Eva modified PVC compounds for engineered membranes

Abstract

Polyvinyl chloride (PVC) coated membranes are disclosed in which a plasticizer system includes an ethylene-vinyl acetate (EVA) containing copolymer. Ketone ethylene ester (KEE) may be used as a co-plasticizer or, alternatively, the plasticizer may contain substantially no KEE. Various phthalate plasticizers may also optionally be present. Associated engineered membrane products, such as reservoir liners and covers and roofing materials are also disclosed.

Description

FIELD OF TECHNOLOGY One or more aspects relate generally to engineered performance membranes for various industrial applications and, more specifically, to modified PVC compounds for use in such membranes. BACKGROUND PVC coated fabrics have been used for roofings, reservoir covers and liners, among other industrial applications, for a long time and conventionally include liquid monomeric phthalate plasticizers. Environmental concerns have emerged pertaining to migration of liquid monomeric phthalate plasticizers into potable water. Loss of plasticizer in PVC coatings may also be associated with degradation and poor aging performance of the membranes which can multiply the problem. Engineered membranes may be in service for thirty years or more and can therefore have long-term environmental impact. A rising awareness has led environmental protection and public safety regulatory organizations to restrict the use of certain phthalate plasticizers across various products and industries. Additional plasticizers may be phased out in the future. SUMMARY In accordance with one or more aspects, a polyvinyl chloride (PVC) coated membrane is disclosed. The membrane may include a scrim coated with a composition comprising PVC resin blended with a plasticizer. The plasticizer may comprise an ethylene-vinyl acetate (EVA) containing copolymer with a VA content of at least about 35%. The plasticizer may comprise substantially no ketone ethylene ester (KEE). In accordance with one or more aspects, a PVC coated membrane is disclosed. The membrane may include a scrim coated with a composition comprising PVC resin blended with a plasticizer. The plasticizer may comprise an EVA containing copolymer at a content of at least about 10 pails per hundred parts PVC (PHR) by weight and KEE at a content of less than about 60 PHR by weight. In accordance with one or more aspects, a PVC coated membrane is disclosed. The membrane may include a scrim coated with a composition comprising an acrylic-grafted-PVC (ACR-co-PVC) resin blended with a plasticizer. The plasticizer may optionally comprise a ketone ethylene ester (KEE) but comprises substantially no ethylene-vinyl acetate (EVA) containing copolymer and substantially no liquid phthalate plasticizer. In accordance with one or more aspects, a reservoir liner or cover comprising any PVC coated membrane as described herein is disclosed. In accordance with one or more aspects, a waterproof roofing membrane comprising any PVC coated membrane as described herein is disclosed. The disclosure contemplates all combinations of any one or more of the foregoing aspects and / or embodiments, as well as combinations with any one or more of the embodiments set forth in the detailed description and any examples. DETAILED DESCRIPTION In accordance with one or more embodiments, engineered performance membranes are disclosed for a variety of industrial applications. The membranes may generally be polyvinyl chloride (PVC) coated membranes in which a scrim is coated with a composition comprising a PVC resin blended with a plasticizer. The plasticizer may be a system of plasticizer compounds as described further herein and may generally be formulated to impart various desired properties. Beneficially, in at least some embodiments, the PVC coating does not include any liquid monomeric phthalate plasticizers. The disclosed PVC coated membranes may also exhibit superior material and / or performance characteristics. For example, PVC compounds as described herein may have similar or better physical and light aging properties than plasticized compounds including liquid phthalate. Conventional liquid monomeric phthalate plasticizers may leach causing health and environmental concerns. Liquid monomeric phthalate plasticizers have lower molecular weight than solid, polymeric plasticizers and therefore have a propensity to migrate from the surface to adjacent subject, liquid, or air. Solid, high molecular weight plasticizers have emerged as a viable alternative for use in engineered membranes, with ketone ethylene ester (KEE) plasticizers (commercially available as Elvaloy® plasticizer from Dow Chemical) being a market leader. KEE is associated with desired levels of sustained durability and flexibility, as well as improved performance due to less plasticizer migration, but tends to be expensive and thus cost prohibitive for certain applications. In accordance with one or more embodiments, a plasticizer system for use in engineered membrane coatings may include one or more ethylene interpolymers to supplement or replace KEE. In accordance with one or more specific embodiments, a plasticizer system may