Process for Eliminating Surface Melt Fracture During Extrusion of Thermoplastic Polymers

This invention relates to a process for substantially eliminating melt fracture, particularly surface melt fracture, during extrusion of thermoplastic polymers susceptible to melt fracture, under conditions of flow rate and melt temperature which would otherwise produce such melt fracture.

In a more specific aspect, the invention relates to a process for substantially eliminating surface melt fracture during extrusion of a molten narrow molecular weight distribution, linear, ethylene copolymers, under conditions of flow rate and melt temperature which would otherwise produce such melt fracture.

Most commercial low density polyethylenes are polymerized in heavy walled autoclaves or tubular reactors at pressures as high as 50,000 psi and temperatures up to 300.degree. C. The molecular structure of high pressure low density polyethylene is highly complex. The permutations in the arrangement of its simple building blocks are essentially infinite. High pressure resins are characterized by an intricate long chain branched molecular architecture. These long chain branches have a dramatic effect on the melt rheology of the resins. High pressure low density polyethylene resins also possess a spectrum of short chain branches generally 1 to 6 carbon atoms in length which control resin crystallinity (density). The frequency distribution of these short chain branches is such that, on the average, most chains possess the same average number of branches. The short chain branching distribution characterizing high pressure low density polyethylene can be considered narrow.

The term "linear" is defined as identifying a polymer chain which is predominantly free of long chain branching. By "predominantly free of long chain branching" is meant less than 0.5 branches/per 1000 carbon atoms in the polyethylene molecule. "Long chain branching" characterizes branching within polymeric structures which exceeds short branch lengths of pendant groups derived from individual alpha-olefin comonomers. A long chain branch of polyethylene should have at least a sufficient number of carbon atoms to provide significant modifications in rheological behavior, such as caused by chain entanglement. The minimum number of carbon atoms is usually greater than about 100. Short chain branching introduced through comonomer polymerization provides branch lengths of usually less than about 10 carbon atoms per branch. Noncrosslinked LLDPE possesses little, if any, long chain branching such that the only branching to speak of is short chain branching, with such branch length controlled by the pendant chain length of the comonomeric alpha-olefins provided.

The term "narrow molecular weight distribution" as used herein refers to the ratio of weight average molecular weight to number average molecular weight. This ratio can be between 1 and about 10, preferably between about 2 to about 6.5, and most preferably between about 3 to about 5. The lower limit of this ratio is defined by the theoretical limit since number average molecular weight cannot exceed weight average molecular weight by definition.

Low density polyethylene can exhibit a multitude of properties. It is flexible and has a good balance of mechanical properties such as tensile strength, impact resistance, burst strength, and tear strength. In addition, it retains its strength down to relatively low temperatures. Certain resins do not embrittle at temperatures as low as -70.degree. C. Low density polyethylene has good chemical resistance, and it is relatively inert to acids, alkalis, and inorganic solutions. It is, however, sensitive to hydrocarbons, halogenated hydrocarbons, and to oils and greases. Low density polyethylene has excellent dielectric strength.

More than 50% of all low density polyethylene is processed into film. This film is primarily utilized in packaging applications such as for meat, produce, frozen food, ice bags, boilable pouches, textile and paper products, rack merchandise, industrial liners, shipping sacks, pallet stretch and shrink wrap. Large quantities of wide heavy gauge film are used in construction and agriculture.

Most low density polyethylene film is produced by the tubular blown film extrusion process. Film products made by this process range in size, from tubes which are about two inches or less in diameter, and which are used as sleeves or pouches, to huge bubbles that provide a lay flat of up to about twenty feet in width, and which, when slit along an edge and opened up, will measure up to about forty feet in width.

Polyethylene can also be produced at low to medium pressures by homopolymerizing ethylene or copolymerizing ethylene with various alpha olefins using heterogeneous catalysts based on transition metal compounds of variable valence. These resins generally possess little, if any, long chain branching and the only branching to speak of is short chain branching. Branch length is controlled by comonomer type. Branch frequency is controlled by the concentration of comonomer(s) used during copolymerization. Branch frequency distribution is influenced by the nature of the transition metal catalyst used during the copolymerization process. The short chain branching distribution characterizing transition metal catalyzed low density polyethylene can be very broad.

Linear low density polyethylene can also be produced by high pressure techniques as is known in the prior art.

