THERMOPLASTIC ELASTOMERIC COMPOSITIONS BASED ON COMPATIBLE BLENDS OF AN ETHYLENE COPOLYMER AND VINYL OR VINYLIDENE HALIDE POLYMER

Abstract: A thermoplastic elastomeric composition based on compatible blends of an ethylene copolymer and a vinyl or vinylidene halide polymer.

Description: TITLE THERMOPLASTIC ELASTOMERIC COMPOSITIONS BASED ON COMPATIBLE BLENDS OF AN ETHYLENE COPOLYMER AND VINYL OR VINYLIDENE HALIDE POLYMER The subject application is a continuation of copending application U.S.S.N. 394,329 filed July 1, 1982. BACKGROUND Blends of ethylene copolymers and vinyl halide polymers crosslinked during or subsequent to molding into shaped articles are known in the art as detailed in French Patent 2,148,496. The molded articles prepared from these compositions, however, suffer the disadvantage of being thermoset due to the high degree of crosslinking effectuated and, hence, are not reprocessible or remoldable. Elastomeric thermoplastic compositions based on partially crosslinked incompatible blends of polypropylene and ethylene/vinyl acetate copolymers are also known in the art as detailed in U.S. Patent 4,232,132. This incompatibility results in a multiphase system having a crosslinked elastomeric phase and an uncross linked hard phase. However, the elastomeric properties of these compositions (e.g. % permanent tensile set) are poor relative to the elastomeric properties of the compositions of the subject invention. SUlEMARY OF THE INVENTION The subject invention is a thermoplastic, inherently melt processible elastomeric composition based on partially crosslinked compatible blends of an ethylene copolymer and a vinyl or vinylidene halide polymer. The melt processibility of these compositions allows shaped articles to be molded therefrom without the time consuming cure step required with conventional rubbers. More specifically, the subject invention is a thermoplastic elastomeric composition comprising a partially crosslinked blend of (a) a copolymer of ethylene and one or more copolymerizable comonomers selected from the group consisting of ethylenically unsaturated organic monomers, carbon monoxide and sulfur dioxide; and (b) between 5 and 75 weight percent based on the composition of a vinyl halide or vinylidene halide polymer, wherein the comonomer content is such that the copolymer exhibits compatiblity with the vinyl or vinylidene halide polymer. DETAILED DESCRIPTION The ethylene copolymers useful in the practice of the subject invention include, for example, those dipolymers having the formula E/X and Ely, and those terpolymers having the formula E/X/Y, where X is an ethylenically unsaturated organic monomer and Y is either carbon monoxide or sulfur dioxide. Exemplary of the organic monomers are those selected from the group consisting of unsaturated mono- or dicarboxylic acids of 3-20 carbon atoms, esters of said unsaturated mono- or dicarboxylic acids, vinyl esters of saturated carboxylic acids where the acid group has 2-18 carbon atoms, vinyl alkyl ethers wherein the alkyl group has 1-18 carbon atoms, vinyl or vinylidene halides, acrylonitrile, methacrylonitrile, norbornene, alpha olefines of 3-12 carbon atoms, and vinyl aromatic compounds. Preferred organic monomers include methyl acrylate, butyl acrylate and vinyl acetate. Of course, more than one of these organic monomers may be copolymerized with ethylene to form the ethylene copolymer useful in the practice of the subject invention. The melt index range for these copolymers is 0.1 to 1000 (ASTM D-1238), preferably 1 to 100. The ethylene copolymers useful in the practice of the subject invention need have sufficient comonomer copolymerized therein to exhibit compatability with the vinyl and vinylidene halide polymers described below. Generally speaking, when the ethylene copolymer is represented by the formula E/X, copolymers having a comonomer content of greater than 45 percent based on the weight of the copolymer are useful in the practice of this invention; when the ethylene copolymer is represented by the formula E/Y, copolymers having a comonomer content greater than about 15 percent are useful in the practice of this invention; and when the