt mixed in a 93:8 wt ratio and subsequently, 0.5 wt% of the Bio Terge ® AS-90B beads were added. A 12% torque reduction is measured. EXAMPLE 12 Example 5 procedure is repeated using Exact ® 4049 and Exact ® 3033 materials with a wide range of fluorocarbon-based materials (Fluorad Fluorochemical Surfactants produced by 3M, St. Paul, MN, USA). All materials used were free of solvent(s) using conventional drying procedures prior to melt mixing. The data in Table 7 describes the products used in this example as well as their chemical structures and the measured torque reductions at 193° C at a 0.5 wt% concentration. The data demonstrates that no torque reductions are observed for both the potassium and ammonium perfluoroalkyl sulfonates. However, a range of torque reductions are observed which is dependent on the specific fluorocarbon structure. Table 7 Fluorocarbon-Based Materials 3M Product Type Description Torque Reduction- Torque Reduction- Number Exact ® 4049 (%) Exact ® 3033 (%) FC-93 Anionic Ammonium perfluoroalkyl 0 0 sulfonates FC-95 and Anionic Potassium perfluoroalkyl 0 0 FC-98 sulfonates. 0 0 FC-99 Anionic Amine perfluoroalkyl 35 35 sulfonates FC-100 Amphoteric Fluorinated alkyl 6 6 amphoteric mixture FC-120 Anionic Ammonium perfluoroalkyl 0 25 sulfonates FC-129 Anionic Potassium fluorinated alkyl 7 7 carboxylates FC-135 Cationic Fluorinated alkyl 17 58 quaternary ammonium iodides FC-143 Anionic Ammonium perfluoralkyl 17 34 carboxylates FC-431 Nonionic Fluorinated alkyl esters 37 30 FC-740 Nonionic Fluorinated alkyl esters 12 8 EXAMPLE 13 Example 5 procedure is repeated using sodium and calcium dodecylbenzene sulfonate materials. The former material is a product of the Witco Coφ., Houston, Texas, USA and the latter material is a product of Stepan Co., Northfield, Illinois, USA. The data in Table 8 shows that the calcium-based material provides no reduction in the torque, while the sodium-based material provides only a relatively modest reduction (or no enhancement). Table 8 Dodecyl benzene Sulfonate Product Concentration Torque Reduction Designation (%) (%) Sodium Witconate 90 3.0 11 Sodium Witconate LX 3.0 6 Sodium Witconate SK 3.0 0 Calcium Experimental 1.0 0 Product Calcium Experimental 3.0 0 Product Calcium Experimental 5.0 0 Product

Claims: CLAIMS We Claim: 1. A method for processing a linear polyethylene comprising: a) selecting a linear polyethylene from the group consisting of LLDPE, m-LLDPE, HDPE, plastomers, MDPE, UHMW-HDPE and combinations thereof; b) selecting a surfactant, said surfactant is a non-aromatic alkyl sulfonate or sulfate salt, wherein a cation of said salt is selected from the group consisting of Na, K, Li, and a quaternary ammonium, wherein said alkyl group is a Cβ-C 30 alkyl group, wherein said surfactant alkyl group is selected from the group consiting of branched or straight chain alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl, and combinations thereof c) placing an amount of said surfactant into said polyethylene sufficient to reduce melt fracture; and d) melt processing said polyethylene and said surfactant to form an article. 2. The method of claim 1 wherein said linear polyethylene is selected from the group consisting of copolymers of ethylene and at least one α-olefin selected from the group consisting of 1-butene, 1-pentene, 4-methyl- 1- pentene, 1-hexene, 1-octene, 1 -decene, and combinations thereof, preferably wherein said linear polyethylene has a density in the range of from 0.86 - 0.94 g/cc, more preferably from 0.88 - 0.930 g/cc. 3. The method of any of the previous claims wherein said surfactant is present up to 5 wt %, based on the total weight of said polyethylene and said surfactant, wherein said article is a film, optionally containing at least a second polymer selected from the group consisting of LDPE, EVA, EEA, EnBA, EMAA, EMA, EAA and ionomers of the acids, and combinations thereof. 4. The method of any of the preceeding claims wherein said article is a blown film substantially free of melt fracture said linear polyethylene is selected from the group consisting of ethylene 1-butene, ethylene 4-methyl- 1- pentene, ethylene 1-pentene, ethylene 1-hexene, and ethylene 1-octene and combinations thereof; wherein said surfactant is a sodium alkyl sulfate or sulfonate, wherein said alkyl group is a C 6 - C 30 alkyl group, wherein said alkyl group is selected from the group consisting of branched or straight chain alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl, and combinations thereof, and wherein said surfactant is present in said blown film up to 0.5 weight percent based on the total weight of said polyethylene, preferably wherein said surfactant is a sodium α-olefin sulfonate, wherein said α-olefin has 12 to 18 carbon atoms, and said surfactant is present in said blown film up to 0.35 weight percent. 