include an ethylene vinyl acetate (EVA) copolymer to supplement or replace KEE. The ratio of EVA to any KEE in the plasticizer system, and the loading of vinyl acetate (VA) in the EVA, may vary as disclosed further herein. Higher levels of KEE may be used as a stabilizer or co-plasticizer when using a lower loading of VA in the EVA containing copolymer, e.g. 18% VA versus 40% VA. In some embodiments, the plasticizer system may be formulated without low molecular weight plasticizer. In accordance with one or more embodiments, various low molecular weight plasticizers may be replaced. Conventional low molecular weight plasticizers for PVC will be commonly recognized by those of skill in the art, including various phthalates (e.g. orthophthalate and terephthalate), aliphatic dibasic acid esters, benzoate esters, and trimellitate esters. EVA has been used in healthcare products and has no known adverse effect on human health. When the VA content of EVA is greater than about 50%, it becomes very compatible with PVC. Due to its low-temperature toughness, stress-crack resistance and excellent light stability, VA is often used to modify PVC compounds. However, when the VA content is over 50%', the material will grow tacky which makes it very difficult to make a PVC / EV A compound with conventional, less expensive compounding processes. When the VA content is at about 40%' or below, EVA is not totally compatible with PVC, but it is less tacky, and it can be processed on conventional compounding equipment. In accordance with one or more embodiments, a compatibilizer between PVC and EVA having a VA content of 40% or below is disclosed. In accordance with one or more embodiments, PVC coated membranes may exhibit desired levels of temperature and UV resistance. The PVC coated membranes may also be characterized by desired levels of chemical resistance, for example, to chlorine, solvents, acids, brines, base, biogases and various hydrocarbons. The PVC coated membranes may have desired impact strength and melt strength. The PVC coated membranes may have a desired level of flexibility and flow / fusion for processing. The plasticizer sy stem may include elevated levels of filler to help reduce associated cost. Other important material properties may include blocking, long-term stability, ply adhesion, ozone / weathering resistance, abrasion resistance and water absorption rate. In accordance with one or more embodiments, PVC coated membranes may include a scrim for reinforcement and support. The scrim may impart dimensional stability, puncture resistance and desired tensile properties. Various scrims me commonly known to those of ordinary skill in the relevant art, including various woven and nonwoven fabric materials. For example, the scrim may be a polyester nonwoven geotextile of various weight per square yard. Currently, PVC coated geomembranes are being commercially produced in both unreinforced (monolithic) products from 20 mil to 120 mil (0.5 mm to 3.00 mm) thick as well as reinforced (scrim fabric included) grades typically ranging from 30 mil to 60 mil thick (0.76 mm to 1.5 mm). Thickness may vary based on intended application. In accordance with one or more embodiments, a plasticizer system for the scrim coating may not include any plasticizer having a molecular weight of less than about 450 grams / mole. Traditional plasticizers (phthalates) are generally characterized by a molecular weight of about 200 to about 530 grams / mole. Low molecular weight plasticizers include substituted phthalate and terephthalate esters with molecular weights of less than 450 grams / mole. High molecular weight plasticizers include epoxidized soybean oil (ESO) and epoxidized linseed oil (ELO) both of which have a molecular weight of about 950g / mole. Other high molecular weight plasticizers such as KEE and EVA generally have a molecular weight of much greater than 1,000 g / mole. In some embodiments, KEE and / or EVA may have a molecular weight of about 100,000 to about 260,000 grams / mole. Higher molecular weights may be associated with lower levels of leaching but may also impact effective blending between the PVC resin and copolymer during manufacture. In at least some embodiments, to ensure robust compounding and extrusion processes, the melt flow index of EVA should be below 55 g / lOmin. Downstream processing of the disclosed PVC coated membranes to form end-products may be impacted based on the nature of the plasticizer system. For example, PVC coated membranes in accordance with some embodiments may require thermal welding due to their resistance to solvents and / or adhesives. In at least some embodiments, such PVC coated membranes may be conducive to customizable product design. In accordance with one or more embodiments, the plasticizer system can be customized to contain an optimized ratio of an EVA containing copolymer and any KEE, and the VA content of the EVA can likewise be optimized, to ensure that various performance and longevity requirements for a particular project are met. Relevant industry standards for assessing various material and performance metrics of the PVC coated membranes as described herein will be recognized