VINYL HALIDE POLYMER BARRIER PACKAGING COMPOSITIONS

Abstract: Vinyl halide polymer compositions exhibiting reduced gas permeability are described which comprise a mixture of: (a) at least one vinyl halide polymer; (b) from about 1 to about 40 % by weight, based on the weight of the vinyl halide polymer (a), of an ethylene-vinyl alcohol copolymer containing from about 15 to about 55 mole percent of ethylene; and (c) at least one carbonyl-containing polymer wherein the carbonyl group is selected from the group consisting of: -C(O)-, -C(O)O-, -N-C(O)-, and -N-C(O)O-. The compositions of the present invention can be thermoformed into a wide variety of useful articles such as films, sheets and hollow articles which are characterized as having good impact strength and mechanical integrity.

Description: Title: VINYL HALIDE POLYMER BARRIER PACKAGING COMPOSI¬ TIONS Field of the Invention This invention relates to vinyl halide polymer compositions modified with ethylene-vinyl alcohol poly¬ mers, and more particularly, to vinyl halide polymer compositions modified with vinyl alcohol polymers and a carbonyl-containing polymer composition. The polymer compositions have good impact strength and exhibit reduced gas permeability. The invention also relates to films, sheets and hollow articles fabricated from the vinyl halide compositions. Background of the Invention Polyvinyl chloride (PVC) compositions are commonly used as packaging materials for cosmetics, phar¬ maceuticals, foods and health care products. Polyvinyl chloride is preferentially selected for these packaging applications due to its low cost, clarity and ease of processing. In some packaging applications it is very desirable that plastic materials exhibit a very high gas impermeability. The gas barrier properties of PVC compo¬ sitions are adequate for some applications but require improvement for the protection of extremely oxygen-sensi¬ tive materials. The gas barrier properties of PVC may be improved by chemical or physical modification, or by the addition of a filler or a protective coating. A prefer- red approach to improving the gas barrier properties of PVC is by blending with barrier materials. Blends in general do not always have the additive properties of the two components. The properties of the blend in some instances are worse than the properties of the pure components. Therefore, blending a barrier polymer with PVC polymers does not necessarily lead to a composite with improved gas impermeability relative to PVC. Packaging materials based on copolymers of ethylene and vinyl alcohol (EVOH) are excellent barriers to oxygen at low relative humidity, but are rather poor barriers at higher humidity conditions. One method for overcoming this problem is to blend the EVOH copolymer with a polymer that is primarily hydrophobic such as polyvinyl chloride. U.S. Patent 4,003,963 describes vinyl chloride polymer barrier packaging compositions which are blends of vinyl chloride polymers containing no carboxyl groups and about 20 to 30% by weight of an ethylene-vinyl alco¬ hol copolymer containing greater than 50 mole percent of vinyl alcohol. The compositions are reported to have enhanced resistance to gas permeability and moisture vapor transmission. The addition of ethylene-vinyl alcohol copoly¬ mers to polyvinyl chloride can produce a transparent compound with a permeability to oxygen that is lower than a polyvinyl chloride itself. These compounds, however, suffer from very poor mechanical properties. Adhesion is generally very low at the PVC/EVOH inter¬ face, and fracture is initiated at this site. Thus, polymer blends such as PVC/EVOH often do not have or exhibit the desired degree of mechanical integrity. Summary of the Invention Vinyl halide polymer compositions exhibiting reduced gas permeability are described which comprise a mixture of (A) at least one vinyl halide polymer; (B) from about 1 to about 40% by weight, based on the weight of the vinyl halide polymer (A), of an ethylene-vinyl alcohol copolymer containing from about 15 to about 55 mole percent of ethylene; and (C) at least one carbonyl-containing polymer wherein the carbonyl group is selected from the group consisting of -C(0)-, -C(0)0-, -N-C(O)-, and -N-C(0)0- The compositions of the present invention can be thermo¬ formed into a wide variety of useful articles such as films, sheets and hollow articles