U.S. Pat. No. 4,302,566 in the names of F. J. Karol et al and entitled Preparation of Ethylene Copolymers in Fluid Bed Reactor, discloses that ethylene copolymers, having a density of 0.91 to 0.96, a melt flow ratio of greater than or equal to 22 to less than or equal to 32 and a relatively low residual catalyst content can be produced in granular form, at relatively high productivities if the monomer(s) are copolymerized in a gas phase process with a specific high activity Mg-Ti containing complex catalyst which is blended with an inert carrier material.

U.S. Pat. No. 4,302,565 in the name of G. L. Goeke et al and entitled Impregnated Polymerization Catalyst, Process for Preparing, and Use for Ethylene Copolymerization discloses that ethylene copolymers, having a density of 0.91 to 0.96, a melt flow ratio of greater than or equal to 22 to less than or equal to 32 and a relatively low residual catalyst content can be produced in granular form, at relatively high productivities, if the monomer(s) are copolymerized in a gas phase process with a specific high-activity Mg-Ti-containing complex catalyst which is impregnated in a porous inert carrier material.

The polymers as produced, for example, by the processes of said applications using the Mg-Ti containing complex catalyst possess a narrow molecular weight distribution, Mw/Mn, of about greater than or equal to 2.7 or less than or equal to 4 1.

The rheology of polymeric materials depends to a large extent on molecular weight and molecular weight distribution.

In film extrusion, two aspects of rheological behavior are important: shear and extension. Within a film extruder and extrusion die, a polymeric melt undergoes severe shearing deformation. As the extrusion screw pumps the melt to, and through, the film die, the melt experiences a wide range of shear rates. Most film extrusion processes are thought to expose the melt to shear at rates in the 100-5000 sec.sup.-1 range. Polymeric melts are known to exhibit what is commonly termed shear thinning behavior, i.e., non-Newtonian flow behavior. As shear rate is increased, viscosity (the ratio of shear stress, .tau., to shear rate, .lambda.) decreases. The degree of viscosity decrease depends upon the molecular weight, its distribution and molecular configuration, i.e. long chain branching of the polymeric material. Short chain branching has little effect on shear viscosity. In general, high pressure low density polyethylenes have a broad molecular weight distribution and show enhanced shear thinning behavior in the shear rate range common to film extrusion. The narrow molecular weight distribution resins used in the present invention exhibit reduced shear thinning behavior at extrusion grade shear rates. The consequences of these differences are that the narrow distribution resins used in the present invention require higher power and develop higher pressures during extrusion than the high pressure low density polyethylene resins of broad molecular weight distribution and of equivalent average molecular weight.

The rheology of polymeric materials is customarily studied in shear deformation. In simple shear, the velocity gradient of the deforming resin is perpendicular to the flow direction. The mode of deformation is experimentally convenient but does not convey the essential information for understanding material response in film fabrication processes. As one can define a shear viscosity in terms of shear stress and shear rate, i.e.:

where

.eta. shear=shear viscosity (poise)

.tau..sub.12 =shear stress (dynes/cm.sup.2)

.lambda.=shear rate (sec.sup.-1) an extensional viscosity can be defined in terms of normal stress and strain rate, i.e.,:

.eta. ext=.pi./.epsilon.

ext=extensionaI viscosity (poise)

.pi.=normal stress (dynes/cm.sup.2)

.epsilon.=strain rate (sec.sup.-1)

During extrusion of a high molecular weight ethylene polymer having a narrow molecular weight distribution through dies, as with other such polymeric materials, "melt fracture" occurs when the extrusion rate exceeds a certain critical value. "Melt Fracture" is a general term used by the polymer industry to describe a variety of extrudate irregularities observed during extrusion of molten polymers. The occurrence of melt fracture severely limits the rate at which acceptable products can be fabricated under commercial conditions. The occurrence of melt fracture was first described by Nason in 1945 and since then several investigators have studied this in an attempt to understand the underlying mechanism(s) for its occurrence. C. J. S. Petrie and M. M. Denn (Amer. Inst. Chem Engrs Journal, Vol. 22, pages 209-236, 1976) have presented a critical review of the literature which indicates that the present understanding of the mechanism(s) leading to melt fracture is far from complete.

The melt fracture characteristics of a molten polymer is usually studied using a capillary rheometer. The polymer at a given temperature is forced through a capillary die of known dimensions at a given flow rate. The pressure required is noted and the emerging extrudate is examined for surface characteristics.