by those of skill in the art. In accordance with one or more embodiments, a PVC coated membrane generally includes a scrim coated with a composition comprising polyvinyl chloride (PVC) blended with a plasticizer system. The plasticizer system may include KEE, one or more EVA containing copolymers and / or other conventional plasticizers. In some embodiments, the plasticizer system does not include ketone ethylene ester (KEE). In certain embodiments, the plasticizer system comprises substantially no substituted phthalate or terephthalate esters having a molecular weight of less than about 450 grams / mole. In at least some nonlimiting embodiments, the plasticizer system comprises substantially no compound(s) having a molecular weight of less than about 900 g / mole. In accordance with one or more embodiments, the coating composition may also include one or more other conventional compounds including various heat stabilizers, UV stabilizers, antioxidants, fillers and / or other inorganic particles, lubricants, pigments, process aids and biocides. In accordance with one or more embodiments, a PVC coated membrane may include a scrim coated with a composition comprising PVC resin blended with a plasticizer. The plasticizer may comprise an EVA containing copolymer with a VA content of at least about 35%. The plasticizer may comprise substantially no KEE. In some embodiments, the EVA containing copolymer has a VA content of at least about 40%, the plasticizer having an EVA containing copolymer content of less than about 55 PHR by weight. The EVA containing copolymer may have a VA content of at least about 45%. The EVA containing copolymer may have a VA content of at least about 50%. The EVA containing copolymer may have a VA content of at least about 60%, the plasticizer having an EVA containing copolymer content of at least about 30 PHR by weight. In at least some embodiments, the EVA containing copolymer may have a VA content of about 65%. In some embodiments, the plasticizer may comprise an EVA containing copolymer at a content of about 40 PHR to about 50 PHR, and the EVA containing copolymer may have a VA content of about 60% to about 70%. In accordance with one or more embodiments, a PVC coated membrane may comprise a scrim coated with a composition comprising PVC resin blended with a plasticizer. The plasticizer may comprise an EVA containing copolymer at a content of at least about 10 PHR by weight and KEE at a content of less than about 60 PHR by weight. The EVA containing copolymer may have a VA content of less than about 45%. The EVA containing copolymer may have a VA content of at least about 15%. The EVA containing copolymer may have a VA content of about 18% to about 45%. In some embodiments, the plasticizer may comprise less than about 20 PHR of an EVA containing copolymer having a VA content of less than about 20%. In at least some embodiments, the plasticizer may comprise less than about 20 PHR of an EVA containing copolymer having a VA content of about 18%. For example, the plasticizer may comprise about 10 PHR to about 15 PHR of an EVA containing copolymer having a VA content of about 18%. In some specific non-limiting embodiments, the total content of the EVA containing copolymer and KEE is about 40 PHR by weight. In some embodiments, the plasticizer may comprise about 30 PHR to about 50 PHR of an EVA containing copolymer having a VA content of about 40%. In some embodiments, the composition may further comprise epoxidized soybean oil (ESO) or epoxidized linseed oil (ELO). For example, the composition may comprise ESO or ELO at a content of at least about 5 PHR by weight. In some examples, the composition may comprise ESO or ELO at a content of less than about 15 PHR by weight. In some embodiments, the plasticizer may comprise substantially no substituted phthalate or terephthalate esters having a molecular weight of less than about 450 g / mole. In at least some non-limiting embodiments, the plasticizer may comprise substantially no compound(s) having a molecular weight of less than about 900 g / mole. In some specific non-limiting embodiments, without using liquid phthalate plasticizer, a semi-flexible PVC compound may be formed by using a blend of EVA containing copolymer, KEE and a small amount of ESO. The EVA may have a VA content of about 18 to about 45%. The KEE may function as a compatibility agent or co-plasticizer in the plasticizing system. In some specific non-limiting embodiments and for illustration purposes only, at 18% VA content, a plasticizer may include up to about 10 PHR to about 15 PHR of the EVA containing copolymer (total KEE + EVA of about 40 PHR) while keeping good properties. A lack of compatibility may be exhibited at 18% VA content and EVA containing copolymer loading above 20 PHR. In accordance with one or more embodiments, a conventional PVC material may be used in the scrim coating. Other PVC-based materials may be implemented. In some non-limiting embodiments, an acrylic-grafted-PVC may be used in the scrim coating. For example, Vinnolit® K 707 E free-flowing powder, commercially available from Westlake Vinnolit GmbH & Co. KG (Germany), is produced by graft polymerization