which are character¬ ized as having good impact strength and mechanical integrity. Description of the Preferred Embodiments (A) The Vinyl Halide Polymers. The vinyl halide polymers which are utilized in preparation of the improved polymer compositions of the present invention include the homopolymers and copoly- mers of vinyl halides including, for example, vinyl chloride and vinyl bromide. The vinyl halides may be copolymerized with each other or each of them may be copolymerized with one or more polymerizable olefinic monomers having at least one terminal CH2=C< grouping. As examples of such olefinic monomers, there may be mentioned the alpha, beta-olefinically unsaturated car- boxylic acids such as acrylic acid, methacrylic acid, ethacrylic acid, alpha-cyanoacrylic acid, etc.; esters of acrylic acid such as methylacrylate, ethylacrylate, butylacrylate, octylacrylate, cyanoethylacrylate, etc.; esters of methacrylic acid such as methylmethacrylate, butylmethacrylate, etc.; nitrile such as acrylonitrile, methacrylonitrile, etc.; acrylamides such as me hylacryl- amide, N-meth lol acrylamide, N-butoxy methylacrylamide, etc.; vinyl ethers such as ethyl vinyl ether, chloroeth- yl vinyl ether, etc.; the vinyl ketones; styrene and styrene derivatives such as methyl styrene, vinyl tol¬ uene, chlorostyrene, etc.; vinyl naphthalene; esters such as allyl " or vinyl chloroacetate, vinyl acetate, etc.; vinyl pyridene; methyl vinyl ketone; the diole- fins, including butadiene, isoprene, chloroprene, etc.; and other polymerizable olefinic monomers of the types known to those skilled in the art. The vinyl halide polymers particularly useful in the present invention as component (A) are homopoly- mers and copolymers made by the polymerization of vinyl chloride alone or in admixture with one or more polymer¬ izable olefinic monomers copolymerizable therewith in amounts up to about 20% by weight based on the weight of the monomer mixtures. The most preferred vinyl polymer, or resin, is polyvinylchloride (PVC) homopolymer pro¬ duced by mass polymerization or suspension polymeriza¬ tion. In order to simplify the discussion and to mini¬ mize the examples used to illustrate the invention, the invention generally will hereinafter be described in connection with PVC, it being understood that this is merely intended to be illustrative and not limiting. The preparation of vinyl halide polymers, and particularly, polyvinylchloride polymers including homopolymers and copolymers, is well known in the art. Examples of patents describing polyvinyl halides and the preparation of polyvinyl halides include U.S. Patents 4,751,118, 4,748,218 and 4,728,677. Vinyl halide poly¬ mers and copolymers, and in particular polyvinylchloride homopolymers and copolymers are available commercially such as, from the B.F. Goodrich Company, Akron, Ohio under the general trade designation Geon. (B) The Ethylene-Vinyl Alcohol Copolymers (EVOH). Ethylene-vinyl alcohol copolymers (EVOH) suit¬ able for use in this invention will generally contain from about 15% to about 55 mole percent of ethylene and from about 45 to about 85 mole percent of vinyl alcohol. The preferred copolymers will contain from about 20 to about 50 mole percent of ethylene. Since these copoly¬ mers generally are prepared by the hydrolysis of ethyl¬ ene-vinyl acetate copolymers, some residual vinyl ace¬ tate may be present in the copolymers. Generally, there will be less than about 3% by weight of residual vinyl acetate in the EVOH copolymers. The EVOH copolymers typically have molecular weights in the range of from about 10,000 to about 40,000 corresponding roughly to melt indicies of about 0.5 to about 15 or higher, and more generally from about 0.5 to about 6.0 as determined by ASTM Test D-1238 Procedure E or L using a weight of 2160 grams and a temperature of 190°C. Typically, the EVOH copolymers will have densities of about 1.1 to 1.2, and the melting points of from about 150 to about 200°C or higher. Ethylene-vinyl alcohol copolymers useful in this invention are commercially available from the EVAL Co pany of America under "SC" designations. Examples of EVOH copolymers available from this company are identi¬ fied in the following Table I. * Melt index at 190°C/2160 gm., gm/10 min, A series of EVOH copolymers is also available from DuPont with about the same range of ethylene content under the