EXTRUDABLE FILM-FORMING COMPOSITIONS OF ZIEGLER-NATTA CATALYZED OLEFIN POLYMERS INCLUDING ANTI-GEL AND ANTI-BLOCK COMPONENTS

Abstract: A non-volatile, anti-gel compound having a chain of at least about 5 repeat units of an alkylene oxide and which is sol­ uble in olefin polymers, and an inorganic anti-block agent hav­ ing a substantially neutral pH are added to a film grade Ziegler-­ Natta catalyzed olefin polymer composition to prevent: (1) gel streaking/pinstriping during film extrusion processes; (2) blocking of the extruded film; and (3) discoloration of the ex­ truded film upon aging. The anti-gel compound has a molecu­ lar weight between about 200 and about 4,000,000 Daltons. A masterbatch concentrate and extrusion method and al­ so disclosed.

Description: EXTRUDABLE FILM-FORMING COMPOSITIONS OF ZIEGLER-NATTA CATALYZED OLEFIN POLYMERS INCLUDING ANTI-GEL AND ANTI-BLOCK COMPONENTS This invention relates to anti-gel and anti-block componants useful for reducing optical degradation phenomena and discoloration in extruded film. Olefin polymers such as polyethylene have been used for a number of years for the preparation of films by extrusion processes. Unlike high pressure, free radical polymerized polyethylenes, lov pressure, low density poly ethylene a prepared in the presence of Ziegler-Natta catalysts frequently develop gel-like defect: when extruded, e.g., when extruded'as blown films. In a blown film process, polyethylene pellets or granules are melted and extruded from an annular die to form a film envelope. In the extruder and die system, there are typically "dead spots" or "hangup areas" where molten polyethylene does not love rapidly, resulting in long heat histories for portions of the melt. As portion of the polymer are flushed from these hangup areas, they cause optical degradation phenomena in the film, known as "pinatriping" and "gel streaking". By "pinstriping" is meant haze bands resulting from accumulations of micro-gels which are aligned in the machine direction during the film forming process. By "gel-streaking" is meant surface roughness in the form of the inclusion, either singularly or in rovs, of "v-shaped" gels ("arrowheads" or "chevrons"). streaks of soft gels, or, in extreme cases, film texture completely permeated by soft gels. Such optical degradation phenomena. not only detract from film optical and mechanical strength properties, but also can cause severe problems vith respect to maintaining bubble geoMetry during the film forming process. Because of the fact that the extrusion processes usually involve the use of relatively high extrusion temperatures and prolonged extrusion times, in commercial practice, various anti-oxidants. such as hindered phenollcs, are admixed with the olefin polymer, to prevent undesirable degradation of the polymer during the preparation of the film. When such anti oxidants are used, however, with the film forming grades of olefin polymers in certain types of extrusion equipment, the anti oxidants appear to pronounce, if not create gel-streaking and pinstriping in the products thus formed. Blocking of olefin polymer films is a well known pheno mena By.blocking is meant the tendency of films or sheets to stick or adhere to each other or to other surfaces whenever adhe sion is undesirable. Various anti-block agents are commonly incorporated into film forming polymers or applied to film surfaces to reduce blocking. For example, stearamide, stearoguan 1 amine, metal salts of fatty acids such as calcium stearate; sodium dioctylsulfosuccinate; finely divided silica or calcium carbonate; alkylamines and alkyl quaternary ammonium conpounds 1 are anti-block agents which have been incorporated into the film forming polymer before extrusion. Many solutions have been proposed to eliminate gel streaking and pinstriping. Por example, it is known to physically remove the chloride catalyst residue, prior to axersion, 5 leaching the reaction product of polymer and chloride catalyst residue with alcohols1 aqueous acid, water, or treating the polymer and catalyst with propylene oxide followed by an alcohol or witter wash and the like. Such treatments usually produce white polymers initially, but a yellow or tan colon returns when the polymers are subjected to molding andlor heating operations. In order to avoid this undesirable color formation, it is usually necessary to use a second or even a third clo-n-up procedure requiring the use of large quantities of deactivating materials Another practice in the art involves drying the after-treated polymer prior to fabrication. Because they usually must be repeated several times in order to obtain a polymer having acceptable color upon exposure to heat, such cleanup procedures are both expensive and time consuming Illustrative of such prior art treatments are those disclosed. in U.S. patents 3,925,i41; 3,962,199; 3,247,351; 4,029,877; 4,117,219; 3,299,027; 3,923,760; 3,308,105; and 4,d98,990. Other treatments disclosed in the prior art involve the addition of compounds to the polymer prior to fabrication in order to complex with the harmful components in the chloride catalyst residue and deactivate them. Illustrative of these prior art treatments are those disclosed in Canadian patent 961,998, U.S. patent 4,013,622 and in U.S. patent 3,773,743 U.S. patent 3,773,743 discloses a method for improving the stability and color of olefin polymers by deactivating their Ziegler-Natta chloride catalyst residues. This method involves high temperature (190iC-2504C) processing with hydroxyl compounds (R20 and primary alcohols) and with an organic base such as an alkyl amine; aryl amine; Li, Ca and Zn salts of carboxylic acids; trialkyl phosphites; and metal alkoxides. The concentration disclosed for the hydroxy source is the range of 0.5 to 1.5 weight percent and a concentration of 50 to 2500 parts per million (ppm) is disclosed for the organic base. At the processing temperatures disclosed, some of the organic bases and the hydroxy sources would be volatile and cause forming of the product if the processing were not done in a way to remove volatiles, e.g., as in devol-tilizing extruders Canadian patent 961,998 and U.S. patent 4,013,622 disclose the addition of polyalkylene glycol having a molecular weight between 100 and 20,000 to film grade olefin polymers to prevent gel streaking during film extrusion processes. In commercial practice, however, it has been found that extruded film made according to Canadian patent 961,998 subsequently discolors in a few weeks even at ambient temperatures i.e., it turns a yellowish color which is, of course, undesirable. The primary cause for discoloration in extruded films or molded articles is generally recognized as related to the presence of hindered phenolic anti-oxidants. Discoloration generally is believed to result from the reaction or breakdown products of such anti-oxidants. Exposure of these anti-oxidant stabilized compositions to air pollution in the form of oxides of nitrogen can promote discoloration. Thermal abuse in processing, especially in the presence of prodegradants, can lead to the build-up of chromophoric quinoid structures from break-down of the hindered phenolic anti-oxidants. Prodegradants can be additives used to control surface slip or release properties, anti-static. properties, and gel streaking tendencies. For