Polymer compositions and applications of polymer plasticizers incorporating the polymer compositions

Abstract

This disclosure provides embodiments of quaternary copolymer compositions. In these embodiments, the quaternary copolymer composition may have the formula E / P / X / CO, comprising 25% to 90% by weight ethylene (E), 0.1% to 5.0% by weight propylene (P), 5% to 40% by weight alkyl acrylate (X), and 3% to 30% by weight carbon monoxide (CO). X may be selected from the group consisting of vinyl acetate or n-butyl acrylate. When measured according to ASTM 1238 at 2.16 kg and 190°C, the quaternary copolymer composition may have a melt index I2 of 10 g / 10 min to 1,000 g / 10 min. Additionally, this disclosure provides embodiments of polymer formulations comprising the quaternary copolymer composition and polyvinyl chloride.

Description

TECHNICAL FIELD

[0001] The embodiments described herein generally relate to polymers, and specifically to tetrapolymer compositions for use in plasticizer applications. BACKGROUND

[0002] Polyvinyl chloride (PVC) is one of the most commonly used polymers. PVC polymers are halogen vinyl polymers, which can be further classified as “rigid” (unplasticized) PVC polymers or “flexible” (plasticized) PVC polymers depending on their stiffness. As such, flexible PVC polymers are softer and more easily bendable than rigid PVC polymers. Flexible PVC polymers are commonly used in building applications as insulation on electrical wires, house flooring, roofing materials, and geomembrane applications. SUMMARY

[0003] Conventionally, flexible PVC applications utilize PVC polymers that require plasticizers to soften the PVC enough to become flexible and elastomeric. For example, phthalate-based liquid plasticizers are commonly used plasticizers for flexible PVC applications. However, due to the small molecule nature of phthalate-based liquid plasticizers, phthalate-based liquid plasticizers migrate out of the PVC polymer over time, leading to degradation in performance of the flexible PVC polymer.

[0004] To address the migration issue, polymeric plasticizers can be applied to replace the phthalate-based plasticizers. However, studies have shown that polymeric plasticizers can have lower plasticizing efficiency than conventional phthalate-based plasticizers. As such, higher amounts of polymeric plasticizers can be required to achieve the desired softness or flexibility in the overall PVC polymer formulation.

[0005] Accordingly, there is a need for alternative compositions that have flexible and elastomeric properties that exhibit improved plasticizing efficiency when used as plasticizers in PVC polymer formulations compared to conventional polymeric plasticizers.

[0006] Embodiments of the present disclosure address those needs by providing compositions comprising tetrapolymer that can exhibit improved flexible and elastomeric properties when compared to conventional polymeric plasticizers. As such, the tetrapolymer compositions described herein can allow for the polymer formulation to maintain performance properties or have increased resistance to failure modes such as rutting or fatigue cracking under various temperature regimes when used in flexible PVC polymer formulations.

[0007] According to at least one embodiment of the present disclosure, a tetrapolymer composition is provided. In embodiments, the tetrapolymer composition can have the formula E / P / X / CO, the tetrapolymer composition can include 25 wt% to 90 wt% ethylene (E), 0.1 wt% to 5.0 wt% propylene (P), 5 wt% to 40 wt% alkyl acrylate (X), and 3 wt% to 30 wt% carbon monoxide (CO). X can be selected from the group consisting of vinyl acetate or n-butyl acrylate. The tetrapolymer composition can have a melt index, I2, of 10 g / 10 min to 1,000 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190 °C.

[0008] According to at least one embodiment of the present disclosure, a tetrapolymer composition is provided. In embodiments, the tetrapolymer composition can have the formula E / P / X / CO, the tetrapolymer composition can include 25 wt% to 90 wt% ethylene (E), 0.1 wt% to 5.0 wt% propylene (P), 5 wt% to 40 wt% alkyl acrylate (X), and 3 wt% to 30 wt% carbon monoxide (CO). X can be selected from the group consisting of vinyl acetate or n-butyl acrylate. The tetrapolymer composition can have a melt index, I2, of 10 g / 10 min to 1,000 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190 °C.

[0009] These and other embodiments are described in more detail in the detailed description below. DETAILED DESCRIPTION

[0010] Specific embodiments of the application will now be described. These embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the subject matter to those skilled in the art.

[0011] The term “polymer” refers to a polymeric compound prepared by polymerizing monomers, either of the same or a different type. Thus, the general term polymer encompasses the term “homopolymer,” which generally refers to a polymer prepared from only one type of monomer, and “copolymer,” which refers to a polymer prepared from two or more different monomers. The term “interpolymer” as used herein means a polymer prepared by the polymerization of at least two different types of monomers. Thus, the general term interpolymer includes copolymers or polymers prepared from more than two different types of monomers, such as terpolymers and tetrapolymers.

[0012] “Polyethylene” or “ethylene-based polymer” shall mean a polymer comprising greater than 50 mole percent of units derived from ethylene monomer. This includes ethylene-based homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene-based polymers known in the art include, but are not limited to: low density polyethylene (LDPE); linear low density polyethylene (LLDPE); ultra low density polyethylene (ULDPE); very low density polyethylene (VLDPE); single-site catalyzed linear low density polyethylene, including both linear low density resins and substantially linear low density resins (m-LLDPE); medium density polyethylene (MDPE); and high density polyethylene (HDPE).

[0013] As used herein, the term “propylene-based polymer” refers to a polymer in polymeric form that means a polymer comprising greater than 50 mole percent of units that have been derived from propylene monomer. This includes propylene homopolymers, polypropylene random copolymers, impact copolymer polypropylenes, propylene / alpha olefin copolymers, and propylene / alpha olefin copolymers.