ethylene copolymer is represented by the formula E/X/Y, copolymers with substantially lower comonomer content exhibit compatibility with vinyl and vinylidene halide polymers, i.e. the ethylene content in these terpolymers should be 40 to 85 percent, the organic monomer content 1 to 60 percent, and the carbon monoxide or sulfur dioxide content 1 to 30 percent, all based on polymer weight. Since copolymers of the E/X type require such a high comonomer content to exhibit compatibility with vinyl and vinylidene halide polymers as compared to copolymers of the E/X/Y type, these E/X/Y copolymers are especially preferred for purposes of the subject invention. When an ethylene copolymer is used which is not sufficiently compatible with the vinyl or vinylidene polymers, shaped articles molded from the blends are opaque, show stress whitening when stretched and lack the required recovery to be considered elastomeric. A more detailed discussion of the compatability of these ethylene copolymers with vinyl and vinylidene halide polymers, as well as a discussion of the preparation of the copolymers can be found in Polymer-Polymer Miscibility, O. Olabisi, L. M. Robeson and M. T. Shaw, Academic Press, N.Y., N.Y., 1979, U.S. Patent 3,684,778 and U.S. Patent 3,780,140, all herein incorporated by reference. The ethylene copolymers described above are blended in accordance with the subject invention with 5 to 75, preferably 20 to 60, weight percent based on the blended composition of vinyl or vinylidene halide polymers including copolymers resulting from copolymerization with a comonomer selected from the group consisting of vinyl esters, acrylonitrile, acrylic esters, vinylidene chloride, vinyl chloride, esters of unsaturated carboxylic acids and vinyl ethers. For example, polyvinyl chloride having an inherent viscosity of 0.30 to 1.4 (ASTM D-1243) is generally useful in the practice of the subject invention. The blending of the ethylene copolymer with the vinyl or vinylidene halide polymer is accomplished by any one of a number of conventional techniques, for example, in a Banbury mixer, two-roll mill or extruder. This blending is done at a temperature high enough to soften the polymers for adequate blending, but not so high as to degrade the vinyl or vinylidene halide polymer. Generally speaking this blending temperature ranges from 140 to 200"C, and blending is carried out for a time sufficient to homogeneously blend the components. The critical aspect of the subject invention is the partial crosslinking of the compatible blend. This can be carried out using any one or more of the well known crosslinking techniques including electron beam irradiation, gamma irradiation and free radical curatives such as peroxides. The cross linking of the polymer blends of the subject invention can be carried out before or concurrently with blending with the vinyl or vinylidene halide polymers, or after such blending when using radiation techniques to effectuate the crosslinking. If the ethylene copolymer in the blend contains carbon monoxide, diamines such as methylene dianiline or p-phenylene diamine can be used to effectuate the desired crosslinking. If the ethylene copolymer is ethylene/vinyl acetate/carbon monoxide, sulfur vulcanizing agents can be used as detailed in U.S. 4,172,939. For crosslinking ethylene copolymers containing carboxylic acid functionalities, the formation of ionic crosslinks is suitable in the practice of the subject invention, and is achieved with various metal oxides or hydroxides such as ZnO and NaOH, or with organometallics such as chromium acetylacetone, as detailed in U.S. 4,304, 887. The term 1'partially crosslinked" refers to a degree of cross linking sufficient to transform a blend of an ethylene copolymer as detailed above and a- vinyl or vinylidene halide polymer into the thermoplastic elastomeric blends of the subject invention. To quantify the degree of crosslinking, the amount of insoluble, and hence crosslinked, polymer is determined by soaking a sample of the polymer, after crosslinking, in tetrahydrofuran at 23"C for 16 hours, isolating the insoluble portion and weighing the dried residue, making suitable