example* prodegradants act to provide hydroperoxides to accelerate auto-oxidation. Polyethylene glycols used to control gel streaking and unsaturated fatty amides used for slip control can act with thermal abuse as prodegradants. Trace metals from inorganic snti-blocks or fillers can act as reduction-oxidation catalysts to accelerate hydroperoxide decomposition. especially at low temperatures where the peroxide decomposition is the rate limiting step. At uch low temperature, normally volatile, anti-oxidant reaction or break-down products can accumulate, promoting discoloration. Moreover. inorganic additives or fillers such as finely divided silica with iron conta;ination can interact with the hindered phenolic anti-oxidant to form chronophoric, phenolate species. The The present invention seeks to provide an extrudable, film forming composition comprising a Ziegler-Natta catalyzed olefin polymer and an extruded film made from such extrudable composition, which film is free from gel streaking and pinstriping. The present invention also seeks to provide a process wherein a film forming composition containing a Ziegler-Natta catalyzed olefin polymer may be extruded without optical degradation phenomenon appearing within the extruded film or film discoloration occurring subsequently. The present invention further seeks to provide an anti-gel and an inorganic anti-block compound which, when added to a Ziegler-Natta catalyzed olefin polymer, is useful in removing or reacting with the chloride catalyst residue in the olefin polymer to prevent gel streaking or pinstriping from occurring in a subsequent extrusion process, as well as preventing discoloration from occurring upon aging of the extruded film. The present invention additionally seeks to provide an improved process for extruding tubular olefin polymer film. The present invention still further seeks to provide masterbatch concentrate which can be admixed'with a Ziegler-Natta composition of this invention. This invention is based on the discovery that an optical degradation phenomenon, known as gel streaking and pinstriping, present in extruded Ziegler-Natta catalyzed olefin polymer, can be substantially prevented through the addition of small amounts of an anti-gel compound of low volatility. In addition, when extrusion is also carried out in the presence of an inorganic anti-block compound having a substantially neutral pE, i.e., between about 6 and about 8, film sticking or tackiness is prevented without leading to discoloration of the film upon raging. The anti-gel compound is characterized by having a chain of at least about 5 repeat units of an alkylene oxide and by having a molecular weight between 200 and 4,000,000 Daltons. According to the present invention, the incidence of gel streaking or pinstriping in the film during the extrusion of a Ziegler-Natta catalyzed olefin polymer and discoloration of the extruded film upon aging are both minimized through the use of a composition comprising a majority of a Ziegler-Natta catalyzed olefin polymer; and a @ minor amount of at least one hindered phenolic anti-oxidant, an inorganic anti-block compound and an anti-gel compound as defined herein. This invention also relates to an improved method of extruding a Ziegler-Natta catalyzed olefin polymer which comprises extruding a film forming composition containing a Ziegler-Natta catalyzed olefin polymer and minor amounts of at least one hindered phenolic anti-oxidant, an inorgamicanti-block compound and an anti-gel compound as defined herein. Mor@over, this invention relates to a masterbatch concentrate which may be admixed with a Ziegler-Natta catalyzed olefin polymer to yield the film forming composition of this invention. In one aspect, the present invention relates to an extrudable film forming composition which, when extruded, forms film essentially devoid of gel streaking and pinstriping and which does not discolor upon aging at 60*C for 4 weeks. The film forming composition is comprised of at least one olefin polymer containing a chloride catalyst residue, at least one hindered phenolic anti-oxidant, an inorganic antiblock compound having a substantially neutral pE, and an anti-gel compound characterized by having at least about 5 repeat units of an alkylene oxide. The anti-gel compound is present in a concentration sufficient to neutralize the chloride catalyst residue in the composition. The concentra tion of anti-gel compound is at least about 0.8 times the concen tration of the anti-oxidant. The residues of Ziegler-Natta catalysts include trace amounts of magnesium, titanium, aluminum and chlorine. By chloride residues, as used herein, is meant the chlorides of magnesium, titanium and aluminum present in a Ziegler-Natta catalyst residue. Chloride catalyst residue concentrations between about 5 and about 50 ppm are typical for ethylene polymers and chloride catalyst residue concentrations between about 10 and about 500 ppm are typical for propylene polymers and butene polymer made with Zlegltr-Natta catalysts. Anti-oxidants in a concentration of 20 to 500 ppm are typically added to ethylene polymer compositions. According to the present invention, the anti-gel compound is present in a concentration of 25 to 10,000 ppm for polyethylene resin composi- tions. And concentrations of 200 to 5000 ppm of anti-oxidant are typically added to propylene polymer or butenc polymer composi- tions. Concentrations of anti-gel compound of 200 to 10,000 are added to propylene polymer or butene polymer composition. Inorganic anti-block compounds in a concentration of 500 to 5: by weight are typically added to olefin polymer compositions. In another aspect, the present invention' relates to a process for extruding a film forming olefin polymer based composition into film. The film is essentially free-from gel streaking and pinstriping and does not discolor upon aging at 60aC for 4 weeks. Prior art polymer based compositions comprised a Ziegler-Natta catalyzed film grade olefin polymer which contained at least one anti-oxidant having a concentration between about 20 and about 5000 ppm. and an inorganic anti-block compound having a concentration between about 500 ppm and about 571 by weight. The prior art inorganic anti-block typically had a pH above about 8. The aforementioned prior art polymer based compositions were susceptible to gel streaking and pinstriping during formation of the film. It also has been discovered that when inorganic anti-block compounds having a pH belov 6 or above 8 were present in the aforementioned prior art compositions, film that was formed discolored after aging a few weeks at 600C or months at ambient temperature. In still another aspect, the present invention relates to a masterbatch concentrate which, when admixed with a Ziegler-Natta catalyzed olefin polymer in pro4 portions defined herein, provides a film forming composition capable of being extruded into a film which is essentially free from gel streaking and pinstriping and which does not discolor upon aging at 60*C for 4 weeks. This invention is based upon the discovery that such prior art compositions and prior art extrusion processes may be improved by extruding a Ziegler-Natta catalyzed olefin polymer based composition into film in the presence of a hindered phenolic anti-oxidant, an anti-block compound having a