of vinyl chloride onto polyacrylate (ACR). The product can contain 30-70% ACR, more preferably 40-60%, and the material that was used in the current Example Set 2 contained roughly 50% ACR. The K-value of the material can range between 65 and 80, more preferably between 68 and 80, and the material that was used in the current Example Set 2 had a K-value of 70. In some embodiments, the EVA containing copolymer may be characterized by a melt flow index of below about 55 g / lOmin. In accordance with one or more embodiments, the scrim may be extrusion coated on both sides with the composition. In accordance with one or more embodiments, the PVC coated membrane may exhibit chemical resistance to oil, fuel, acid, brine, base, solvent and / or biogas. The PVC coated membrane may exhibit thermal and / or UV resistance. In some embodiments, the PVC coated membrane may be characterized by a tensile strength of at least about 1000 PSI. In some embodiments, the membrane may be characterized by a tensile modulus of at least about 3000 PSI. In accordance with one or more embodiments, the disclosed PVC coated membranes may be used in various applications. The PVC coated membranes may be used as flexible membrane liners in a variety of applications including environmental containment of, for example, acid, brine, base or solvent, and hydrocarbon (oil / fuel / diesel) containment. The PVC coated membranes can be used as geomembranes and floating covers, for example, in various water applications including potable, wastewater, brine, leachate, municipal, brownfield and remediation applications including those for both primary and secondary containment. The PVC coated membranes can be used as anaerobic treatment digester covers and liners. Various mining, soil and waste applications may involve use of the disclosed PVC coated membranes, for example, as covers. The PVC coated membranes may be used as residential or industrial tank liners for water storage (rainwater / fire suppression / agricultural water). The PVC coated membranes may be used in roofing applications. The PVC coated membranes may be used in various backfilled or other unexposed applications including swimming pools and relining projects. No-dig water and sewer pipe repair liners can make use of the disclosed PVC coated membranes. The PVC coated membranes may be used for wire or cable coatings. Various coated 5 fabrics and footwear might involve the disclosed PVC coated membranes. In accordance with one or more embodiments, a reservoir liner or cover may comprise any PVC coated membrane disclosed herein. The reservoir liner or cover may be compatible with potable and non-potable water containment applications. The reservoir liner or cover may be configured for primary or secondary containment. The reservoir liner or cover may comprise 10 substantially no liquid monomeric phthalate plasticizer and / or substantially no ketone ethylene ester (KEE) plasticizer. In accordance with one or more embodiments, a waterproof roofing membrane may comprise any PVC coated membrane disclosed herein. The roofing membrane may comprise substantially no liquid monomeric phthalate plasticizer and / or substantially no ketone ethylene 15 ester (KEE) plasticizer. EXAMPLES The function and advantages of these and other embodiments can be better understood from the following examples. These examples are intended to be illustrative in nature and are not considered to be limiting the scope of the invention. EXAMPLE SET 1: Materials PVC compounds were produced on standard extrusion equipment blending a 70K PVC resin with a standard additive package of heat stabilizers, UV stabilizers, antioxidants, antimicrobial additives, lubricants, and fillers. The formulations were plasticized with the following additives: - Low molecular weight phthalate plasticizers, such as Palatinol 91 IP (DPHP, BASF) and Jay flex™ DINP (Exxon Mobil); - Epoxidized linseed oil (ELO) and epoxidized soybean oil (ESO) (Arkema); - High molecular weight ketone ethylene esters (KEE, ELVALOY™ 741 & ELVALOY™ HP662, DOW); - High molecular weight ethylene vinyl acetate copolymers, ATEVA 1821A(18% Vinyl Acetate, MFI 3 g / 10 min (190°C, 2.16kg), Celanese), ATEVA 4030AC (40% Vinyl Acetate, MFI 55 g / 10 min (190°C, 2.16kg), Celanese), Elvax 40L-03 (40% Vinyl Acetate, MFI 3 g / 10 min (190°C, 2.16kg), Dow), Baymod L 6515 VP (65% Vinyl Acetate, MFI 4 g / 10 min (190°C, 2.16kg), Arlanxeo), Baymod L 6520 SP (65% Vinyl Acetate, Arlanxeo). - Acrylic vinyl copolymer, polyacrylate content 50%, Vinnolit K 707 E. 1) Compatibility of an EVA containing copolymer in PVC formulations with KEE as compatibility agent a) Test formulations: Plasticizer DINP COMPARATIVE EXAMPLE 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 PHR* PHR PHR PHR 25 25 25 25 ESO 6 6 6 6 KEE (Elvaloy 741) 40 29 20 11 EVA (ATEVA 1821 A) 11 20 29 5              *Parts per hundred resin by weight b) Properties of the compounds: Properties COMPARATIVE EXAMPLE 1 EXAMPLE 1 EXAMPLE 2 EXAMPLE 3 Hardness Shore A (Instant 15 Sec) 84 89 92 92 Specific Gravity (g / cmA3) 1.34 1.33 1.33 1.32 Tensile Strength (psi) 2,700 2,600 1,800 1,300 Modulus (psi) 2,500 3,800 5,300 9,700 Tensile