corrections based upon knowledge of the composition. For example, the weight of components soluble in tetrahydrofuran such as plasticizers are subtracted from the initial weight; and components insoluble in tetrahydrofuran, such as pigments, fillers, etc. are subtracted from both the initial and final weight. The insoluble polymer recovered is reported as percent gel content. This procedure is based on a conventional procedure for quantifying degree of crosslinking that is more fully detailed in U.S. 3,203,937. For purposes of the subject invention, the polymer blends need be partially crosslinked so that they have a gel content of 5 to 90 percent, preferably 10 to 70 percent based on total polymer. The conditions under which this crosslinking is carried out, i.e., type and quantity of crosslinking agent, cross linking time and temperature, to arrive at a composition having a gel content within this operable range, can be determined empirically. Vihen chemical crosslinking agents are utilized, it is preferable that they be substantially totally consumed during the crosslinking step. when polyvinyl chloride (PVC) is utilized as the vinyl halide polymer in the practice of the subject invention, spectroscopic evidence indicates that the gel fractions isolated from those partially crosslinked polymer blends contain only crosslinked ethylene copolymer, with no detectable PVC present. It is theorized, therefore, that essentially no crosslinking of the PVC occurs. Although not essential components of the composition of this invention, various amounts of any number of conventional fillers or compounding ingredients may be admixed. Examples of such ingredients include various carbon blacks, clays, silica, alumina, calcium carbonate, titanium dioxide, antioxidants, antidegradants, tackifiers, processing aids such as lubricants and waxes, and plasticizers such as dialkylphthalates, trialkylmellitates and polyester oligomers. The amounts used depend, at least in part, upon the quantities of other ingredients in the composition and the properties desired from the composition. Also, minor amounts of other saturated and unsaturated polymers such as alpha-olefins may be added to reduce the cost or modify the properties of the composition. The compositions of the subject invention are melt processible using conventional plastic processing equipment. Articles molded from the unique thermoplastic elastomeric compositions of the subject invention exhibit properties generally only associated with vulcanized rubber. For example, these compositions have resistance to compression set values of about 20 to 70 percent (70 to 100XC): and elongation at break values of 150 to 600 percent without substantial permanent tensile set (i.e., less than about 15 percent). Various uses for these compositions include wire coverings, seals and gaskets, automotive parts, sheet liners and packaging films. They can be used to coat fabric, industrial belts and various hard surfaces by extrusion coating, for example, polyester, polyamide, polyimide or metal fibre or fabric reinforcement. They find utility in adhesive and sealant applications, as well as for modification of other polymer systems. Further, compositions within the scope of this invention can be fabricated into tubing for laboratory, medical and industrial uses. Such tubing could also be used as the inner tube of reinforced hoses, wherein the extruded tube is overlaid with wire or textile cords, applied as a spiral, knit or braid. Optionally, a polymeric covering may be applied (extruded or spiral wound calendered sheet) over the reinforced tubing to provide protection from the working environment and mechanical abuse. Compositions within the scope of this invention can be used as the protective covering of reinforced tubes of similar or different composition. The subject invention will be more fully appreciated with reference to the examples that follow: EXAMPLE 1 Unless otherwise specified, the percentages given in all examples herein are on a weight percent basis. The intrinsic viscosities (iv) given for the polyvinyl chloride (PVC) are measured in solutions of 0.2 g of the polymer in 100 ml of