5. The method of any of the preceeding claims wherein said polyethylene has a M w /M n not exceeding 2.5, said alkyl group has 8-24 carbon atoms and said sulfonate or sulfate is present in said polyethylene in the range of 0.01 - 0.5 weight percent based on the total weight of said polyethylene. 6. The method of claim 1 wherein said surfactant is represented by the general formula: where x = 3 or 4 M] is selected from the group consisting of: Li, Na, K, and other alkali cations, and M] optionally includes NH4 + or quaternary ammonium salts of the structure: R ] is selected from the group consisting of: branched or straight chain mono or di unsaturated alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl, and combinations thereof; and R 2 , R 3 , R are selected from the group consisting of: branched or straight chain alkyl, branched or straight chain alkenyl, branched or straight chain alkoxy, wherein said R 2 , R 3 , and R4 may optionally contain hydroxyl groups; and wherein the carbon number of said Ri, ranges from 6 to 30; and wherein the carbon number of said R 2 , R 3 , Rt ranges from 2 to 8; wherein said surfactant is present in said combination in a range of 0.005 - 5.0 weight percent, based on the total weight of the combination. 7. The method of claim 1 wherein said surfactant is represented by the formula: where x = 3 or 4 Mi is selected from the group consisting of: Li, Na, K, and other cations. Mj optionally includes NH4 + or quaternary ammonium salts of the structure, R j is selected from the group consisting of: branched or straight chain mono or di unsaturated alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl, and combinations thereof; and R 2 , R 3 , R 4 are selected from the group consisting of: branched or straight chain alkyl, branched or straight chain alkenyl, branched or straight chain alkoxy, wherein said R 2 , R 3 , and R_ι may optionally contain hydroxyl groups; and wherein the carbon number of said Ri, ranges from 6 to 30; and wherein the carbon number of said R 2 , R 3 , R» ranges from 2 to 8; wherein said surfactant is present in said combination in a range of 0.005 to 5.0 weight percent. 8. The method of any of claims 1-5 wherein said surfactant is selected from the group consisting of alpha-olefin sulfonates of alkali-metals, wherein said alpha-olefin group has a carbon number greater than 6, preferably wherein said surfactant is sodium alkenyl sulfonate combined with a sodium hydroxyl alkane sulfonate. 9. The method of any claims 1-8 wherein said surfactants have a melting point below 240° C, preferably below 230° C, more preferably below 220° C. 10. The use of any of the methods of any of claims 1, 2, 3, 5, 6, 7, 8 or 9 to form a film or blow molded article. 11. A method for processing a linear polyethylene during blown film extrusion in the substantial absence of polypropylene homopolymers or copolymers, comprising: a) selecting a linear polyethylene from the group consisting of LLDPE, m-LLDPE, HDPE, plastomers, MDPE, UHMW-HDPE and combinations thereof wherein said linear polyolefin has a M w /M n less than 3; b) selecting a surfactant, said surfactant having a melting point not exceeding the processing temperature of said linear polyethylene by more than 30° C, and surfactant is an alkyl sulfonate or sulfate salt, the cation of said salt is selected from the group consisting of Na, K, Li and a quaternary ammonium, wherein said alkyl group is a Cβ- C 3 o alkyl group, wherein said alkyl group is selected from the group consisting of branched or straight alkenyl, branched or straight chain alkoxy, branched or straight chain hydroxyl substituted alkyl, and combinations thereof, and wherein said surfactant is present in said polyolefin up to 5.0 wt. % based on the total weight of said polyethylene and said surfactant being substantially free of halogens; c) placing an amount of said surfactant into said polyethylene sufficient to reduce melt fracture; and d) melt processing said polyethylene and said surfactant to form an article.

Inventors: CHLUDZINSKI JAMES J, ERDERLY THOMAS CRAIG, PEIFFER DENNIS G, SCHMIEG JOEL E, CHLUDZINSKI, JAMES, J., ERDERLY, THOMAS, CRAIG, PEIFFER, DENNIS, G., SCHMIEG, JOEL, E.
Applicants: EXXON CHEMICAL PATENTS INC, EXXON CHEMICAL PATENTS INC.
Application year: 1997
Main classification: C08K5
IPC codes: B29C55, B29K23, B29L7, C08J5, C08K5, C08L23, C08L101