The extrudate surface characteristics of linear low density polyethylene (LLDPE) resins, as determined with a capillary rheometer are typical of many linear narrow distribution polymers. They indicate that at low shear stresses (less than approximately 20 psi), the emerging extrudates from a capillary die are smooth and glossy. At a critical shear stress (approximately 20-22 psi), the extrudates exhibit loss of surface gloss. The loss of gloss is due to fine scale roughness of the extrudate surface which can be perceived under a microscope at a moderate magnification (20-40X). This condition represents the "onset" of surface irregularities and occurs at a critical shear stress in the die. Above the critical stress, two main types of extrudate melt fracture can be identified with LLDPE resins: surface melt fracture and gross melt fracture. The surface melt fracture occurs over a shear stress range of approximately 20-65 psi and results in increasing severity of surface roughness. In its most severe form, it appears as "sharkskin". The surface irregularities occur under apparently steady flow conditions. That is, no fluctuation in either the pressure or the flow rate is observed with time. At a shear stress of approximately 65 psi, the flow becomes unsteady when both the pressure and the flow rate fluctuate between two extremes and the emerging extrudates correspondingly exhibit smooth and rough surfaces. This is the onset of gross melt fracture and has been a subject of intense investigation by several investigators because of its severity. With further increase in shear stress, the extrudates become totally distorted and show no regularity.

Several mechanisms have been proposed in the literature for the occurrence of surface and gross melt fracture. Surface melt fracture of the sharkskin type has been proposed to be due to effects at the die exit where the viscoelastic melt is subjected to high local stresses as it parts company with the die surface. This leads to cyclic build up and release of surface tensile forces at the die exit resulting in the observed surface melt fracture. Another mechanism for surface melt fracture proposes differential recovery, due to the elasticity between the skin and core of the extrudate as a primary cause. On the other hand, gross melt fracture has been proposed to be due to die land and/or die entry effects. The proposed mechanisms include: "slip-stick" in the die land region; tearing of the melt in the die entry region due to exceeding the melt strength; and, propagation of spiralling flow instabilities in the die entry region.

Under commercial film fabrication conditions (shear stress range approximately 25-65 psi) with conventional blown film dies, predominantly surface melt fracture of the sharkskin type occurs with LLDPE resins resulting in commercially unacceptable products.

There are several methods for eliminating surface melt fracture under commercial film fabrication conditions. These are aimed at reducing the shear stresses in the die and include: increasing the melt temperature; modifying the die geometry; and use of slip additives in the resin to reduce friction at the wall. Increasing the melt temperature is not commercially useful since it lowers the rate for film formation due to bubble instabilities and heat transfer limitations. Another method for eliminating sharkskin is described in U.S. Pat. No. 3,920,782. In this method, surface melt fracture formed during extrusion of polymeric materials is controlled or eliminated by cooling an outer layer of the material, so it emerges from the die with a reduced temperature while maintaining the bulk of the melt at the optimum working temperature. However, this method is difficult to employ and control.

The invention of U.S. Pat. No. 3,920,782 is apparently based on the inventor's conclusions that the onset of surface melt fracture under his operating conditions with his resins is a function, basically, of exceeding a critical linear velocity with his resins through his dies at his operating temperatures. In the process of the present invention, however, the onset of surface melt fracture in the present applicant's resins under his operating conditions is a function, primarily of exceeding a critical shear stress.

U.S. Pat. No. 3,382,535 discloses a means for designing dies which are to be used for the high speed extrusion coating of wire and cable with plastic materials such as polypropylene, high density and low density polyethylene together with their copolymers, which are responsive, or sensitive, to the taper angles of the extrusion die. The dies of this patent are designed to avoid gross melt fracture of the extruded plastic wire coating which is encountered at significantly higher stresses than that for surface melt fracture encountered during film formation.

The invention of U.S. Pat. No. 3,382,535 resides in the designing of the taper angle of the die entry so as to provide a curvilinear die configuration (FIG. 6 and 7 of the patent) which converges in the direction of flow of the resin. This procedure however, of, in effect, decreasing the taper angle of the die, will result in an increase in the critical shear rate of the resin processed through the die. This reduces gross distortions as a function only of the angle of entry in and/or to the die. Surface melt fracture is insensitive to taper angles at the die entry and the present invention relates to reducing surface melt fracture as a function of the materials of construction of the die land region including the die exit whereby significantly higher shear rates can be obtained without encountering surface melt fracture during film fabrication.