cyclohexanone at 25 C. The melt indexes (MI) of the ethylene copolymers are measured at 1900C according to ASTM D-1238. The following formulations were blended as described below. The PVC, due to its thermal instability, was dry blended with the following stabilizer package as is typical in PVC compounding (percentages based on weight of PVC): Component Ba/Cd laurates available from 2.5 Argus Chemical Co. as "Mark" WS Epoxidized soy oil available 8.2 from Rohm and Haas Co. as "Paraplex" G62 Liquid phosphite chelator 0.8 available from Argus Chemical Co. as "Mark" 517 Acrylic fusion aid available 2.5 from Rohm and Haas Co. as "Acryloid" K120N Polyethylene wax available from 3.3 Allied Chemical Co. as "Allied" 6A Stearic acid 0.3 Batches A, B and C were blended in a Banbury internal mixer at 1800C for 6 minutes and sheeted out on a conventional two-roll mill. Batch E was blended in a 28 mm twin screw co-rotating self wiping extruder having a barrel temperature of 200µC throughout with an extrusion rate of 10 kg/hr. The blended composition exited the extruder through a strand die and was cut into 0.5 cm (3/16 inch) pellets. Batches D and F were prepared directly from batches C and E respectively by adding carbon black on a two-roll rubber mill at 160 to 1700C after the crosslinking described below. Electron beam irradiation crosslinking of the ethylene copolymers PVC blends in these batches was performed under atmospheric conditions and at ambient temperatures with high energy electrons using a 2 Mev General Electric resonant transformer at 0.3 milliamp (dose rate, 3.0 Mrad/min). Doseage was controlled by the amount of time the blends were subjected to radiation. The blends were irradiated in the form of either 15 cm X 15 cm X 0.3 cm (6" x 6" X 1/8") plaques (batch C & D) or as a layer of 0.5 cm (3/16") pellets (batches A, B, E and F). Degree of crosslinking was monitored by observing the change in melt index as the dosage was increased. Irradiation was stopped when the melt index approached or reached a no-flow (no measurable melt index). Batch: A B C D E F E/28% VA1/10% CO (MI g 35) 53% 53t - - - - E/61% MA1 (MI - 6) - - 70% 64% - - E/25t VA/10% CO (MI - 35) - - -' - 66.5% 60.5% PVC ("Geon" 92)2 iv = 1.02 23% - 30% 27% - PVC (FPc-9300)3 iv - 0.96 - 23% - - 33.5% 30.4% Carbon black N-6504 15% 15% - - - Carbon black N-7744 - - - 9.0% - 9.1% Polyester Oil ("Santicizer" 429)5 9% 98 - - - Irradiation Dosage (Megarads) 1.3 1.0 0.9 0.9 1.0 1.0 1. VA s vinyl acetate, EIA = methyl acrylate 2. Sold by B. F. Goodrich Co. 3. Sold by Firestone Plastics Co. 4. ASTM grade designation 5. Sold by Monsanto Chemical Co. After blending and crosslinking, to demonstrate that these compositions were melt processible, each batch was placed in a mold at ambient temperature and loaded into a Pasadena hydraulic press, both platens of which had been preheated to 200-C. The pressure was raised to about 1.3 MPa (200 psig) and held for 5 minutes. The pressure was then slowly increased over a 3 minute period to 276 MPa (40,000 psig) and held for an additional 2 minutes. The press was then rapidly cooled to ambient temperature and the molded article removed. Physical measurements taken of each sample are tabulated below, showing that these samples exhibited properties of vulcanized rubber. The molded articles were re-melt processible. Batch: A B C D E F Shore A Hardness1 74 74 52 75 69 85 Compression set B (%)ê 60 63 55 62 57 51 (22 hrs at 70 C) % Volume swell , - - 80 78 68 64 (7 days at 100 c) Clash-Berg Temp. C4 - - -25 -23 -13 -B Tensile at break (MPa) 7.76 8.17 5.95 9.03 8.10 9.12 Elongation at break (%)5 250 300 440 530 430 470 M100 (YJPa)5 4.62 4.21 1.40 2.62 3.62 4.69 H200 (MPa) 7.24 6.48 3.12 4.16 5.03 6.49 1. ASTM D-2240 2. ASTM D-395 3. ASTM n-200 (f3 Oil, 7 days at l00 c) 4. ASTM D-1043 5. ASTM D-412 EXAMPLE I I The following formulations were blended as described below (values are in weight percent, and the PVC was stabilized as per Example 1): Batch: A B C D E E/62% MA/3.5% MAME1 68.6 E/308 n-Bh2/10\ CO (MI - 5) 57.2 48.6 - E/62% MA (MI " 5) - - 66.7 - - E/28% VA/108 CO (MI - 35) - - - 68.8 PVC ("Geon" 92) iv = 1.02 30.1 26.2 31.5 - 