general trade designation "Selar". The amount of EVOH incorporated into the vinyl halide polymer compositions of the present invention may vary over a wide range although amounts are from about 1 to about 40% by weight, based on the weight of the vinyl halide polymer generally is found to provide desirable results. In another embodiment, from about 5 to about 40% by weight of the EVOH copolymer is included in the compositions of the present invention. (C) Carbonyl Containing Polymers. The vinyl halide polymer compositions which comprise at least one vinyl halide polymer (A) and at least EVOH copolymer <B) as described above, also con¬ tain at least one carbonyl-containing polymer wherein at least one carbonyl group is selected from the group consisting of -C(0)-, -C(0)0-, -N-C(O)-, and -N-C(0)0- Examples of polymers containing these groups are polyke- tones, polyesters, polyamides, polyurethanes and graft copolymers such as described below. The incorporation of the carbonyl-containing polymers (C) into the vinyl halide polymer compositions of the present invention results in an improvement in mechanical integrity of the composite and an improvement in impact properties. One particular advantageous result obtained by including the carbonyl-containing polymers (C) in the composition is that the tendency of some compositions comprising a mixture of the vinyl halide polymer (A) and the EVOH copolymers (B) to delaminate is significantly reduced. In general, the carbonyl-containing copolymer (C) should be melt processable within a temperature range in which the polyvinyl chloride is typically processed. Generally, such temperatures range from about 160°C to about 225°C. The amount of the carbonyl- containing polymer (C) included in the vinyl chloride compositions of the present invention may vary over a wide range and generally, the vinyl halide compositions may contain from about 1% to about 20% by weight of the carbonyl-containing polymer, based on the weight of the vinyl chloride polymer present in the composition. Generally amounts of from about 2% to about 15% are sufficient to provide the desired results. (C-1 ) The carbonyl containing polymer compositions utilized in the present invention may be graft or block copolymers of polyvinyl chloride with an ethylene-alkyl acrylate copolymer. The alkyl acrylate reacted with the ethylene to form the copolymer may be represented by the formula CH 2 =C(R)C(0)OR 1 (I) wherein R is hydrogen or a methyl or ethyl group and R- j is an alkyl group containing from 1 to about 8 carbon atoms. Generally R is hydrogen and R^ contains from 1 to 4 carbon atoms. A preferred alkyl acrylate is ethyl acrylate. The ethylene-alkyl acrylate copolymers include copolymers comprising about 60 to about 97% by weight of ethylene and from about 3 to about 40% by weight of one or more alkyl acrylates as defined by Formula I. The copolymer can be prepared from ethylene and an acrylic acid followed by esterification of the acid group. Copolymers of ethylene and ethylacrylate are available commercially from Union-Carbide Company under designa¬ tions such as DPD 6169. The graft or block polymers of polyvinyl chloride with the ethylene-ethylacrylate copolymer are readily prepared by polymerizing a mixture of a vinyl halide monomer such as vinyl chloride monomer and an ethylene-alkylacrylate copolymer in the presence of an initiator such as a peroxide in water. The weight ratio of the polyvinyl halide to ethylene-alkyl acrylate copolymer may range from about 75:25 to about 25:75. In one embodiment, a graft copolymer comprising about 50% by weight of polyvinyl chloride and about 50% by weight of the ethylene-ethylacrylate copolymer is prepared and utilized as component (C) in the compositions of the present invention. (C-2)(C-3) The carbonyl-containing copolymers useful in the compositions of the present invention also may be polyurethanes (C-2) or graft copolymers of a polyvinyl halide and a polyurethane (C-3) which are melt-process- able within the range of polyvinyl chloride processing temperatures. The polyurethane polymers useful in the invention are those formed by reacting an organic diiso- cyanate with an active hydrogen-containing material such as polyalkylene ether glycols and hydroxy-terminated polyesters. In the preparation of polyester-urethane elas¬ tomers, there preferably are used hydroxy-terminated