substantially neutral pH, and an anti-gel compound characterized by containing at least about 5 repeat units of an alkylene oxide. Preferably, the anti-gel compound is characterized by having more than about 10 repeat units of an alkylene oxide. The anti-gel compound typically is present in a concentration between about 25 and 10,000 ppm, based upon the weight of the polymer and has a molecular weight between about 200 and 4,000,000 Daltons. The hindered phenolic anti-oxidant, inorganic antiblock compound and anti-gel compound are uniformly dispersed in the olefin polymer based extrudable composition. The dispersion can be effected by various dispersion techniques commonly employed by those skilled in the art of preparing extrudable composition. The three aforementioned additives could be directly introduced into the olefin polymer (e.g., polyethylene) via a V-type blender or by mixing via a Henschel type intensive mixer. The three aforementioned additives also could be directly hot compounded into the olefin polymer or made into a masterbatch for final letdown using conventional hot processing equipment such as a Banbury mixer, a Werner Pfleiderer twin screw mixing extruder or a single screw mixer extruder that has pell@tization equipment on the head of the extruder. The Anti-G@l Compound The anti-gel compound of this invention may be represented by the following structural formula: R-(A-R1)n' wherein R R is a hydroxyl group; a C1-C24 alkyl alcohol; a C1-C12 alkylated phenol; a C12-C24 alkyl or alkylene amine; or a C12-C24 alkyl or alkylene amide; In is 1 or 2; R1 is a hydrogen atom or lower alkyl; EMI10.1 wherein R2 is ethylene, propylene or mixtures thereof; x is a number between about 5 and less than about 20,000; and y is a number between about 2 and about 6; and R1 is as defined hereinabove. Thase anti-gel compounds are of lov volatility and have a molecular weight in the range of about 200 to about 4,000,000 Daltons, preferably in the range of about 800 to about 200,000 Daltons. Below a molecular weight of about 200 Daltons, volatility is high and causes smoking and equipment plate-out problems. Above a molecular weight of about 4,000,000 Daltons and depending upon the molecular weight of the polymer, poor dispersion of the anti-gel compound may occur causing gellike defects to result in the film. IF Suitable ant4-gel compounds according to the present invention include: ' low molecular weight oligomers up to high molecular weight polymers such as polyethylene and polypropylene glycols and interpolymers thereof having a molecular weight greater than about 200 and less than about 20,000 Daltons, and polyethylene and polypropylene oxides and interpolyters thereof having a molecular weight greater than about 20,000 and less than about 4,000,000 Daltons; ; the reaction product of an alkanol with more than about 5 moles of an alkylene oxide such as ethylene or Pro@ylene beside adducts of lauryl alcohol, mystearyl alcohol, palmityl alcohol, stearyl alcohol, arachidyl alcohol, behenyl alcohol, oleyl alcohol and erucyl alcohol, and mixtures thereof; and the reaction product of an alkyl phenol such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, un- decyl, or dodecyl phenol vith more than about 5 moles of an alkylen oxide such as ethylene or propylene oxide, and mixtures thereof. Other anti-gel compounds considered suitable according to the present invention include the reaction product of a C12-C24 alkyl amine or amide 11such as lauryl, mistearyl, palmytyl, stearyl, arachidyl, and behenyl amine or amide, respectively, with more than about 5 moles of an alkylene oxide such as ethylene or propylene oxide, and mixtures thereof; the reaction product of a C12-C24 alkylene amine or amide such as oleyl and erucyl amine or amide with more than about 5 moles of an alkylene oxide- such as ethylene or propylene oxide, and mixtures thereof; and the reaction product of polyols or monoalkyl substitute polyols such as glycerol, manaltol, or sorbitol with more than about 5 moles of an alkylene oxide such as ethylene oxide or propylene oxide, and mixtures thereof. Olefin Polymers The extrudable olefin polymers employed in the extrudable compositions of the present invention are normally solids materials, that is, solid at room temperature. Any extrusion grade olefin polymer can be used in the compositions of the present invention. The term "olefin polymer thus includes ho@opolymers of the olefins, as well as interpolymers of one or more olefins with each other, andlor up to about 30 weight percent of one or more monomers which are vith such olefins. The olefins such as ethylene, propylene, butene-l, isobutylene, pentene-l, 4-methyl-pentene-l, hexene-1, octene-1, nonene-l, decane-l, as vell as interpolymers of one or more of such olefins and one or more other monomers which are interpolymerizable with such olefins, such as other vinyl and diene compounds, i.e., those having the group -C-C-. Preferred copolymers are the ethylene copolymers such as ethyleneipropylene copolymers, ethylenelbutene-l copolymers, ethyleneipentene-l copolymers, ethylenel4-methyl-pentene-l copolymers, ethylenelhexene-l copolymers, othyleneloctene-l copolymers, and the like. Preferred ethylene interpolymers would include two or more of the following: propylene, butene-1, pentene-l, hexene-l, 4-methyl-pentene-l and octene-l. Preferred propylene interpolymers would include ethylene, butene-l, pentene hexene-l, 4-methyl-pentene-l and octene-l as monomers. Preferred butene-l interpolymers would include ethylene, propylene, hexene-l 4-methyl-pentane-L and octane-i as monomers. Also included in the term polymer are blends of one polymer with one or more other polymers. Illustrative of such blends are ethylene polymers vith one or more of the foilowing: polypropylene, high pressure low density polyethylene, high density polyethylene, polybutene-l, and polar monomer containing olefin copolymers such as ethylene/acrylic acid copolymers, ethylene/methyl acrylate copolymer, methylene/ ethylacrylate copolymer, ethylene/vinyl acetate copolymer, ethylene/acrylic acid/ethyl acrylate terpolymer, ethylene/ acrylic c-id/vinyl acetate terpolymer, end the like. I Also included within the term polar monomer containing olefin copolymers are the metallic salts of those olefin copolymers, or blends thereof, which contain free carboxylic acid groups. Illustrative of such polymers are ethylene/acrylic acid copolymer, ethylene/methacrylic acid copolymer, propylene/acrylic acid copolymer, butene/acrylic acid copolymer, an oxidized olefin polymer, and the like. Illustrative of the metals which can be used to provide the salts of said carboxylic acid polymers are the one, two and three valence metals, such as sodium, lithium, potassium, calcium, magnesium, aluminum, barium, zinc, zirconium, beryllium, iron, nickel, cobalt, and the like. The preferred olefin polymers for use in the present invention are polymers of ethylene, and the most preferred polymers are those having a melt index of about 0.1 to 10 deci grams per 10 minutes, a density of about 0.910 to 0.955 gm/cc. Low density ethylene polymer has a density of between approrimatel 0.910 and 0.925 gm/cc, medium density ethylene polymer has a density of between approximately 0.925 and 0.940 gm/cc, and high density ethylene polymer has a density of between