U.S. Pat. No. 3,879,507 discloses a means of reducing melt fracture during the extrusion of foamable composition into film or sheet. This method involves increasing the length of the die land and/or slightly tapering the die gap, while retaining or decreasing the die gap, which is apparently to be relatively narrow, as compared to the prior art (see column 4, lines 2-6) and of the order of 0.025 inches or 25 mils (column 5, line 10). This kind of melt fracture is produced by premature bubble formation at the surface. This melt fracture, however, is totally different than the melt fracture experienced in processing LLDPE resins for film formation. In other words, the melt fracture is not as a result of rheological properties as discussed herein. Die modifications are designed to reduce the shear stress in the die land region to be below the critical stress level (approximately 20 psi) by either enlarging the die gap (U.S. Pat. Nos.: 4,243,619 and 4,282,177) or heating the die lip to temperatures significantly above the melt temperature. Enlarging the die gap results in thick extrudates which must be drawn down and cooled in the film blowing process. While LLDPE resins have excellent drawdown characteristics, thick extrudates increase the molecular orientation in the machine direction and results in directional imbalance and reduction in critical film properties such as tear resistance. Also, thick extrudates limit the efficiency of conventional bubble cooling systems which result in reduced rates for stable operation. The wide gap technology has other disadvantages. The required gap is a function of extrusion rate, resin melt index and melt temperature. The wide gap configuration is not suitable for processing conventional Low Density Polyethylene (HP-LDPE) resins. Thus, die gap changes are required to accommodate the flexibility expected by the fabricator with a given line.

The heated lip concept is aimed at reducing stresses at the die exit and involves extensive modifications requiring efficient insulation of the hot lips from the rest of the die and from the air ring.

Additives for use as processing aids to obtain melt fracture reduction in extrudates, are expensive and the added cost, depending on the required concentration, may be prohibitive in resins, such as granular LLDPE, intended for commodity applications. Additives influence the rheological properties of the base resin and, in excess amounts, may adversely affect critical film properties including gloss, transparency, blocking and heat sealability characteristics of the product.

More recently surface melt fracture is virtually eliminated by changes in the die land surface. Thus, U.S. Pat. No. 4,522,776, issued to A. V. Ramamurthy on June 11, 1985 eliminates melt fracture by using a die having a die land surface fabricated of a material which increases adhesion between the die land surface and the polymer.

U.S. Pat. No. 4,552,712 issued to A. V. Ramamurthy on Nov. 12, 1985 reduces melt fracture by using a die having a die land region fabricated from stainless steel and wherein the length of the die land to the width of the die gap is about 35:1 to about 60:1.

U.S. Pat. No. 4,554,120 issued to A. V. Ramamurthy on Nov. 19, 1985 substantially eliminates surface melt fracture by using a die having a die land region defining opposing surfaces at least one of which is fabricated from an alloy containing 5 to 95 parts by weight zinc and 95 to 5 parts by weight copper.

We have found that in the process of the present invention, surface melt fracture, can be virtually eliminated by extruding the narrow molecular weight distribution ethylene polymer at normal film extrusion temperatures through a die having a die land region defining opposing die exit surfaces and wherein at least one, and preferably both of the opposing die exit surfaces are coated with a composition comprising about 80% to about 95% nickel and about 5 to about 20% phosphorous to provide at least one and preferably two nickel/phosphorous coated surfaces in contact with the molten polymer.

In the case where only one surface of the opposing die land surfaces is coated with the nickel/phosphorous composition, then surface melt fracture is reduced or eliminated on the surface of the polymer adjacent to the coated surface. If both surfaces of the opposing die land are coated, then both surfaces of the polymer would have reduced melt fracture.