Strain (%) 380 330 200 120 Brittle Point Degree C -34 -21 4 4 Capillary Viscosity @190C, Shear rate 100 (1 / s) 840 940 820 750 The EVA had a VA content of 18% and a melting point of 87°C. Alone, it has very poor 10 compatibility with PVC. However, when replacing 11 PHR of KEE (total 40 PHR) with EVA in the formula (EXAMPLE 1), the compound had increased hardness, increased modulus, slightly reduced tensile strength and elongation, and lower temperature resistance. Thus, for certain applications, when low temperature performance is not critical and harder or less flexible properties are required, KEE can be partially replaced by EVA with the advantage of lower cost. 15 Further increasing the EVA loading in the compounds while lowering the KEE content yields poor properties (EXAMPLES 2 and 3). 2) Test compatibility of EVA (40% VA) in PVC formulations with KEE as compatibility agent a) Test formulations Plasticizer COMPARATIVE EXAMPLE 2 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 PHR PHR PHR PHR DPHP 29 - - - ELO 2 - ESO - 8 10 12 KEE (Elvaloy 741) 51 51 51 51 EVA (Elvax 40L-03) - 45 41 37 COMPARATIVE EXAMPLE 2 contains phthalate liquid plasticizer. In EXAMPLES 4-6, the liquid phthalate plasticizer was replaced with EVA and ESO at various ratios. Liner samples were made on a 1” extruder with process temperature from 340°F to 38O°F. The compounds were extrusion-coated on both sides of a polyester scrim with a coating thickness is 10 about 26mil on the back and 24mil on the face. b) Properties of the compounds Physical Properties Properties COMPARATIVE EXAMPLE 2 EXAMPLE 4 EXAMPLE 5 EXAMPLE 6 Hardness Shore A 76 90 88 86 Tensile Strength (psi) 3,700 3,700 3,900 3,700 Tensile Strain (%) 300 260 270 270 Capillary Viscosity @ 190C, Shear rate 100 (1 / s) 970 970 1,050 1,100 Tg (DSC), °C -13 -27 -28 -29 Tm (DSC), °C 43 43 43 43 When using non-phthalate plasticizers as dominant plasticizers in the PVC formulas, increased compound hardness and melt viscosity were observed. The decreased Tg of the test compounds means that the EVA / KEE / ESO plasticizing system produced good low temperature performance. 5 The single melting peak of the compounds from DSC analysis shows that the EVA (40% VA) and KEE did not form separate domains, or the domains are not big enough to be identified by DSC. The increased tensile strength of EXAMPLES 4-6 further demonstrates that the plasticizing system KEE / EVA / ESO is very compatible. 10          c) Properties of the liners coated with the compounds Property Unit Method Orientation CEX2 EX 4 EX 5 EX 6 Avg Avg Avg Avg Weight oz / sq yd - - 45.3 45.3 44.7 45.9 Thickness mil caliper - 48.5 49.3 48.2 50.3 Tensile Strength, Grab lbs ASTM D751, Grab warp 302 329 331 334 fill 378 360 367 369 Elongation, Grab % ASTM D751, Grab warp 33.0 32.4 30.4 34.4 fill 33.0 31.3 32.0 32.3 Puncture lbs ASTM D751 Screwdriver 94 90 91 96 Ball 480 463 444 450 Hydrostatic Resistance psi ASTM D751 - 576 601 593 594 Low Temp Bend, -30F Pass / Fail ASTM D2136 warp, face Fail (0 of 5) Pass (4 of 5) Pass (5 of 5) Fail (2 of 5) fill, face Fail (0 of 5) Fail (0 of 5) Fail (0 of 5) Fail (0 of 5) The low temperature bend test results of EX 4-6 are better than CEX 2, which is consistent with the Tg measurements of the compounds with the Tg of EX 4-6 being lower than Tg of CEX 2. 3) Test compatibility of EVA (40% VA) in PVC formulations with KEE as compatibility agent a) Test formulas (Test-4 formula is the control in this experiment) Name CEX2 EX7 EX8 EX9 PHR PHR PHR DPHP 29 - ELO 2 - - - ESO - 15 15 15 KEE 51 51 51 51 EVA (Elvax 40L-03) - 40 50 60 b) Properties of the compounds Physical Properties Property lillll Orientation CEX 2 ■■■■ liiMiill ■■iiB iillMiil® Hardness, Shore A, 15 s llliilllll 80 llliilllll Dogbone Tensile psi ASTMD412 warp 3,200 2,500 2,100 1,600 fill 2,600 1,600 1,400 900 Dogbone Elongation llijjl ililBiilil 250 1111^111111 illliililill lliiillliis 400 290 lillllli 15 The tensile and the elongation results of EX 7-9 are lower than CEX 2, which may indicate that the plasticizer systems formed by the combination of ELO / KEE / EVA at increasing levels of ESO and / or EVA with 40%VA content are not as effective as the control example with the liquid phthalate plasticizer and EX 4-6. 20 4) Test compatibility of EVA (40% VA) in PVC formulations with KEE as compatibility agent a) Test formulas Name CEX2 EX10 EX11 PHR PHR PHR DPHP 29 ELO 2 ESO - 10 10 KEE (ELVALOY 741) 51 57 43 EVA (ATEVA 4030AC) - 68 83 b) Properties of the compounds: Property Orientation EX 10 EX 11 liiiiii ililM Dogbone Tensile llltlMillll 1,100 llliisill iisiiiiiiii 2.600 iiiiiiiii 560 Dogbone Elongation % ASTM D412 warp 340 100 60 fill 400 80 40 10 The grade ATEVA 430AC used in EX 10 and 11 had a higher melt flow index and lower viscosity than the EVA Elvax 40L-03 that was used in EX 3-9, which caused process problems during compounding and extrusion due to the stickiness of the material and the compound. The lower tensile strength and lower elongation of EX 10 and 11 reconfirmed that high levels of EVA and / or low molecular weight of the EVA (high MFI) are detrimental to the properties of the 15 final products. 