polyesters prepared by polycondensation of an aliphatic dicarboxylic acid and a molar excess of an aliphatic glycol, and those prepared by ring-opening polymeriza¬ tion of a cyclic ester in the presence of a difunctional compound as an initiator. The polyesters obtainable by polycondensation of an aliphatic dicarboxylic acid and an aliphatic glycol are exemplified by those obtained by reaction between adipic acid, sebacic acid,, aleic acid and other dicarboxylic acids with ethylene-glycol, 1,2- propylene glycol, 1,4-butylene glycol, 1,3-butylene glycol, etc. Examples of the polyesters prepared by polymerization of cyclic esters are those prepared from epsilon-caprolactone, delta-methyl-epsilon-caprolactone and beta-propiolactone in the presence of an initiator such as, for example, 1,4-butylene glycol, ethylene glycol or diethylene glycol. The polyalkylene ether urethanes are those prepared by reacting the isocyanates with polymeric polyhydroxy compounds which include polyether polyols such as polyalkylene ether glycols, polyalkylene arylene ether-thioether glycols and polyalkylene ether triols. The polyalkylene ether glycols and triols are preferred and these include glycols having the formula H0(R0) n H wherein R is an alkylene radical which need not neces¬ sarily be the same in each instance, and n is an inte¬ ger. Representative glycols include polyethylene ether glycol, polypropylene ether glycol and pol tetramethyl- ene ether glycol. Representative polyalkylene ether triols are made by reacting one or more alkylene oxides with one or more low molecular weight aliphatic triols. The alkylene oxides most commonly used have molecular weights between about 44 and 250 and these include ethyl¬ ene oxide, propylene oxides, butylene oxides, 1,2-epoxy- butane and 2,3-epoxybutane. The ethylene, propylene and butylene oxides are preferred. The ethylene, propylene and butylene oxides are preferred. The aliphatic triols most commonly used have molecular weights between about 92 and 250. Examples include glycerol, 1,2,6-hexane triol and 1 ,1 , 1-trimethylol propane. Other active hydrogen-containing compounds which can be reacted with pol isocyanates to form ure- thanes useful in the invention are long-chain polymers containing at least two groups having at least one active hydrogen atom as determined by the Zerewitinoff method. Examples of such compounds include in addition to the polyesters and polymeric polyhydroxy compounds described above, polyamides, polyepoxides, reaction products of phenols and alkylene oxides, formaldehyde resins, hydrogenation products of olefin-carbon monoxide copolymers and polyepihalohydrins. A ong the suitable isocyanates that may be used in the preparation of the polyurethanes are included aryl diisocyanates such as 2,4-toluene diisocyanate (TDI), 2,6-toluene diisocyanate, 4,4'-diphenylmethane diisocyanate (MDI), 1 ,5-naphthylene diisocyanate and xylene-1 ,4-diisocyanate; alicyclic diisocyanates such as dicyclohexamethane-4,4'-diisocyanate; alkylene diisocyan¬ ate such as tetramethylene diisocyanate and hexamethyl- ene diisocyanate; as well as mixtures thereof and includ¬ ing the equivalent isothiocyanates. Chain extenders which may be utilized in the preparation of the urethanes are substantially difunc- tional or polyfunctional active hydrogen-containing com¬ pounds such as ethylene glycol, 1 ,2-propylene glycol, neopentyl glycol, dipropylene glycol, hydrazine, ethyl¬ ene diamine, N,N,N' ,N'-tetrakis (dihydroxy propyl) ethylene diamine, etc. Particularly useful in this invention are thermoplastic polyurethanes based on polyester polyols and diisocyanates such as MDI. Such thermoplastic poly¬ urethanes are available commercially from the B.F. Good¬ rich Company under the general trade designation "Estane". For example Estane 58271 is a thermoplastic polyurethane derived from MDI and a polyester polyol obtained by the reaction of adipic acid with 1 ,4-butane diol, the polyester polyol having a molecular weight of about 1000. Graft copolymers of polyvinyl chloride and polyurethane prepared by milling polyvinyl chloride, a stabilizer, polyurethane and a catalyst such as a perox¬ ide also may be utilized in the compositions of the present invention. (C-4) As noted above, the carbonyl-containing polymer may be a graft copolymer of a polyvinyl halide and an alpha,beta-olefinically unsaturated carboxylic