approximately 0.940 and 0.970 gm/cc. Thus, the low density ethylene polymers a are the most preferred olefin polymers to be used in the present invention, although the medium and high density polymers also may be used. Preferred low pressure, lov density ethylene copolymers for use in the present invention include those which may be pro duced in accordance with the procedures set forth in U.S. Patent Application Serial No. 892,325, filed March 31, 1975, and refilled as Serial No. 014,414 on February 27, 1979, in the names of F.J. Karol et al. and entitled "Preparation of Ethylene Copolymers in Fluid Bed Reactor", and the procedures set forth in U.S. Patent Application Serial No. 892,322, filed March 31, 1978, and refilled as Serial No. 012,720 on February 16, 1979, in the names of G.L. Goeke ct al. and entitled "Impregnated Polymerization Catalyst, Process for Preparing, and Use for Ethylene Copolymerization" as well as procedures which will produce ethylene hydrocarbon copolymers with properties as heretofore described. U.S. Application Serial No. 014,414 corresponds to European Patent Application No. 79100953.3 which was opened to the public on October 17, 1979 as Publication No. 4645 and U.S. Application Serial No. 012,720 corresponds to European Patent Application No. 79100958.2 which vas opened to the public on October 17, 1979 as Publication No 4647. The disclosures of Publications Nos. 4645 and 4647 are incorporated herein by reference. Other low pressure, low density ethylene hydrocarbon polymers preferred for use in the present invention are those which may be prepared as described in U.S. Patent 4,011,382, entitled "Preparation of Low and Medium Density Ethylene Polymer in Fluid Bed Reactor" by I.J. Levine at-al., the disclosure of which is incorporated herein by reference. The olefin polymers may be used in the form of powders. pellets, granule$, or any other form that can be fed to an extruder. The Anti-Oxidants As noted above, the extrudable compositions of the present invention contain at least one anti-oxidant for the olefin polymer. These anti-oxidants are present in atabilizingly effective quantities. Such anounts are about 0.002 to 0.5, and preferably about 0.01 to 0.05, percent by weight, based on the weight of the olefin-polymer. The anti-oxidant stabilizers which may be employed in the conpositions of the present invention include all those polyolefin anti-oxidants commonly employed in olefin polymer based film extrusion compositions. These material are such as are capable of providing anti-oxidant protection at processing temperatures of the order of about 135 C to about 3400C or higher. Such anti-oxidant stabilizers include hindered phenols, such as p-hydroxyphenylcyclohexane; di-p-hydroxyphenylcyclohexane dicresylolpropane; tertiary butyl para cresol; 2,6-di-tertbutyl-p-cresol; 2,4,6-tri-tert-butylphenol; octadcyl-3-(3',5# di-tert-butyl-4'-hydroxyphenol)propionate; tetra bia(methylene 3 (3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate@methane; 1,3,5-trimethyl-2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl benzene; tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanate; 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6 dimethyl benzyl)-1,3,5triazine-2,4,6-(lH,3H,5H)-trione; and bis-[3,3-bis-4'-hydroxy-3'tert-butyl-phenyl)-butanoic acidi-glycol ester; condensation products of dialkylphenols with formaldehyde; reaction products of phenol with styrene, z @,l'-methylene-bis(4-hydroxy-3,5-tert-butyl- phenol), 2,2'-methylene-bis-(4-methyl-6-tert-butylphenol), 2,6 (2-t@rt-butyl-4-methyl-6-methylphe@ol)-p-cresol, phenylethylpyrocatechol, phenolisopropylpyrocatechol, 1,1,3-tris(2'-methyl3'-t-butyl-4-hydroxy phenol)butane, 2,2-methylene-bis[6-(@)- methylcyclohexyl)-4-methylphenol], 1,3,5-trimethyl-2,4,6-tris (3',5'-di-t-butyl-4-hydroxybenzyl)benzene and #-napthol; and sulfur containing compounds such as 2,2'-thio-bi@-(4-methyl-6- tert-butylphenol), 4,4-thio-bis(3-methyl-6-tert-butylphenyl), distearyl thiodipropionate and dilauryl thiodipropionate; and phosphite compounds such as tri(mixed mono and dinonyl pbenyl)phosphites; phosphite esters of lauryl and stearyl alcohol; di-stearyl-pentaerythritol-diphosphite; bis(2,4-di-tert-butyl phenyl)pentaerythritol diphosphite; and tri-2,4-di-tert-butyl phenyl phosphate ester The preferred primary or hindered phenolic anti oxidant stabilizers which arc employed in the compositions of the present invention are 2,6-ditertiary-butyl-paracresol, or butylated hydroxy toluene (BHT); octadecyl-3-(3,5-di-tert-butyl4-hydroxy phenyl)propionate (Irganox 1076); tetra-bis[methylene 3-(3' *5'ditert-butyl-4'-hydroxyphenyl)propionateimethane (Irganox 1010); 2,2' ethylene bis(4,6-di-tert-butylphcnol) (Isonox 129); or 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (Cyanox 1790). The preferred secondary' stabilizers include dilauryl thiodipropionate (DLTDP); distearyl thiodiproptionate (DSTDP); tri(mixed mono and dinonyl phenyl)phosphite (Polygard); di-stearyl-pentaerythritol- diphosphite (Weston 618); tri(2,4-di-tert-butylphenyl)phosphite (Hark 2112); bis(2,4-di-tert-butylphenyl)pentaerythritol diphos phite (Weston XP-1532); or tri(nonylphenol)phosphite (Veston 399, TNPP). The hindered phenolic anti-oxidants may be used indivi dually or in various combinations with one another or the econdary stabilizers in the compositions of the present invention. Inorganic Anti-Block Compounds The extrudable compositions of the present invention contain a finaly-dividet, inorganic material for use as an anti-block or release reagent. It has been found that certain finely divided inorganic compounds of a substantially neutral pH do not promote discoloration between the hindered phenolic anti-oxidants and the polyalkylene glycol or oxide or polyalkoxyla ed compounds used to control gel streaking and pinstriping. The anti-block compounds are present in quantities that effect anti-block/release properties Such anounts are about 0.02 to about 5Z, and preferably about 0.08 to about 1X by veight, based on the weight of the film forming composition. The pH of the inorganic anti-block is between about 6 and about 8, preferably as close to a neutral pH of 7 as possible. The average particle site of the anti-block compounds of this invention are from about 0.5 to about 10 microns ( m), preferably from about ?. to about 7 microns ( m) in diameter The average surface area of the inorganic anti-block compounds of this invention are from about 1 to about 500 m2/g. Suitable anti-block compounds according to the present !invention are finely divided diatomaceous earth fluxed with sodium phosphate (White Floss); finely divided diatomaceous earth fluxed with sodium carbonate (Super Floss) which has been eutralized with an acid wash such as dilute phosphoric acid; finely divided calcium carbonate; synthesized and naturally occurring amorphous finely divided silica (Sylolt 72, 385, 266 jad Imsil A-15); talcs; and the like. Ii Masterbatch Concentrate As previously described herein, the hindered phenolic anti-oxidant, inorganic anti-block compound and anti-gel compound of this invention nag be admixed with a Ziegler-Natta catalyzed olefin polymer via a masterbatch concentrat to yield the extrudable film forming composition of this invention. The Ziegler-Natta cataly:ed olefin polymer typically is admixed with the