Films suitable for packaging applications must possess a balance of key properties for broad end-use utility and wide commercial acceptance. These properties include film optical quality, for example, haze, gloss, and see-through characteristics. Mechanical strength properties such as puncture resistance, tensile strength, impact strength, stiffness, and tear resistance are important. Vapor transmission and gas permeability characteristics are important considerations in perishable goods packaging. Performance in film converting and packaging equipment is influenced by film properties such as coefficient of friction, blocking, heat sealability and flex resistance. Low density polyethylene has a wide range of utility such as in food packaging and non-food packaging applications. Bags commonly produced from low density polyethylene include shipping sacks, textile bags, laundry and dry cleaning bags and trash bags. Low density polyethylene film can be used as drum liners for a number of liquid and solid chemicals and as protective wrap inside wooden crates. Low density polyethylene film can be used in a variety of agricultural and horticultural applications such as protecting plants and crops, as mulching, for storing of fruits and vegetables. Additionally, low density polyethylene film can be used in building applications such as a moisture or moisture vapor barrier. Further, low density polyethylene film can be coated and printed for use in newspapers, books, etc.

Possessing a unique combination of the aforedescribed properties, high pressure low density polyethylene is the most important of the thermoplastic packaging films. It accounts for about 50% of the total usage of such films in packaging. Films made from the polymers of the present invention, preferably the ethylene hydrocarbon copolymers, offer an improved combination of end use properties and are especially suited for many of the applications already served by high pressure low density polyethylene.

An improvement in any one of the properties of a film such as elimination or reduction of surface melt fracture or an improvement in the extrusion characteristics of the resin or an improvement in the film extrusion process itself is of the utmost importance regarding the acceptance of the film as a substitute for high pressure low density polyethylene in many end use applications.

In accordance with the present invention, there is provided a process for substantially eliminating surface melt fracture during extrusion of a molten narrow molecular weight distribution, linear, ethylene copolymer, under conditions of flow rate and melt temperature which would otherwise produce such surface melt fracture which comprises extruding said polymer through a die having a die land region defining opposing surfaces, and wherein at least one of said opposing surface is coated with a composition comprising about 80% to about 95% by weight of nickel and about 5% to about 20% by weight phosphorous preferably about 85% to 90% nickel and about 10% to 15% by weight phosphorous whereby melt fracture is substantially eliminated on the surface of the polymer adjacent to said coated surface.

Preferably both opposing surfaces contain the nickel phosphorous coating adjacent the polymer.

In a still broader aspect of the invention, in addition to the ethylene polymers recited herein, the practice of the present invention is also applicable to thermoplastic polymers which experience surface melt fracture during extrusion at flow rates and melt temperatures which produce such melt fracture. Examples of thermoplastic materials in which surface melt fracture can be observed include polypropylene, polystyrene, ethylene-propylene rubbers, styrene-butadiene-styrene, polyvinylchloride, polyacrylonitrile, and like polymers.

Thus, in a broader aspect the present invention provides a process for substantially eliminating surface melt fracture during extrusion of a thermoplastic polymer under conditions of flow rate and melt temperature which would otherwise produce such melt fracture which comprises extruding said thermoplastic polymer through a die having a die land region defining opposing surfaces, wherein at least one of said opposing surface is coated with a composition comprising about 80% to about 95% nickel and about 5% to about 20% phosphorous, whereby melt fracture is substantially eliminated on the surface of the polymer adjacent to said nickel/phosphorous containing surface.

In addition in a preferred operative mode, it is desirable to minimize moisture content in the resin entering the extruder. This can be accomplished by hopper dryers, or use of an inert gas such as nitrogen in the hopper or preferably at the throat of the extruder or hopper.

Advantageously, the molten ethylene polymer can be extruded through a die such as a spiral annular die, slit die, etc., preferably an annular die, having a narrow die gap up to about 50 mils and preferably about 5-40 mils. Advantageously, when processing LLDPE resins, it is no longer required to extrude the molten ethylene polymer through a die having a die gap of greater than about 50 mils to less than about 120 mils, as described in U.S. Pat. No. 4,243,619. Conventionally, die land region construction has been largely based on nickel or chrome plated steel surfaces.

The melt fracture is reduced on the surface of the polymer adjacent to the coated surface. As a result, the process can be practiced with the invention disclosed in U.S. Pat. No. 4,348,349 issued on Sept. 7, 1982. Advantageously, therefore, melt fracture can be reduced on both sides of a film by directing the molten polymer through the die land region wherein only the surface of film in which melt fracture is to be reduced or eliminated is adjacent to the coated surface and on the other surface melt fracture would also be eliminated as disclosed in the patent. Also, according to the present invention, processing of multi-layer films is also possible wherein one layer is formed of LLDPE and another layer is formed from a resin which under the conditions of operation is not subject to melt fracture. Thus, by the process of the instant invention, the LLDPE resin can be passed through the die in contact with the coated surface whereas the resin not subject to melt fracture is extruded in contact with the other die land surface thereby producing a multi layer film, both outer surfaces of which would be free of melt fracture.