acid or acid anhydride. Any of the polyvinyl halides described above, and in particular, polyvinyl chloride, can be utilized. These copolymers can be prepared by tech¬ niques well-known to those skilled in the art. Olefin- ically unsaturated dicarboxylic acid anhydrides are preferred and these include maleic acid anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. Maleic anhydride is the preferred anhydride. For example, a mixture of maleic anhydride, a free radical catalyst, and polyvinyl chloride is reacted by heating the mixture to a temperature above its melting point in ther absence of a solvent. The grafting reaction can be conducted on standard polymer processing equip¬ ment such as a two-roll mill. Free radical initiators or catalysts are utilized in effecting the polymeriza¬ tion, and among the free radical initiators, peroxides, hydroperoxides, ketone peroxides, etc., are preferred. The weight ratio of polyvinyl halide to maleic acid in the graft polymer may be from about 100:0.05 to about 100:5. The following examples illustrate the prepara¬ tion of various carbonyl-containing polymers useful as component (C) in the vinyl halide polymer compositions of the present invention. Unless otherwise indicated in the following examples and elsewhere in the specifica¬ tion and claims, all parts and percentages are by weight, all temperatures are in degrees centigrade, and pressures are at or near atmospheric. Example C-1 Approximately equal parts of vinyl chloride monomer and ethylene-ethylacrylate copolymer (DPD 6169 Natural, Union Carbide) are charged to a polymerization reactor containing water and a polyvinyl alcohol dispers- ant. Peroxide (t-butyl peroxypivalate) is added to the suspension in the reactor, and the temperature is raised to about 60°C whereupon polymerization begins. The poly¬ merization reaction is continued for about 13 hours as additional vinyl chloride is added incrementally to the suspension. Incremental addition of vinyl chloride is necessary to keep the ethylene-ethylacrylate pellets from sticking together during polymerization. After about 13 hours of heating, the reaction is terminated, excess vinyl chloride is removed by steam stripping, and the pelletized product is dried. The final composition is a graft polymer comprising about 50% by weight of polyvinyl chloride and about 50% by weight of ethylene- ethylacrylate copolymer. Example C-2 A mixture of 20 parts of polyvinyl chloride, 80 parts of polyurethane resin (Estane 58271), 2 parts of a tin stabilizer, 0.25 part of stearic acid and 0.4 part of benzoyl peroxide is milled at about 175°C on a two- roll mill for 3 minutes. After banding, the sheet is removed and cut into cubes. Example C-3 The procedure of Example C-2 is repeated except that the mixture comprises 50 parts of polyvinyl chlor¬ ide and 50 parts of polyurethane. Example C-4 The procedure of Example C-2 is repeated except that the mixture comprises 80 parts of polyvinyl chlor¬ ide and 20 parts of polyurethane. Example C-5 A mixture of 60 parts of polyvinyl chloride, 40 parts of Estane 58271, 2 parts of tin stabilizer, 0.25 part of stearic acid and 0.1 part of catalyst (Triganox B) is milled at about 175°C on a two-roll mill. After banding, the sheet is removed and cut into cubes. Example C-6 A mixture comprising 500 parts of polyvinyl chloride, 0.51 part of maleic anhydride, 0.051 part of benzoyl peroxide, 10 parts of tin stabilizer and 1.25 parts of stearic acid is prepared and compounded on a two-roll mill. The desired graft copolymer is recov¬ ered. Example C-7 A mixture comprising 500 parts of polyvinyl chloride, 2.05 parts of maleic anhydride, 0.205 part of benzoyl peroxide, 10 parts of tin stabilizer and 1.25 parts of stearic acid is prepared and compounded on a two-roll mill. The desired graft copolymer is recovered. Example C-8 A mixture comprising 500 parts of polyvinyl chloride, 5.12 parts of maleic anhydride, 0.51 part of benzoyl peroxide, 10 parts of tin stabilizer and 1.25 parts of stearic acid is prepared and compounded on a two-roll mill. The desired graft copolymer is recover¬ ed. The vinyl halide polymer compositions of the present invention, in addition to the vinyl halide poly¬ mer (A), the EVOH copolymer (B) and the carbonyl-contain¬ ing polymer (C) generally will contain additional mater¬ ials normally incorporated into vinyl chloride polymers for