masterbatch concentrate in a letdown ratio of between about 5 and about 100 to 1 by weight. Preferably, a letdown ratio of between about -5 and about 30 to 1 by weight Is employed. The masterbatch concentrate is comprised of between about 40Z and about 98Z by weight, preferably between about 60% and about 95Z by weight, of an olefin polymer compatible with the Ziegler-Natta catalyzed olefin polymer vith which the masterbatch concentrate is admixed. Compatibility of the olefin polymers can be judged by the general quality of the extruded film product in terms of the increased presence of haze, gel-iike defects or gross distortions of the surface texture, commonly referred to as an "applesauce" or "sharkskin-like" surface. The masterbatch concentr:te further includes between about 0,1Z and about 5Z by weight of a hindered phenolic anti oxidant; between about 0.1: and about 5Z by weight of the anti-gel compound of this invention; and between about 2X and about 48:, by weight, preferably between--about 3Z and about 20Z by weight, of an inorganic anti-block compound of this invention having a substantially neutral pi. Extrudable Compositions The extrudable compositions of the present invention may be used in any of -the forms of such compositions which are - commonly employed in the extruded film arts, such as compounds modified with various slip agents such as fatty acid asides and anti-static additives for specific end use applications. These extrudable compositions are thermoplastic in nature. In addition to the olefin polymer, anti-gel compound, hindered phenolic anti-oxidant1 near neutral pH inorganic, anti-block compound* the compositions of the present invention may contain other adjutant materials which are commonly employed in olefia polymer-based extrudable film compositions. Such other adjutants would include plasticizers, fillers, pigments, lubricants, slip agents, modifiers and similar materials. The fillers which may be used in the olefin polymerbased extrudable compositions of the present invention are the fillers which are commonly used with such polymer.. The fillers are used in amounts which correspond to about 1 to 20 percent by weight, based on the weight of the olefin polymer Such fillers would include materials such as carbon black, titanium dioxide, clays, calcium silicates and others known in the art. The plasticizers which may be employer in the olefin polymer-based extrudable compositions of the present invention are the plasticizers which are commonly used with such polymers. The plasticizers are used in amounts which would correspond to about 1 to 25 percent by weight based on the weight of olefin olymer. Such plasticizers would include materials such as phthalates, phosphates, adipates, azelates, amine based polyols, and a number of other similar products. Process lubricants which are commonly employed in the olefin polymer-based extrudable compositions are the lubricants which are commonly used with such polymers. The lubricants are used in amounts which correspond to about 0.02 to 2 percent by weight of lubricant agent based on the weight of the olefin polymer. Examples of such lubricants are ethylene bis stearamide; zinc, ealciun and/or m@gnesium steerates; hydrocarbon vases; and the like. Estrudlnz Conditions The extrudable conditions of the present invention are particularly designed for use in equipment utilized for tubular: film, Cast film and extrusion coating products. Such equipment may have hold-up areas or areas of stagnation that retard the flow of extrudate therethrough, leads to the development of gel streaking and pinstriping in the presence of hindered phenolic anti-oxidants and in the absence of the use of the anti-gel additives of the present invention. In such equipment, the olefin polymer based extrudable compositions are subjected to extrusion temperatures of about 135iC to about 340 C, and preferably about 190-C to about 340 C, under varying conditions of heat and pressure, and for periods of time of about 0.5 to 10 minutes. The film is usually prepared in sheets which are about 2.5 jim to 250 pm-mils thick. According to the present invention, the olefin polymer compositions are not exposed to post-reactor high tempera ture compounding or finishing which could introduce hydroperoxides into the composition prior to film extrusion. Instead the three aforementioned additives are admixed via a masterbatch concentrate or by directly dry blending the anti-gel and anti oxidant compounds into tbe granular blefin polymer with the anti-block compound separately admixed prior to extrusion of the composition. Another advantage of this invention is that gas treatment (e.g., with propylene oxide) after polymerization of the olefin polymer is not required nor are subsequent alcohol washes required to remove the propylene oxide or ethylene oxide gas products nor the subsequent drying process to remove the 1alcohol. Also unnecessary is the need for devolatilization of 1alcohols or water which could be added to neutralize and break down catalyst residue. The following examples are illustrative of the present invention and are not intended as a limitation of the scope thereof. Example l Preparation of Polymer Resins Two low pressure, lov density ethylene-butene-l copolymers were prepared according to the procedure disclosed in South African Patent Publication No. 79-01365, published September 22, 1980, entitled "Process for Making Film Prom Low Density Ethylene Rydrocarbon Copolymer" by W.A. Fraser et al. The properties of the ethylene butene-l copolymer were determined by the following methods: Density was determined according to ASTM D-1501. A plaque vas conditioned fo one hour at 100 C to approach equilibrium crystallinity. Density is reported as gms/cm Melt Index (MI) was determined according to ASTM D-1238, Condition E. It was measured at 190 C and 303kPa and reported as grams/lQ minutes. Flow Index (HLMI) was measured according to ASTM D-1238, Condition F. It vas measured at 10 times the weight used in the melt index test above and reported as grams per 10 minutes. Melt Flow Ratio (MFR) was calculated as Flow Index Melt Index. Ti, Mg, Al and Si catalyst residues in the ethylene1butene-l copolymer in ppm was measured by induction coupled plasma emission spectro@copy. Cl cataLyst residue in the ethylene-butene-l copolymer in ppm was measured by a Dohrmann micro-coulometric titration system. One of the ethylane-butene-l copolymers, designated A, had the following properties: a melt index of 1.0; a MFR of 28; a density of 0.918 gmlcm3; and a catalyst residue in ppm of Ti-2, Mg-2, A1-73, Si-56 and C1-13. The other ethylene-butane-i copolymer, designated B, had the following' properties: a melt index of 2.0; a MFR of 28; a density of 0.918 gm/cm3; and a catalyst residue in ppm of Ti-3, Mg-4, A1-89, Si-97 and Cl-16. Either polymer A or B was used in the polymer compositions of all the subsequent examples herein. Preparation of Polymer Compositions One of two methods to prepare polymer compositions vas employed in the examples. In one method, the components ere dry blended in a roll drum for 20 minutes at room temperature with a virgin olefin polymer. In the other method, the components were compounded into masterbatch concentrates utilizing r Banbury batch mixer coupled to a Barrel Birmingham single screw extruder