The nickel/phosphorous containing composition was found to be particularly suitable when used in amounts of about 80% to 95% nickel and about 5% to about 20% phosphorous.

Preferred amounts are 85% to 90% nickel and 10% to 15% phosphorous. Superior results are obtained when the nickel/phosphorous composition contains about 88% nickel and about 12% phosphorous.

The coating can be applied by a variety of techniques such as electrolytic coating, electroless coating deposition, and like techniques well known to the art.

I. Blown Film Extrusion

The films formed as disclosed herein may be extruded by tubular blown film extrusion process. In this process a narrow molecular weight distribution polymer is melt extruded through an extruder. This extruder may have an extrusion screw therein with a length to diameter ratio of between 15:1 to 21:1, as described in U.S. Pat. No. 4,343,755 in the names of John C. Miller et al and entitled "A Process For Extruding Ethylene Polymers". This application describes that this extrusion screw contains a feed, transition and metering section. Optionally, the extrusion screw can contain a mixing section such as that described in U.S. Pat. Nos. 3,486,192; 3,730,492 and 3,756,574, which are incorporated herein by reference. Preferably, the mixing section is placed at the screw tip.

The extruder which may be used herein may have a 18:1 to 32:1 length to internal diameter barrel ratio. The extrusion screw used in the present invention may have a length to diameter ratio of 15:1 to 32:1. When, for example, an extrusion screw of a length to diameter ratio of 18:1 is used in a 24:1 extruder, the remaining space in the extrusion barrel can be partially filled with various types of plugs, torpedoes, or static mixers to reduce residence time of the polymer melt.

The extrusion screw can also be of the type described in U.S. Pat. No. 4,329,313. The molten polymer is then extruded through a die, as will hereinafter be described.

The polymer is extruded at a temperature of about 163.degree. C. to about 260.degree. C. The polymer is extruded in an upward vertical direction in the form of a tube although it can be extruded downward or even sideways. After extrusion of the molten polymer through the annular die, the tubular film is expanded to the desired extent, cooled, or allowed to cool and flattened. The tubular film is flattened by passing the film through a collapsing frame and a set of nip rolls. These nip rolls are driven, thereby providing means for withdrawing the tubular film away from the annular die.

A positive pressure of gas, for example, air or nitrogen, is maintained inside the tubular bubble. As is known in the operation of conventional film processes, the pressure of the gas is controlled to give the desired degree of expansion to the tubular film. The degree of expansion, as measured by the ratio of the fully expanded tube circumference to the circumference of the die annulus, is in the range 1:1 to 6:1 and preferably, 1:1 to 4:1. The tubular extrudate is cooled by conventional techniques such as, by air cooling, water quench or mandrel.

The drawdown characteristics of the polymers disclosed herein are excellent. Drawdown, defined as the ratio of the die gap to the product of film gauge and blow up ratio, is kept less than about 250. Very thin gauge films can be produced at high drawdown from these polymers even when said polymer is highly contaminated with foreign particles and/or gel. Thin gauge films of about 0.5 to 3.0 mils can be processed to exhibit ultimate elongations MD greater than about 400% to about 700% and TD greater than about 500% to about 700% Furthermore, these films are not perceived as "splitty". "Splittiness" is a qualitative term which describes the notched tear response of a film at high deformation rates. "Splittiness" reflects crack propagation rate. It is an end use characteristic of certain types of film and is not well understood from a fundamental perspective.

As the polymer exits the annular die, the extrudate cools and its temperature falls below its melting point and it solidifies. The optical properties of the extrudate change as crystallization occurs and a frost line is formed. The position of this frost line above the annular die is a measure of the cooling rate of the film. This cooling rate has a very marked effect on the optical properties of the film produced herein.

The ethylene polymer can also be extruded in the shape of a rod or other solid cross section using the same die geometry for only the external surface. Additionally, the ethylene polymer can also be extruded into pipe through annular dies.