various purposes. For example, the vinyl halide polymer compositions may contain various additives including: impact modifiers such as methyl methacryl- ate-butadiene-styrene terpoly ers; extrusion aids such -16- Measurements of the oxygen transmission rate are performed on 4in. x 4in. samples with a maximum thickness of 0.060 inch at room temperature. One side of the sample is exposed to oxygen-free nitrogen and the other side is exposed to oxygen at atmospheric pressure. An oxygen-sensitive coulometric fuel cell is used for the detection and measurement of the transmission rate of the oxygen which passes through the sample. The gas transmission rates for the vinyl halide polymer composi¬ tions of the present invention (and control examples) are reported in cubic centimeters-mils per 100 sq. inches - 24 hour - atmosphere. Toughness and stiffness were measured by dropped dart impact which is reported in inch/pounds per one-thousandth of an inch or (in.lbs/mil) . TABLE II -1 5- as methyl methacrylate polymers; heat stabilizers such as dioctyl tin mercaptide and maleates; antioxidants such as epoxidized soybean oil and hydroxy phenyl compounds; lubricants such as hydrocarbon waxes, oils, stearic acid and glycerol monostearate, ultraviolet stabilizers such as benzophenones, colorants, etc. These supplemental additives may be present at levels from 0.01% up to about 20% to about 25% by weight of the vinyl chloride polymer. The various components which comprise the vinyl halide polymer compositions as described above are thor¬ oughly mixed together to form the vinyl halide composi¬ tion before it is shaped into the desired article. Mix¬ ing may be accomplished by any of the customary methods known to those skilled in the art such as with a Ban- bury, Henshel, roll mills or other mixers. Blending of the various components of the vinyl halide compositions can be accomplished on an extruder or a two-roll mill, and the materials can then be cut into strips, cubed and extruded on a Brabender fitted with a strip die. The following examples illustrate the vinyl halide polymer compositions in accordance with the pre¬ sent invention. In each of the examples, parts are by weight, and the identified components are compounded, two-roll milled at temperatures of about 175°C, cubed and extruded. The oxygen transmission rate of the materials prepared from the vinyl halide polymer compo¬ sitions of the following examples is determined utiliz¬ ing the following procedure described in more detail in the Mocon/Modern Controls, Inc. manual, Mocon PN140-042, Revision E. TABLE III TABLE IV The vinyl halide polymer compositions of the present invention are readily processable, and the compo¬ sitions are generally impact-resistant thermoplastic materials which can be thermoformed into a wide variety of useful articles by any of the methods conventionally employed with known thermoplastic polymeric materials. For example, the polymer compositions of the present invention can be formed by extrusion, milling, molding, drawing, blowing, etc. The vinyl halide polymer composi¬ tions of the present invention are characterized as having good mechanical integrity (i.e., the degree of delamination of compositions the invention is less than corresponding compositions which do not contain the carbonyl-containing polymer (O), improved impact strength and low permeability to gases and vapors which make them very useful for manufacturing films, sheets, bottles and other types of containers and hollow arti¬ cles for liquids and solids. Suitable methods for pro¬ ducing hollow articles such as bottles include extru¬ sion-blow molding, injection-blow molding, and stretch- blow molding, and hollow articles such as bottles gener¬ ally will have wall thicknesses of from about 0.005 inch to about 0.100 inch. Films from the vinyl halide poly¬ mer compositions of the present invention may be made by calendering, and films normally will have a thickness of from about 0.001 inch to about 0.100 inch. While the invention has been explained in rela¬ tion to its preferred embodiments, it is to be under¬ stood that various modifications thereof will become apparent to those skilled in the art upon reading the specification. Therefore, it is to be understood that the invention disclosed herein is intended to cover such modifications as fall within the scope of the appended claims.