5) Test compatibility of EVA 65% VA in PVC formulations with No KEE Test Formulations: CEX3 EX12 EX13 Plasticizer PHR PHR PHR DINP 27 30 30 ELO 3 3 3 KEE (Elvaloy741) 38 EVA (Baymod L 6515 VP) 47 EVA (Baymod L 6520 SP) 52 Properties of the compounds Property CEX 3 EX 12 EX 13 Fusion Time [mini 34 45 46 Shear viscosity at shear rate 100 s'1 [Pa.sl 1,010 1,240 1,160 Properties of the coated fabrics using the compounds Property Unit Method Orientation CEX 3 EX 12 EX13 Hardness - Shore A, 15s - 78 84 81 Specific Gravity - - 1.385 1.403 1.397 Tensile strength, grab lbs ASTM D751, grab warp 334 347 317 fill 361 383 372 Elongation, grab % ASTM D751, grab warp 36 33 33 fill 34 34 32 Puncture, screwdriver lbs ASTM D751 - 91 96 93 Low T Bend, 4hrs @ -40C Pass / Fail ASTM 2136 warp, face Fail (0 of 5) Fail (0 of 5) Fail (0 of 5) fill, face Fail (0 of 5) Fail (0 of 5) Fail (0 of 5) warp, back Pass (4 of 5) Pass (5 of 5) Pass (4 of 5) warp, face Fail (0 of 5) Fail (Oof 5) Fail (0 of 5) The physical properties of EX 12 and 13 were comparable to CEX 3. These data demonstrate that it is possible to eliminate all phthalate plasticizer when combining ELO, KEE, and EVA with a high enough % of VA. EXAMPLE SET 2: Test Formulations: A series of materials were prepared using an aery lie-grafted-PVC as summarized in the 5 table below. In accordance with one or more embodiments, none of these test materials included a liquid plasticizer. In accordance with some embodiments, EX 14, 15, 17 and 18 did not contain Elvaloy. In accordance with certain non-limiting embodiments, EX 14, 15, 17 and 18 also do not contain KEE. CEX4 EX 14 EX 15 EX 16 EX 17 EX 18 EX 19 EX 20 EX 21 Ingredient PHR PHR PHR PHR PHR PHR PHR PHR PHR ACR-co-PVC 84 84 84 82 80 75 75 78 EVA (Baymod L6515VP) 16 16 8 18 20 Elvaloy 741 60 8 20 15 17 DPHP 24 ESO 5 10 5 5 5 5 10 5 ELO 2 10 Properties of the coated fabrics using the compounds: Property Unit Method Orientation CEX4 EX 14 EX 15 EX 16 EX 17 EX 18 EX 19 EX 20 EX 21 Capillary Viscosity [Pa.s] 190°C / 100 s 1 - 1,120 2,460 2,050 2,300 2,400 1,970 1,890 1,720 2,090 Tensile Strength [psi] ASTM D751 Warp 3,420 2,420 2,160 2,250 2,430 2,040 1,920 1,870 1,950 Fill 2,660 1,990 1,780 1,730 1,850 1,560 1,480 1,580 1,660 Tensile elongation [%] ASTM D751 Warp 300 200 220 220 210 230 220 230 210 Fill 340 230 250 230 220 250 240 280 250 Flexural modulus [psi] ASTM D747 Warp 3,390 6,850 2,130 2,760 4,810 1,950 1,810 1,370 2,040 Fill 2,690 5,250 1,540 2,460 3,300 1,740 1,770 1,290 1,680 Tm [°C] DSC - 164 145 151 140 153 122 130 130 128 Tg -12 -15 -18 -16 -16 -19 -17 -23 -19 FusionTime [min] Brabender 205°C / 30rpm - 21 22 23 21 23 22 23 25 22 Examples 14, 15, 17 and 18 do not contain any low molecular weight phthalate or terephthalate plasticizers. Because the base material ACR-co-PVC is a graft copolymer, which is 15 inherently plasticized, even no KEE is required, and the total EVA content can be decreased while maintaining a tensile strength larger than 1,500 psi and maintaining a Tg below -10°C. When using KEE, the amount of EVA can further be reduced (EX 16) or eliminated (EX 19-21). The phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. As used herein, the term “plurality” refers to two or more items or components. The terms “comprising,” “including,” “carrying,” “having,” “containing,” and “involving,” whether in the written description or the claims and the like, are open-ended terms, i.e., to mean “including but not limited to.” Thus, the use of such terms is meant to encompass the items listed thereafter, and equivalents thereof, as well as additional items. Only the transitional phrases “consisting of’ and “consisting essentially of,” are closed or semi-closed transitional phrases, respectively, with respect to the claims. Use of ordinal terms such as “first,” “second,” “third,” and the like in the claims to modify a claim element does not by itself connote any priority, precedence, or order of one claim element over another or the temporal order in which acts of a method are performed, but arc used merely as labels to distinguish one claim element having a certain name from another element having a same name (but for use of the ordinal term) to distinguish the claim elements. Having thus described several aspects of at least one embodiment, it is to be appreciated various alterations, modifications, and improvements will readily occur to those skilled in the art. Any feature described in any embodiment may be included in or substituted for any feature of any other embodiment. Such alterations, modifications, and improvements are intended to be part of this disclosure and are intended to be within the scope of the invention. Accordingly, the foregoing description and drawings are by way of example only. Those skilled in the art should appreciate that the parameters and configurations described herein are exemplary and that actual parameters and / or configurations will depend on the specific application in which the disclosed methods and materials are used. Those skilled in the art should also recognize or be able to ascertain, using no more than routine experimentation, equivalents to the specific embodiments disclosed. What is claimed is:

Claims

1. A polyvinyl chloride (PVC) coated membrane, comprising:a scrim coated with a composition comprising:PVC resin blended with a plasticizer, the plasticizer comprising an ethylene-vinyl acetate (EVA) containing copolymer with a VA content of at least about 35%, the plasticizer comprising substantially no ketone ethylene ester (KEE).

2. The membrane of claim 1, wherein the EVA containing copolymer has a VA content of at least about 40%, the plasticizer having an EVA containing copolymer content of less than about 55 PHR by weight.

3. The membrane of claim 2, wherein the EVA containing copolymer has a VA content of at least about 45%.

4. The membrane of claim 3, wherein the EVA containing copolymer has a VA content of at least about 50%.

5. The membrane of claim 4, wherein the EVA containing copolymer has a VA content of at least about 60%, the plasticizer having an EVA containing copolymer content of at least about 15 PHR by weight.

6. The membrane of claim 5, wherein the EVA containing copolymer has a VA content of at least about 60%, the plasticizer having an EVA containing copolymer content of at least about 30 PHR by weight.

7. The membrane of claim 4, wherein the EVA containing copolymer has a VA content of about 65%.

8. The membrane of claim 1, wherein the plasticizer comprises the EVA containing copolymer at a content of about 40 PHR to about 50 PHR, and the EVA containing copolymer has a VA content of about 60 to about 70%.

9. A polyvinyl chloride (PVC) coated membrane, comprising:a scrim coated with a composition comprising:PVC resin blended with a plasticizer, the plasticizer comprising an ethylene-vinyl acetate (EVA) containing copolymer at a content of at least about 10 PHR by weight and ketone ethylene ester (KEE) at a content of less than about 60 PHR by weight.