II. Slot Cast Film Extrusion

The films formed as disclosed herein may also be extruded by slot cast film extrusion. This film extrusion method is well known in the art and comprises extruding a sheet of molten polymer through a slot die and then quenching the extrudate using, for example, a chilled casting roll or water bath. The die will hereinafter be described. In the chill roll process, film may be extruded horizontally and laid on top of the chill roll or it may be extruded downward and drawn under the chill roll. Extrudate cooling rates in the slot cast process are very high. Chill roll or water bath quenching is so fast that as the extrudate cools below its melting point, crystallites nucleate very rapidly, supramolecular structures have little time to grow and spherulites are held to a very small size. The optical properties of slot cast film are vastly improved over those characterizing films using the slower cooling rate, tubular blown film extrusion process. Compound temperatures in the slot cast film extrusion process generally run much higher than those typifying the tubular blown film process. Melt strength is not a process limitation in this film extrusion method. Both shear viscosity and extensional viscosity are lowered. Film can generally be extruded at higher output rates than practiced in the blown film process. The higher temperatures reduce shear stresses in the die and raise the output threshold for surface melt fracture.

The film produced by the method of the present invention has a thickness of greater than about 0.10 mils to about 20 mils, preferably greater than about 0.10 to 10 mils, most preferably greater than about 0.10 to 4.0 mils. The 0.10 to 4.0 mil film is characterized by the following properties: a puncture resistance value of greater than about 7.0 in-lbs/mil; an ultimate elongation of greater than about 400%, tensile impact strength of greater than about 500 to about 2000 ft lbs/in.sup.3 and tensile strength greater than about 2000 to about 7000 psi.

Various conventional additives such as slip agents, antiblocking agents, and antioxidants can be incorporated in the film in accordance with conventional practice.

The polymers which may be used in the process of the present invention are homopolymers of ethylene or copolymers of a major mol percent (greater than or equal to 80%) of ethylene, and a minor mol percent (less than or equal to 20%) of one or more C.sub.3 to C.sub.8 alpha olefins. The C.sub.3 to C.sub.8 alpha olefins should not contain any branching on any of their carbon atoms which is closer than the fourth carbon atom. The preferred C.sub.3 to C.sub.8 alpha olefins are propylene, butene-1, pentene-1, hexene-1, 4-methylpentene-1 and octene 1.

The ethylene polymers have a melt flow ratio of about greater than or equal to 18 to less than or equal to 50, and preferably of about greater than or equal to 22 to less than or equal to 30.

The homopolymers have a density of about greater than or equal to 0.958 to less than or equal to 0.972 and preferably of about greater than or equal to 0.961 to less than or equal to 0.968. The copolymers have a density of about greater than or equal to 0.85 to less than or equal to 0.96 and preferably greater than or equal to 0.917 to less than or equal to 0.955, and most preferably, of about greater than or equal to 0.917 to less than or equal to 0.935. The density of the copolymer, at a given melt index level for the copolymer, is primarily regulated by the amount of the C.sub.3 to C.sub.8 comonomer which is copolymerized with the ethylene. In the absence of the comonomer, the ethylene would homopolymerize with the catalyst of the present invention to provide homopolymers having a density of about greater than or equal to 0.96. Thus, the addition of progressively larger amounts of the comonomers to the copolymers results in a progressive lowering of the density of the copolymer. The amount of each of the various C.sub.3 to C.sub.8 comonomers needed to achieve the same result will vary from monomer to monomer, under the same reaction conditions.

When made in the fluid bed process, polymers of the present invention are granular materials which have a settled bulk density of about 15 to 32 pounds per cubic foot and an average particle size of the order of about 0.005 to about 0.06 inches.

For the purposes of making film in the process of the present invention, the preferred polymers are the copolymers and particularly those copolymers having a density of about greater than or equal to 0.917 to less than or equal to 0.924; and a standard melt index of greater than or equal to 0.1 to less than or equal to 5.0.

The propylene polymers which can be used in the process of the present invention, span a melt flow range (measured according to ASTM 1238 Condition L) from about 0.1 to 100g/10min. and are from among polypropylene homopolymers with an isotatic index (insoluble with reflux in heptane over a 24 hour period) greater than or equal to 85%, random copolymers with a total major molar percent of greater than or equal to 85% of propylene and a minor molar percent of less than or equal to 15% of ethylene and/or one or more of C.sub.3 to C.sub.8 alpha olefins and block (or impact copolymers) with a total major weight percent from about 70% to about 95% of propylene and a minor weight percent from about 5% to about 30% of ethylene and/or one or more of C.sub.3 to C.sub.8 alpha olefins.