malt pump. The components were mixed in the Banbury mixer for 4 to 5 minutes, dropped at 125 C, and extruded through an extruder melt pump using a throat temperature of 104-C, o barrel temperature of 1500C and a die temperature of 150 C. Each masterbatch concentrate was admixed with a high pres@ure, low density ethylene polymer having a melt index of 2.0 and a density of 0.918 gm/cm3 (commercially available under the trade name DED 4140 from, Union Carbide Corporation, Old Ridgebury Road, Danbury, Connecticut 06810). This high pressure, low density polyethylene is designated as Polymer C in Table 1. Ten masterbatch concentrates were prepared and their compositions are set forth in Table I below TABLE I |Masterbatch z Concentration Concentrate No. Comoosition (Weight Z) Polymer C 87.0 Octadecyl 3-(3',5'-di-tert- 0.4 butyl-4'-hydroxyphenyl)propionate Polyethylene glycol (molecular 1.0 weight of 4000) Finely divided diatomaceous 10.0 earth fluxed vith sodium carbonate, having an average particle size of about 6 jim and a pH of about 10 Erucamide 1.6 2 Polymer C 87.0 Octadecyl 3-(3',5'-di-tert- 0.4 butyl-4'-hydroxyphenyl)propionate Polyethylene glycol (molecular 1.0 weight of 4000) Synthetic amorphous finely 10.0 divided silica having a particle size of about 4 jim and a pH of about 6.5 Erucamide 1.6 3 Polymer C 86.6 Octadecyl 3-(3',5'-di-tert- 0.4 butyl-4'-hydroxyphenyl)propionate Di-stearyl-pentaerythritol- 0.4 diphosphite Polyethylene glycol (molecular 1.0 weight of 4000) Finely divided diatomaceous 10.0 earth fluxed with sodium carbonate, having an average particle size of about 6 m and a a pH of about.10 Erucamide 1.6 TABLE 1 (cont'd) Masterbatch Concentration concentrate No composition (Weight %) 4 Polymer C 87.0 Octadecyl 3-(3',5'-di-tert-butyl- 0.4 4'-hydroxyphenyl)propionate Polyethylene glycol (molecular 1.0 weight of 4000) Finely divided diatomaceous 10.0 earth fluxed with sodium phosphate, having an average particle size of about 5 m and a pE of about 7 Erucamide 1.6 5 5 Polymer C 87.0 @c@a@ecy@ @-(@,@-@@-ter@-bty@- 0.4 4'-hydroxyphenyl)propionate a Polyethylene glycol (nolecular 1.0 I weight of 4000) Finely divided calcium carbonate 10.0 having an average particle size of about 3.2 m, and having a p@ of about 8 Erucamide l 6 Polymer C 82.77 Tetra-blstmethylene 3-3',5'-di- 0.4 tert-butyl-4'-hydroxyphenyl) propionatejmethane Polyethylene oxide having a 1.0 molecular weight of 600,000 Finely divided diatomaceous 13.33 earth fluxed vith sodium carbonate, having an average particle size of about 6 m and a pH of about 10 Erucamide 2.5 7 Polymer C 81.97. Tetr@-bis[methylene 3-3'5'-di- 0.4 tert-butyl-4'-hydroxyphenyl) propionatejmethaae Tri-nonyl-phenyl phosphite ester 0.8 Polyethylene oxide having a 1.0 mo@ecu@ar we@gn@ or @00,000 TABLE I (cont'd) Masterbatch Concentration @@@@@@@@@@@ @@ @@@@@@i@ion (Weight Z) Concentrate No. Composition (Weight Z) 7 7 Finely divided diatomaceous 13.33 (cont'd) earth fluxed with sodium carbonate, having an aver@ge particle size of about 6 m and a pH of about 10 Erucamide 2.5 8 Polymer C 98.6 Tetra-bis[methylene 3-3',5'-di- 0.4 tert-butyl-4'-hydroxyphenyl) propionate)methane Polyethylene oxide having a 1.0 molecular weight of 600,000 Polymer C 84.049 Octadecyl 3-(3' ,5'-di-tert-butyl- 0.025 4 '-hydroxyphenyl)propionate Tri-no@yl-phenyl phoaphite ester 0.1 - Finely divided diatomaceous earth 13.33 fluxed with sodium carbonate, having an average particle size of about 6 pn and a pH of about 10 Erucamide 2.5 10 Polymer C 82.77 Tetra-bistmethylene 3-3',5'-di- 0.4 tert-butyl-4'-hydroxyphenyl) propionate]methane Polyethylene oxide having a 1.0 molecular weight of 600,000 Finely divided diatomaceous 13.33 earth fluxed with sodium phosphate, having an average particle size of about 5 um and a pE of about 7 Erucamide 2.5 The measurement of pH of the various @nti-block compounds used in 9 of the masterhatch concentrates of Table I was done using the following procedure. 20 grams of the inorganic anti-block compound was placed in a 200 ml glass beaker with 100 ml of distilled water. The mixture was magnetically stirred for 30 minutes and then the anti-block compound was allowed to settle from the slurred mixture. The pH of the settled water slurry was measured using litmus paper capable of discerning pH values in the 4 to 12 range. Example 2 IA A series of 22 control experiments or runs were conducted to illustrate disadvantages associated with the use of olefin polymer based film extrusion formulations which did not contain one or more of the following the anti-gel compound or near neutral (6-8) pH anti-block compound of this invention or a hindered phenolic anti-oxidant. Films extruded from the 22 control formulations exhibited blocking or gel streaking/pinstriping or discoloration upon aging in the extruded film or a combination thereof. The 22 control formulations were prepared by one of the methods described hereinabove. After the control formulations were prepared, films were extruded in a tubular extrusion device for various periods of tine to assess gel formation/pinstriping. The extruded films were aged at 60 C for 4 weeks to assess discoloration Por runs 1, 3 and 6-15, the following extrusion conditions were employed: Film was extruded at 3 lbs/hr with a 385 F melt temperature using a 1-inch Killion 24 to 1 length to diameter extruder equipped with a 1 1/4-inch die with a 0.30 inch gap. No nitrogen purge was used on the extrusion hopper. For runs 2 and 16-22, the following extrusion conditions were employed: Film was extruded on a 2 1/2-inch diameter 24 to 1 length to diameter Egan extruder equipped with a 6-inch diameter Sano die having a 100 ml die gap. The extrusion rate was about 85 lbs/hr :1 with a melt temperature of about 290 F. The extruded films were approximately 1.5 mils thick. During extrusion, the films were examined periodically for gel streak formation and pinstriping. After aging for 4 weeks at 60 C, the films also were examined for discoloration. Table II hereinbelow sets forth the resin control compositions employed and the results obtained with respect to gel streak formation/pinstriping/discoloration. The number symbols used to designate the visual appearance of the film with respect to gel streaking/pinstriping/discoloration have the following meanings: : 0 - clear of gel streaking/pinstriping/discoloration 1 - slight gel streaking/pinstriping/discoloration 2 - moderate gel streaking/pinstriping/discoloration 3 3 - severe gel streaking/pinstriping/discoloration As can be seen from a review of the information disclosed in Table It, runs 1 and 2 were made with additive-free polymer control compositions, which exhibited slight gel streaking pinstriping and did not discolor upon aging at 600C for 4 weeks. The additive-free polymer control compositions of runs 1 and 2 do not have long term storage stability or reprocessing stability and lack adequate handling characteristics such as anti-block or non-tack properties. Runs 3-5 were made with hindered phenolics anti oxidant stabilized polymer control formulations which exhibited severe gel streaking/pinstriping, but no discoloration in the extruded film upon aging at 600C for 4 weeks. Runs 6-15 were made with polymer control formulations containing a hindered phenolic anti-oxidant, various anti-gel compounds, e.g., polyethylene glycols/oxides on an