29.4 PVC (FPC-9300) iv - 0.9B - - - 29.4 Polyester Oil ("Santicizer" 429) 10.6 9.0 - - Carbon black N-650 - 15.0 - - CROSSLINKING AGENTS and m- , '-bis(t-but-ylper- 0.9 0.8 1.0 1.0 oxy)diisopropylbenzene3 m-phenylenediamine-bis-male- 0.6 0.5 0.7 0.7 imide4 chromium (III) 2,4 pentane- - - - - 2.0 dionate5 1. MAME - maleic acid monoethyl ester 2. n-BA r n-butyl acrylate 3. sold as "Vul-Cup" R by Hercules Chemical Co. 4. sold as "EVA-2" by E. I. du Pont de Nemours and Company 5. sold by Ventron Corp. Batches A and B were blended by adding all ingredients except curatives to a Banbury internal mixer for 7.0 mins at 1500C. Crosslinking agents were then added and the temperature was increased to 1900C and held at that temperature for 4.0 mins while mixing at high speed to-induce partial crosslinking. The compositions were then extruded into tubing at 190-C using a Brabender extruder fitted with a 0.6 cm (1/4") tubing die thereby exhibiting thermoplastic processibility. These blends also easily injection molded at high speed, as illustrated by the following procedure: The compositions were fed to a reciprocating screw type injection molding machine, with all zones of the barrel heated to 1700C and the mold at 25"C. Using a screw rpm of 144 and an injeCtion pressure of 1200 psi., the molten material filled out the cavity of the plaque mold in 15 seconds and was allowed to cool an additional 10 seconds before the mold was opened and the finished part was ejected. Batch C was blended in a Haake Cheocord laboratory mixer as follows: PVC and E/MA polymer were added to the mixer at 1450C, temperature was taken up to 1800C and held for 2 mins while mixing at high speed (64 rpm). The blend was allowed to cool to less than 1250C and the crosslinking agents added. The temperature was increased to 1800C and the mixture held for about 2 mins while mixing at high speed to induce partial crosslinking. Batch D was prepared by blending the PVC and ethylene polymer in a 28 mm twin screw co-rotating self wiping extruder having a barrel temperature of 200"C throughout with an extrusion rate of 10 kg/hr. The blended composition exited the extruder through a strand die and was cut into 0.5 cm (3/16 inch) pellets. The partial cross linking was done in a Brabender laboratory mixer (Plasticord) as follows: polymer blend was added to the mixer and temperature was stabilized at llO"C at slow speed (32 rpm), the cross linking agents were then added and the temperature increased to 1550C while mixing at fast speed (64 rpm) and was held for 15 mins and removed. Batch E was blended in a Banbury mixer at 180 CC for 5 minutes. The blend was then transferred to a Brabender mixer (Plasticord) and the crosslinking agent was added. This mixture was held in the mixer for 5 minutes at 170"C to effect cross linking. Samples of each Batch were compression molded as in Example I, the physical properties of the molded articles tabulated below. Batch: A B C D E Shore A Hardness 64 74 70 72 77 Compression set B (%) 222 372 5 3 383 643 t Volume swell 50 46 - - 62 Clash-Berg Temp. (0C) -26 -23 -22 - -36 Tensile at break (MPa) 4.31 6.72 10.00 12.72 9.92 Elongation at break (t) 200 215 305 250 320 M100 (MPa) 2.07 3.10 3.17 4.48 2.26 M200 (MPa) 4.31 6.70 6.45 10.00 5.79 Permanent tensile setl (t) 8 10 9 - 12 1. ASTM D-412 2. 22 hrs at 100'C, ASTM D-395 3. 22 hrs at 70 C, ASTM D-395 Example III The following formulation was used to illustrate the use of an additional crosslinking agent: Weight % E/30% n-BA/10t CO 54 PVC1 29 Dioctyl phthalate 16.6 LiCl 3MDA2 0.4 1. Stabilized with 2 PER of a tin thioglycolate available from M L T Chemicals, Inc. as 'eThermolite" 133. 2. Lithium chloride complex of 4,4' diaminodiphenyl methane. The E/n-BA/CO was added slowly to molten PVC at l900C and the composition homogeneously mixed on a two-roll mill. The dioctyl phthalate and LiCl-3MDA were then added and the composition milled for 5 minutes at 190'C. The composition was then removed from the mill and compression molded into plagues, the physicai properties tabulated below. Compression set B ($)1 22.5 % Volume swell 36.2 1. 