The process of the present invention is also applicable to extrusion of thermoplastic resins for other than film making purposes. Thus in addition to reduction or elimination of surface melt fracture from films, the process can also be used to reduce or eliminate surface melt fracture in thin wall tubes, pipes etc. which would otherwise be susceptible to surface melt fracture under conventional surface melt fracture conditions.

The films made in the process of the present invention have a thickness of greater than 0.1 mil to less than or equal to 10 mils and preferably of greater than 0.1 mil to less than or equal to 5 mils.

Having set forth the general nature of the invention, the following examples illustrate some specific embodiments of the invention. It is to be understood, however, that this invention is not limited to the examples, since the invention may be practiced by the use of various modifications.

This Example demonstrates the conventional procedure for extruding ethylene polymers into tubes.

An ethylene-butene copolymer was prepared in accordance with the procedure of U.S. Pat. No. 4,302,566. The copolymer had a nominal density of 0.918 gm/cc, a nominal melt index of 1.0 decigrams/minute and a nominal melt flow ratio of 26. The copolymer was formed into a tube by passing the resin after removing moisture with nitrogen gas through a conventional 2 inch diameter screw extruder having a polyethylene screw as described in U.S. Pat. No. 4,329,313 with a Maddock mixing section, and thence into a conventional hard chrome plated steel die having a 0.4 inch land, 3 inch die collar diameter and a die pin diameter normally of 2.96 inches to give a 20 mil die gap. The sides of the die land were parallel with the flow axis of the polymer melt. The resin was extruded for four hours through the die at a rate of 75 lbs/hr. and at a temperature of 226.degree. C. A 1.5 mil film was fabricated at a blow up ratio of 2 and a frost line height of 12 inches employing a conventional due lip air ring. There was severe melt fracture observed on both surfaces of the tube during the entire extrusion period of four hours.

This Example demonstrates the use of nickel as a conventional coating when extruding ethylene polymers into tubes.

An ethylene butene copolymer was prepared in accordance with the procedure of U.S. Pat. No. 4,302,566. The copolymer had a nominal density of 0.918 gm/cc, a nominal melt index of 1.0 decigrams/minute and a nominal melt flow ratio of 26. The copolymer was formed into a tube by passing the resin after removing moisture with nitrogen gas through a conventional 2 inch diameter screw extruder having a polyethylene screw as described in U.S. Pat. No. 4,329,313 with a Maddock mixing section, and thence into a conventional hard nickel plated steel die having a 0.4 inch land, 3 inch die collar diameter and a die pin diameter normally of 2.96 inches to give a 20 mil die gap. The sides of the die land were parallel with the flow axis of the polymer melt. The resin was extruded for four hours through the die at a rate of 75 lbs/hr. and at a temperature of 226.degree. C. A 1.5 mil film was fabricated at a blow up ratio of 2 and a frost line height of 12 inches employing a conventional dual lip air ring. There was severe melt fracture initially during extrusion with decreasing severity as time of extrusion continued. At the end of four hours the melt fracture was moderate on both sides of the film and lower than that of Example 1.

This Example demonstrates the nickel/phosphorous coating of the present invention for extruding ethylene polymers into tubes.

An ethylene butene copolymer was prepared in accordance with the procedure of U.S. Pat. No. 4,302,566. The copolymer had a nominal density of 0.918 gm/cc, a nominal melt index of 1.0 decigrams/minute and a nominal melt flow ratio of 26. The copolymer was formed into a tube by passing the resin after removing moisture with nitrogen gas through a conventional 2 inch diameter screw extruder having a polyethylene screw as described in U.S. Pat. No. 4,329,313 with a Maddock mixing section, and thence into die having the pin and collar coated with a nickel/phosphorous coating containing 88% nickel and 12% phosphorous having a 0.4 inch land, 3 inch die collar diameter and a die pin diameter normally of 2.96 inches to give a 20 mil die gap. The sides of the die land were parallel with the flow axis of the polymer melt. The resin was extruded for four hours through the die at a rate of 75 lbs/hr. and at a temperature of 226.degree. C. A 1.5 mil film was fabricated at a blow up ratio of 2 and a frost line height of 12 inches employing a conventional dual lip air ring. There was initially severe melt fracture observed which rapidly decreased after less than about 1/2 hour after which there was no observable melt fracture of either side of the film for the remaining period of extrusion of about four hours.