ethoxylated linear alcohol. These polymer control compositions exhibited no gel streaking/pinstriping and slightly di@colored upon aging at 60 C for 5 weeks. The control formulations for runs 6-15 lack adequate handling characteristics such as anti-block or non-tack properties. Runs 16-22 were made vith polymer control formulations containing a hindered phenolic anti-oxidant, various anti-gel compounds, e.g., polyethylene glycol or polyethylene oxide, and an inorganic anti-block compound having a pa of about 11. These polymer control formulations did not exhibit gel streaking pinstriping but became highly discolored after aging 4 weeks at 60 C. Induced blocking of the films (@ample conditioned for 24 hours at 60 C under a 1.0 kPa load) produced with the control formulations used in runs 1-22 was measured. For runs 1-15, which did not contain an anti-block compound, induced blocking values were found to be greater than 200 grams force to separate tuo film layers. For runs 16-22, which contained between 2.5% and 8Z by weight anti-block compound, induced blocking values were found to be less than about 50 grams force to separate two film layers. Induced blocking values belou about 50 grams force to separate two film layers are commercially acceptable. TABLE II Additive Concentration Gel Streaking Pinstriping Discolor@tion Run No. Formulation (%) Rating Rating Rating 1 Polymer A 0 1 0 0 2 Polymer B 0 1 0 0 3 Polymer A Octadecyl 3-(3',5'-di-tert- 0.02 3 3 0 butyl-4'-hydroxyphenyl) propionate 4 Polymer B Octadecyl 3-(3',5'-di-tart- 0.02 3 3 0 butyl-4'-hydroxyphenyl) propionate 5 Polymer B Tetra-bis[methylene 3-(3',5'- 0.02 3 3 0 di-tert-butyl-4'-hydroxyphenyl) propionate]methane 6 Polymer A Tetra-bis[methylene 3-(3',5'- 0.02 0 0 0 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Polyethylene glycol (molecular 0.05 weight of 200) 7 Polymer A Tetra-bis[methylene 3-(3',5'- 0.02 0 0 0 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Polyethylene glycol (molecular 0.05 weight of 4000) TA@LE II (cont'd) Additive Concentration Gel Streaking Pinstriping Discoloration Run No. Formulation (%) Rating Rating Rating 8 POlymer A Tetra-bi$[methylene 3-(3',5'- 0.02 0 0 1 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Polyethylene oxide (molecular 0.05 weight of 10,000) 9 Polymer A Tetra-bis[methylene 3-(3',5'- 0.02 0 0 1 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Polyethylene oxide (molecular 0.05 weight of 100,000) 10 Polymer A Tetra-bis[methylene 3-(3',5'-. 0.02 0 0 1 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Polyethylene oxide (molecular 0.05 weight of 600,000) 11 Polymer A Tetra-bis[methylene 3-(3',5'- 0.02 1 0 1 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Polyethylene oxide (molecul@r 0.05 weight of 4,000,000) 12 Polymer A Tetra-bis[methylene 3-(3',5'di-tert-butyl-4'-hydroxyphenyl) propionate]methane; ; Reaction product of nonyl phenol 0 0 1 with 14 moles ethylene oxide TABLE II (cont'd) Additive Concentr@tion Gel Str@@king Pinstriping Discoloration Run No. Formulation (%) R@ting R@ting R@ting 13 Polymer A Tetra-bi@[methylene 3-(3',5'- 0.02 0 0 1 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Reaction product of nonyl phenol 0.05 with 40 moles ethylene oxide 14 Polymer A Tetra-bis[methylene 3-(3',5'- 0.02 0 0 1 di-tert-butyl-4'-hydroxyphenyl) propionate]methane; Reaction product of lauryl alcohol 0.05 with 40 moles ethylene oxide 15 Polymer A Tetra-bi@[methylene 3-(3',5'- 0.02 1 2 1 di-tert-butyl-4'-hydroxyphenyl) propion@te]methane; Reaction product of lauryl alcohol 0.05 with 8 mol@s ethylene oxide 16 Polymer B Masterbatch Concentrate No. I 5.0 0 0 3 17 Polymer B Masterbatch Concentrate No. 3 5.0 0 0 3 18 Polymer B Masterbatch Concentrate No. 1 2.5 0 0 2 19 POlymer A Masterbatch Concentrate No. 6 8.0 0 0 3 20 Polymer A Masterbatch Concentrate No. 6 5.0 0 0 3 TABLE II (cont'd) Additive Concentr@tion Gel Strenking Pinstriping Discoloration Run No. Formulation (%) Rating Rating Rating 21 Polymer A Masterbatch Concentr@te No. 7 5.0 0 0 3 22 Polymer A Masterbatch Concentr@te No. 8 2.5 0 0 3 Masterbatch Concentr@te No. 9 2.5 Example 3 Example 2 was repeated using a polymer formulation according to the present invention. A series of 5 experiments jof the use of the anti-gel and anti-block compounds of this linvention in olefin polymer based film extrusion formulations. Films extruded from the 5 formulations were essentially free from the formation of gel straaks/pinstriping/discoloration in the extruded film upon aging. The formulations were prepared by tone of the methods described hereinabove. After the formulations were pr@pared, films were extruded under the same extrusion condition@ described hereinabove for runs 2 and 16-22. Table III hereinbelow sets forth the polymer formulations employed and the results obtained with respect to gel streak formation/pinstriping/discoloration. As can be seen from a review of the inform@tion disclosed in Table III, runs 23 @nd 26 were made with polymer B and masterbatch concentrates 2, 4 or 5. Films extruded from llthese formulations were essentially free from gel streaking, 'pinstriping and discoloration upon aging. Ii Run 27 was made with polymer A and masterbatch |concentrate 10 Film extruded from this formulation was essentially free from gel streaking, pinstriping and discoloration upon aging. Induced blocking of the films produced with the formulations used in runs 23-27 was measured as previously described herein. For runs 23-27, which contained between 2.5% and 5S by weight near neutral pH anti-block compound of this invention, induced blocking values were found to be less than about 50 grams force to separate two film layers. TABLE III Additive Concentration Gel Streaking Pinstriping Discoloration Run No. Formulation (%) Reting Reting Reting 23 Polymer B Masterbatch Concentrate No. 2 5.0 0 0 1 24 Polymer B Masterbatch Concentrate No. 4 5.0 0 0 0 25 Polymer B Masterbatch Concentrate No. 5 5.0 0 0 0 26 Polymer B Masterbatch Concentrate No. 4 2.5 0 0 0 27 Polymer A Masterbatch Concentrate No. 10 5.0 0 0 0

Claims: CLAIMS: 1. An extrudable film-forming composition which when extruded forms a film which is essentially devoid of gel streaking and pinstriping and which does not discolor upon aging at 600C for 4 weeks, the filmforming composition being comprised of a Ziegler-Natta catalyzed olefin polymer containing a chloride catalyst residue in a concentration between 5 and 500 ppm, at least one hindered phenolic anti-oxidant, at least one inorganic anti-block compound and at least one anti-gel compound, the hindered phenolic anti-oxidant being present in a concentration between 20 and 5000 ppm, the inorganic anti-block compound being present in a concentration between 500 ppm and 5% by weight and having a substantially neutral pH, the anti-gel compound characterized by having at least about 5 repeat units of an.alkylene oxide and being present in a concentration sufficient to neutralize the chloride catalyst residue, the concentration of the anti-gel compound being at least about 0.8 times the concentration of the hindered phenolic anti-oxidant, and the anti-gel compound having a molecular weight between 200 and 4,000,000 Daltons. 