22 hrs at 70 Example IV -- This example serves to illustrate the effect of crosslinking agent concentration on level of gel content. In these formulations the stabilized PVC1 was first mixed with the trioctyltrimellitate in dry blending operation. The total formulations were then blended and simultaneously crosslinked in a 28 mm twin screw, co-rotating, self-wiping extruder as per Example I. The degree of crosslinking was assayed by determination of % gel content in tetrahydrofuran as detailed above (16 hrs, 23*C). Sample A, which contains no curative and is therefore uncrosslinked, contains only a trace of gel (insolubles). All samples were compression molded as per Example I. Formulations Batch A B C D E/308 n-BA/10% Co (MI = 5) 60.0 59.i 59.5 59.3 PVC1 (iv = 1.04) 28.5 28.4 28.3 28.2 trioctyltrimellitate 11.5 11.5 11.4 11.4 Vul-Cup 40KE2. 0 0.3 0.6 0.9 HVA-23 0 0.1 0.2 0.3 8 Gel 0.8 26.2 35.2 39.4 1. Available from Conoco Chemicals as product number 5425 and stabilized with 2.9% Ba/Cd laurates and 1.0% of a phosphite chelator (available from Argus Chemical Co. as Mark WS and Mark 517 respectively). 2. w- and m- i,i'-bis (t-butylperDxy)diisopropyl benzene, 40% on inert clay available from Hercules Chemical Company) 3. m-phenylenediamine-bis-maleimide (available from E. I. du Pont de Nemours and Company) The following illustrates the versatility of the compositions of the subject invention: Profile Extrusion Batch C of Example IV in pellet form was fed to a 1 1/2 inch (4.8cm) diameter Royle extruder with a single stage plastics screw, having a length to diameter ratio of 15:1. The extruder was run at 50 rpm and at temperatures designed to produce melt temperatures of 130"Ct 163 - 1700C and 180 - 193 ec . At all three temperature ranges, the melt was extruded through a feather-edged profile die known as a Garvey Die. The profile extrusion demonstration described above shows that compositions within the scope of this invention can be extruded as complex profiles, at relatively low melt temperatures, using standard extruders of L/D common to the rubber industry. Such extruded profiles could be used as gasketing or miscellaneous mechanical goods. Continuous Extrusion Coating of Wire Formulation C of Example IV, in pellet or cut granule form, were fed to a 1 1/4 inch (3.2cm) diameter Brabender extruder, with a single stage plastics screw, having a length to diameter ratio of 25:1. The extruder was fitted with a crosshead die sized to produce a 0.050 inch (0.13cm) thick coating on 12 AWG aluminum wire at a melt temperature of 197or and at rates of from 20 to 100 feet (0.6-30m) per minute. The wire demonstration described above and the subsequently obtained physical and electrical properties show that compositions within the scope of this invention can be used to fabricate coated wire and cable, either as low voltage primary insulation or as jacketing or semiconductive coating in higher voltage constructions. Milling and Calendering Sheet Formulation C of Example IV, in pellet form, was massed and banded on a 8 X 20 inch (0.2-0.5m) two-rubber mill, with a roll surface speed ratio of 1.2:1, and a roll temperature of 225"F (107 ec ) . The polymer band was cut from the mill roll at a stock temperature of 2700F (132 C) and transferred to a three-roll rubber calender. With all three rolls held at 2600F - 275"F (127 C - 1350C), a reasonably smooth sheet of 0.015 inch (.04cm) thickness was formed and easily released, when cut from the center calender roll. Similar results were obtained when up to 20 phr. fumed silica and 10 phr. dioctyl sebecate were blended into the polymer band on the rubber mill, prior to calendering. The milling and calendering demonstration described above. shows that compositions within the scope of this invention can be fluxed and further compounded on rubber mills and then fabricated into sheet, using moderate processing temperatures, on standard rubber calenders. Such formed sheet may be used unsupported for elastomeric packaging film, or calendered onto fabrics or onto a web of reinforcing cords in single or multiple plies to be used for roofing pit and pond liners, die-cut gasketing, diaphragms; conveyor belting and for general purpose coated fabric applications.