Claims: Claims 1. Vinyl halide polymer compositions exhibit¬ ing reduced gas permeability comprising a mixture of (A) at least one vinyl halide polymer; (B) from about 1 to about 40% by weight, based on the weight of the vinyl halide polymer (A), of an ethylene-vinyl alcohol copolymer containing from about 15 to about 55 mole percent of ethylene; and (C) at least one carbonyl-containing polymer wherein the carbonyl group is selected from the group consisting of -C(O)-, -C(0)0-, -N-C(O)-, and -N-C(0)0- 2. The polymer composition of claim 1 wherein the vinyl halide polymer (A) is a vinyl chloride poly¬ mer. 3. The polymer composition of claim 1 wherein the vinyl halide polymer is a vinyl chloride homopoly- mer. 4. The polymer composition of claim 1 wherein the ethylene-vinyl alcohol copolymer (B) contains from about 20 to about 50 mole percent of ethylene. 5. The polymer compositions of claim 1 con¬ taining from about 1 to about 20% by weight, based on the weight of vinyl halide polymer (A), of polymer (C). 6. The polymer composition of claim 1 wherein polymer (C) is a graft copolymer of a polyvinyl halide and an ethylene-alkyl acrylate copolymer wherein the alkyl acrylate is characterized by the formula CH 2 =C(R)-C(0)0R-, wherein R is an alkyl group containing 1 or 2 carbon atoms and R- j is an alkyl group containing from 1 to about 8 carbon atoms. 7. The polymer composition of claim 6 wherein R is hydrogen and R- | is methyl or ethyl. 8. The polymer composition of claim 1 wherein the polymer (C) is a polyurethane. 9. The polymer composition of claim 1 wherein polymer (C) is a graft copolymer of a polyvinyl halide and polyurethane. 10. The polymer composition of claim 1 wherein polymer (C) is a graft copolymer of a polyvinyl halide and an alpha,beta-olefinically unsaturated carboxylic acid or anhydride. 11. The polymer composition of claim 1 wherein polymer (C) is characterized as being melt-processable in the temperature range which the vinyl halide polymer composition is processed. 12. Vinyl halide polymer compositions exhibit¬ ing reduced gas permeability comprising a mixture of (A) at least one vinyl chloride polymer; (B) from about 5 to about 40% by weight, based on the weight of the vinyl chloride polymer (A) of at least one ethylene-vinyl alcohol copolymer containing from about 20 to about 50 mole percent of ethylene; and (C) from about 1 to 20% by weight, based on the weight of vinyl chloride polymer (A) of at least one carbonyl-containing polymer selected from the group consisting of (C-1 ) a graft copolymer of a polyvinyl halide and an ethylene-alkyl acryl¬ ate copolymer wherein alkyl acrylate is characterized by the formula CH 2 =C ( R) -C ( 0 ) OR 1 wherein R is a methyl or ethyl group and R- j is an alkyl group contain¬ ing from 1 to about 8 carbon atoms; (C-2) a polyurethane; (C-3) a graft copolymer of a polyvinyl hal¬ ide and a polyurethane; and (C-4) a graft copolymer of a polyvinyl hal¬ ide and an alpha,beta-olefinically unsaturated carboxylic acid or anhy¬ dride. 13. The polymer composition of claim 12 where¬ in the vinyl chloride polymer (A) is a vinyl chloride homopolymer. 14. The polymer composition of claim 12 where¬ in the carbonyl-containing polymer (C) is (C-1 ) a graft copolymer of a polyvinyl halide and an ethylene-alkyl acrylate copolymer wherein R is hydrogen and R- j is a methyl or an ethyl group. 15. The polymer composition of claim 14 where¬ in the acrylate is ethyl acrylate. 16. The polymer composition of claim 14 where¬ in the ethylene-alkyl acrylate copolymer comprises from about 60 to about 97% by weight of ethylene and from about 3 to about 40% of the alkyl acrylate. 17. The polymer composition of claim 12 where¬ in polymer (C) is (C-1 ) and the weight ratio of polyvinyl halide to ethylene-alkyl acrylate copolymer is from 75:25 to 25:75. 18. The polymer composition of claim 12 where¬ in the carbonyl-containing copolymer is (C-4) a graft copolymer of polyvinyl chloride and maleic anhydride. 19. The polymer composition of claim 18 where¬ in the weight ratio of polyvinyl chloride to maleic anhy¬ dride in the graft copolymer is from about 100:0.05 to about 100:5. 20. A film of the vinyl halide polymer composi¬ tion of claim 1. 21. A film of the vinyl halide polymer composi¬ tion of claim 12. 22. Packaging films, sheets and hollow arti¬ cles fabricated from the vinyl halide polymer composi¬ tion of claim 1. 23. Packaging films, sheets and hollow arti¬ cles fabricated, from the vinyl halide polymer composi¬ tion of claim 12.

Inventors: BRADEN THOMAS CLIFFORD, KLINE SALLY ANN, PERRY SCOTT, BRADEN, THOMAS, CLIFFORD, KLINE, SALLY, ANN, PERRY, SCOTT
Applicants: GOODRICH CO B F, THE B.F. GOODRICH COMPANY
Application year: 1990
Main classification: C08L27
IPC codes: B29C51, C08J5, C08L23, C08L27, C08L29, C08L31, C08L51, C08L67, C08L75, C08L77