2. A composition as claimed in claim 1 wherein the anti-gel compound is represented by the following structural formula: R-(A-R1)n' wherein n is 1 or 2; R is a hydroxy group; a C1-C24 alkyl alcohol; a C1-C12 alkylated phenol; a C12-C24 alkyl or alkylene amine; or a C12-C24 alkyl or alkylene amide; R1 is a hydrogen atom or lower alkyl; EMI36.1 y, wherein R2 is ethylene, propylene or mixtures thereof; x is a number between 5 and 20,000; as a number between 2 and 6; and R1 is as defined herein. 3. A composition as claimed in claim 2 wherein the anti-gel compound comprises: a polyalkylene glycol having a molecular weight between 200 and 20,000 Daltons or a polyalkylene oxide having a molecular weight between 20,000 and 4,000,000 Daltons. 4. A composition as- claimed in claim 2 wherein the anti-gel compound comprises: the reaction product of either an alkanol or an alkyl phenol with more than about 5 moles of an alkylene. oxide. 5. A composition as claimed in claim 3 wherein the polyalkylene glycol is polyethylene glycol. 6. A composition as claimed in claim 2 wherein the polyalkylene oxide is polyethylene oxide, polypropylene oxide or an interpolymer thereof. 7. A composition as claimed in claim 4 wherein the anti-gel compound is an ethylene or propylene oxide adduct of a lauryl alcohol, mystearyl alcohol, behenyl alcohol, oleyl alcohol or erucyl alcohol, or an adduct of mixtures of the oxides and the alcohols. 8. A composition as claimed in claim 4 wherein the alkyl phenol is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, or dodecyl phenol or mixtures thereof, and the alkylene oxide is ethylene oxide, propylene oxide or mixtures thereof. 9. A composition as claimed in claim 2 wherein the anti-gel compound comprises the reaction product of either (;a) a C12-C24 alkyl or alkylene amine or amide or Cb) a polyol or monoalkyl-substituted polyol with more than about 5 moles of an alkylene oxide. 10. A composition as claimed in claim 9 wherein thg alkyl amine or amide is lauryl, mystearyl, palmytyl, stearly, arachidyl or behenyl amine or amide, respectively, and the alky-lene oxide is ethylene oxide, propylene oxide or mixtures thereof. 11. A composition as claimed in claim 9 wherein the alkylene amine or amide is oleyl or erucyl amine or amide, respectively, or mixtures thereof, and the alkylene oxide is ethylene oxide, propylene oxide or mixtures thereof. 12. A composition as claimed in claim 9 wherein the polyol is glycerol, mannitol or sorbitol and the alkylene oxide is ethylene oxide, propylene oxide or mixtures thereof. 13. A composition as claimed in any one of the preceding claims wherein the inorganic anti-block compound comprises finely divided diatomaceous earth fluxed with sodium phosphate; finely divided diatomaceous earth fluxed with sodium carbonate which has been neutralized with an acid wash; finely divided calcium carbonate; synthesized or naturally occurring amorphous finely divided silica; or a talc. 14. A composition as claimed in any one of the preceding claims wherein the pH of the anti-block compound is between 6 and 8. 15. A composition as claimed in any one of the preceding claims wherein the anti-gel compound is characterized by having at least about 10 repeat units of an alkylene oxide. 16. A composition as claimed in any one of the preceding claims wherein the olefin polymer is an ethylene polymer, the chloride catalyst residue concentration is between 5 and 50 ppm, and the concentration of the anti r C- gel compound is between 25 and 10,000 ppm. 17. A composition as claimed in any one of Claims 1 to 15 wherein the olefin polymer is a propylene polymer or a butene polymer, the chloride catalyst residue con centration is between 10 and 500 ppm, the hindered phenolic anti-aKidant concentration is between-200 and 5000 ppm, and the concentration of the anti-gel compound is between 200 and 10,000 ppm. 18. A composition as claimed in any one of the preceding claims wherein the anti-gel compound is present in an amount at least 5 times the amount of chloride catalyst residue present. 19. A composition as claimed in claim 18 wherein the anti-gel compound to chloride catalyst residue ratio is greater than 10 to 1. 20. A composition as claimed in any one of the preceding claims wherein the olefin polymer is an ethylene/ propylene copolymer, ethylene/butene-l copolymer, ethylene/pentene-l copolymer, ethylene/4-methyl-pentene- 1 copolymer, ethylene/hexene-l copolymer, or ethylene/ octene-l copolymer. 21. A composition as claimed in any one of the preceding- claims wherein the olefin polymer is- an ethylene interpolymer which includes two or more of the following monomers: propylene, butene-l, pentene-l, hexene-l, 4-methyapentene-1 and octene-l. 22. A composition as claimed in any one of the preceding claims wherein the olefin polymer is a propylene interpolymer which includes two or more of the following monomers: ethylene, butene-l, pentene-l, hexene-l, 4-methyl-pentene-l and octene-l. 23. A composition as claimed in any one of the preceding claims wherein the olefin polymer is a butene-l interpolymer which includes two or more of the following monomers: ethylene, propylene, pentene-l, hexene-l, 4-methyl-pentene-l and octene-l. 24. A composition as claimed in any one of the preceding claims further including an organic slip agent. 25. A composition as claimed in Claim 24 wherein the organic slip agent is erucamide or oleamide. 26. A masterbatch concentrate which, when admixed with a Ziegler-Natta catalyzed olefin polymer in a letdown ratio of between 5 and 100 to 1 by weight of the catalyzed olefin polymer to the masterbatch concentrate, provides a film-forming composition capable of being extruded into a film which is essentially free from gel streaking and pinstriping and which does not discolor upon aging at 600C for 4 weeks, wherein the masterbatch concentrate comprises: between 40% and 98% by weight of an olefin polymer compatible with the Ziegler Natta catalyzed olefin polymer; between 0.1% and 5% by weight of a hindered phenolic anti-oxidant; between 0.1% and 5% by weight of an anti-gel compound having at least about 5 repeat units of an alkylene oxide and also having a molecular weight between 200 and 4,000,000 Daltons; and between 2% and 48% by weight of an inorganic anti-block compound having a substantially neutral pH. 27. A concentrate as claimed in Claim 26 wherein the concentration of the olefin polymer is between 608 and 95% by weight and the concentration of the inoraanic anti-block compound is between 4% and 20% by weight. 28. A concentrate as claimed in Claim 26 or Claim 27 when characterised by any of the features of Claims 1 to 25. 29. A process for extruding a film-forming olefin polymer based composition into film which is essentially free from gel streaking and pinstriping and which does not discolor upon aging at 600C for 4 weeks, characterised in that the composition comprises an extrudable film-eorming composition as claimed in any one of Claims 1 to 25. 30. A process as claimed in Claim 29 characterised in that the extrusion temperature is at least 1350C to 3450C and that the throughput time for the olefin polymer based composition in the extruding equipment is from 0.2 to 10 minutes.

Inventors: CORWIN, MICHAEL ALLEN, FOSTER, GEORGE NORRIS
Applicants: UNION CARBIDE CORPORATION
Application year: 1982
Main classification: C08L23
IPC codes: B29C47, C08L21, C08L101, C08L33, C08J3, B29L7, C08K13, C08K5, C08L23, C08K3, C08L71, B29B7, B29K23, C08L7