Claims: What is claimed is: l. A partially crosslinked blend of (a) a copolymer of ethylene and one or more copolymerizable comonomers selected from the group consisting of ethylenically unsaturated organic monomers, carbon monoxide and sulfur dioxide; and (b) between 5 and -75 weight percent, based on the composition, of a vinyl or vinylidene halide polymer wherein the comonomer content in (a) is such that the ethylene copolymer is compatible with the vinyl or vinylidene halide polymer. 2. The blend of Claim 1 wherein is incorporated one or more of the members of the group consisting of carbon black, clay, silica, alumina, calcium carbonate, titanium dioxide, dialkyl pbthalates, trialkylmellitates, polyester oligomers and saturated and unsaturated polymers. 3. The blend of Claim 1 wherein the composition has a gel content of 5 to 90 percent, more preferred 10 to 70 percent and most preferred 20 to 40 percent, based on total polymer weight. 4. The blend of Claims 1 to 3 wherein (b) is polyvinyl chloride. 5. The blend of Claim 2 wherein the copolymer (a) is of ethylene and an ethylenically unsaturated organic monomer, which is selected from the group consisting of unsaturated mono- or dicarboxylic acids of 3-20 carbon atoms, esters of said unsaturated monoor dicarboxylic acids, vinyl esters of saturated carboxylic acids where the acid group has 2-18 carbon atoms, vinyl alkyl ethers wherein the alkyl group has 1-18 carbon-atoms, vinyl or vinylidene halides, acrylonitrile, methacrylonitrile, norbornene, alpha olefins of 3-12 carbon atoms, and vinyl aromatic compounds. 6. The blend of Claim 2 wherein the organic monomer is selected from the group consisting of methyl acrylate, butyl acrylate, vinyl acetate and maleic acid monoethyl ester and is present in the copolymer in an amount greater than about 40 weight percent based on copolymer. 7. The blend of Claim 2 wherein the copolymer (a) is a terpolymer of ethylene, a copolymerizable ethylenically unsaturated organic monomer, and a member of the group consisting of carbon monoxide and sulfur dioxide and the organic monomer is selected from the group consisting of unsaturated mono- or dicarboxylic acids of 3-20 carbon atoms, esters of said unsaturated mono- or dicarboxylic acids, vinyl esters of saturated carboxylic acids where the acid group has 2-18 carbon atoms, vinyl alkyl ethers wherein the alkyl group has 1-18 carbon atoms, vinyl or vinylidene halides, acrylonitrile, methacrylonitrile, norbornene, alpha olefines of 3-12 carbon atoms, and vinyl aromatic compounds. 8. The blend of Claim 2 wherein the organic monomer is selected from the group consisting of methyl acrylate, butyl acrylate and vinyl acetate and is present in the copolymer in amounts of 1 to 60 weight percent based on copolymer and the carbon monoxide or sulfur dioxide is present in amounts of 1 to 30 weight percent based on copolymer. 9. The blend of Claim 2 wherein the copolymer (a) is a copolymer of ethylene and a member of the group consisting of carbon monoxide and sulfur dioxide, the amount of such other comonomer being greater than about 15 weight percent based on polymer. 10. An article in the formofaself-supported film, a self-supported sheet, molded article, extruded profile, tubing, comprised of or a polyester, polyamide, polyimide or metal fibre or fabric extrusion coated by a composition comprised of a partially crosslinked blend of (a) a copolymer of ethylene and one or more copolymerizable comonomers selected from the group consisting of ethylenically unsaturated organic monomers, carbon monoxide and sulfur dioxide; and (b) between 5 and 75 weight percent, based on the- composition, of a vinyl or vinylidene halide polymer wherein the comonomer content in (a) is such that the ethylene copolymer is compatible with the vinyl or vinylidene halide polymer.

Inventors: LOOMIS, GARY LEE, STATZ, ROBERT JOSEPH
Applicants: E.I. DU PONT DE NEMOURS AND COMPANY
Application year: 1983
Main classification: C08J3
IPC codes: C08L27, C08L81, H01B3, C08L31, C08L73, C08L23