10. The membrane of claim 9, wherein the EVA containing copolymer has a VA content of less than about 45%.

11. The membrane of claim 9, wherein the EVA containing copolymer has a VA content of at least about 15%.

12. The membrane of claim 11, wherein the EVA containing copolymer has a VA content of about 18% to about 45%.

13. The membrane of claim 12, wherein the plasticizer comprises less than about 20 PHR of an EVA containing copolymer having a VA content of less than about 20%.

14. The membrane of claim 12, wherein the plasticizer comprises less than about 20 PHR of an EVA containing copolymer having a VA content of about 18%.

15. The membrane of claim 14, wherein the plasticizer comprises about 10 PHR to about 20 PHR of an EVA containing copolymer having a VA content of about 18%.

16. The membrane of claim 15, wherein the total content of the EVA containing copolymer and KEE is about 40 PHR by weight.

17. The membrane of claim 12, wherein the plasticizer comprises about 30 PHR to about 50 PHR of an EVA containing copolymer having a VA content of about 40%.

18. The membrane of claim 9, wherein the composition further comprises epoxidized soybean oil (ESO) or epoxidized linseed oil (ELO).

19. The membrane of claim 18, wherein the composition comprises ESO or ELO at a content of at least about 5 PHR by weight.

20. The membrane of claim 19, wherein the composition comprises ESO or ELO at a content of less than about 15 PHR by weight.

21. The membrane of claim 9, wherein the plasticizer comprises substantially no substituted phthalate or terephthalate esters having a molecular weight of less than about 450 g / mole.

22. The membrane of claim 9, wherein the plasticizer comprises substantially no compound(s) having a molecular weight of less than about 900 g / mole.

23. The membrane of claim 9, wherein the EVA containing copolymer is characterized by a melt flow index of below about 55 g / lOmin.

24. A polyvinyl chloride (PVC) coated membrane, comprising:a scrim coated with a composition comprising:an aery lie-grafted-PVC (ACR-co-PVC) resin blended with a plasticizer, the plasticizer optionally comprising a ketone ethylene ester (KEE) but comprising substantially no ethylene-vinyl acetate (EVA) containing copolymer and substantially no liquid phthalate plasticizer.

25. The membrane of any of the preceding claims, wherein the PVC is a ACR-co-PVC.

26. The membrane of any of the preceding claims, wherein the coating does not include any liquid phthalate plasticizer.

27. The membrane of any of the preceding claims, wherein the coating does not contain any ketone ethylene ester (KEE) plasticizer.

28. The membrane of any of the preceding claims, wherein the coating does not include any ketone ethylene ester (KEE) plasticizer and does not include any liquid phthalate plasticizer.

29. The membrane of any of the preceding claims, wherein the scrim is extrusion coated on both sides with the composition.

30. The membrane of any of the preceding claims, wherein the composition further comprises a filler, a processing aid, a stabilizer, a lubricant, or a pigment.

31. The membrane of any of the preceding claims, exhibiting chemical resistance to oil, fuel, acid, brine, base, solvent and / or biogas.

32. The membrane of any of the preceding claims, exhibiting thermal or UV resistance.

33. The membrane of any of the preceding claims, characterized by a tensile strength of at least about 1000 PSI.

34. The membrane of any of the preceding claims, characterized by a flexural modulus of at least about 1000 PSI.

35. The membrane of any of the preceding claims, characterized by a flexural modulus of at least about 3000 PSI.

36. A reservoir liner or cover comprising the PVC coated membrane of any of the preceding claims.

37. The reservoir liner or cover of claim 36, compatible with potable and non-potable water containment applications.

38. The reservoir liner or cover of claim 36, configured for primary or secondary containment.

39. The reservoir liner or cover of claim 36, wherein the reservoir liner or cover comprises5 substantially no liquid monomeric phthalate plasticizer.

40. The reservoir liner or cover of claim 36, wherein the reservoir liner or cover comprises substantially no ketone ethylene ester (KEE) plasticizer.10   41. A waterproof roofing membrane comprising the PVC coated membrane of any of thepreceding claims.

42. The waterproof roofing membrane of claim 41, wherein the waterproof roofing membrane comprises substantially no liquid monomeric phthalate plasticizer.1543. The waterproof roofing membrane of claim 41, wherein the waterproof roofing membrane comprises substantially no ketone ethylene ester (KEE) plasticizer.