[0014] Reference will now be made in detail to embodiments of the polymer composition as described herein. Embodiments of the polymer composition can include a tetrad copolymer composition represented by the formula E / P / X / CO, the tetrad copolymer composition including polymer units E, P, X, and CO. According to at least one embodiment of the present disclosure, the tetrad copolymer composition can have the formula E / P / X / CO, the tetrad copolymer composition can include from 25 wt% to 90 wt% of ethylene (E), from 0.1 wt% to 5.0 wt% of propylene (P), from 5 wt% to 40 wt% of alkyl acrylate (X), and from 3 wt% to 30 wt% of carbon monoxide (CO). X can be selected from the group consisting of vinyl acetate or n-butyl acrylate. The tetrad copolymer composition can have a melt index, I2, of from 10 grams per 10 minutes (g / 10 min) to 1,000 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190°C.

[0015] In embodiments, E can be a polymer unit derived from ethylene monomer - (CH2CH2)-. The tetrapolymer composition can comprise 25 wt% to 90 wt%, 25 wt% to 80 wt%, 25 wt% to 70 wt%, 25 wt% to 60 wt%, 25 wt% to 50 wt%, 25 wt% to 40 wt%, 25 wt% to 30 wt%, 30 wt% to 90 wt%, 30 wt% to 80 wt%, 30 wt% to 70 wt%, 30 wt% to 60 wt%, 30 wt% to 50 wt%, 30 wt% to 40 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 40 wt% to 50 wt%, 50 wt% to 90 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, 50 wt% to 60 wt%, 60 wt% to 90 wt%, 60 wt% to 80 wt%, 60 wt% to 70 wt%, 70 wt% to 90 wt%, 70 wt% to 80 wt%, or 80 wt% to 90 wt% E, based on the total weight of the tetrapolymer.

[0016] In embodiments, P can be a polymer unit derived from propylene monomer. The tetrapolymer composition can comprise 0.1 wt% to 5 wt%, 0.1 wt% to 4 wt%, 0.1 wt% to 3 wt%, 0.1 wt% to 2 wt%, 0.1 wt% to 1 wt%, 0.1 wt% to 0.5 wt%, 0.5 wt% to 5 wt%, 0.5 wt% to 4 wt%, 0.5 wt% to 3 wt%, 0.5 wt% to 2 wt%, 0.5 wt% to 1 wt%, 1 wt% to 5 wt%, 1 wt% to 4 wt%, 1 wt% to 3 wt%, 1 wt% to 2 wt%, 2 wt% to 5 wt%, 2 wt% to 4 wt%, 2 wt% to 3 wt%, 3 wt% to 5 wt%, 3 wt% to 4 wt%, or 4 wt% to 5 wt% P, based on the total weight of the tetrapolymer.

[0017] In embodiments, X can be a polymer unit comprising an alkyl acrylate. In further embodiments, X can be a polymer unit selected from the group consisting of vinyl acetate or n-butyl acrylate. The tetrapolymer composition can comprise 5 to 40 wt%, 5 to 35 wt%, 5 to 30 wt%, 5 to 25 wt%, 5 to 20 wt%, 5 to 15 wt%, 5 to 10 wt%, 10 to 40 wt%, 10 to 35 wt%, 10 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 15 to 40 wt%, 15 to 35 wt%, 15 to 30 wt%, 15 to 25 wt%, 15 to 20 wt%, 20 to 40 wt%, 20 to 35 wt%, 20 to 30 wt%, 20 to 25 wt%, 25 to 40 wt%, 25 to 35 wt%, 25 to 30 wt%, 30 to 40 wt%, 30 to 35 wt%, or 35 to 40 wt% of X based on the total weight of the tetrapolymer.

[0018] In embodiments, CO can be a polymer unit derived from a comonomer comprising carbon monoxide. The tetrapolymer composition can comprise 3 to 30 wt%, 3 to 25 wt%, 3 to 20 wt%, 3 to 15 wt%, 3 to 10 wt%, 3 to 5 wt%, 5 to 30 wt%, 5 to 25 wt%, 5 to 20 wt%, 5 to 15 wt%, 5 to 10 wt%, 10 to 30 wt%, 10 to 25 wt%, 10 to 20 wt%, 10 to 15 wt%, 15 to 30 wt%, 15 to 25 wt%, 15 to 20 wt%, 20 to 30 wt%, 20 to 25 wt%, 25 to 30 wt%, or 25 to 30 wt% of CO based on the total weight of the tetrapolymer.

[0019] In embodiments, the tetrapolymer composition can have a melt index, I2, of 10 grams per 10 minutes (g / 10 min) to 1,000 g / 10 min, 10 g / 10 min to 800 g / 10 min, 10 g / 10 min to 600 g / 10 min, 10 g / 10 min to 400 g / 10 min, 10 g / 10 min to 200 g / 10 min, 10 g / 10 min to 100 g / 10 min, 10 g / 10 min to 50 g / 10 min, 50 g / 10 min to 1,000 g / 10 min, 50 g / 10 min to 800 g / 10 min, 50 g / 10 min to 600 g / 10 min, 50 g / 10 min to 400 g / 10 min, 50 g / 10 min to 200 g / 10 min, 50 g / 10 min to 100 g / 10 min, 100 g / 10 min to 1,000 g / 10 min, 100 g / 10 min to 800 g / 10 min, 100 g / 10 min to 600 g / 10 min, 1,00 g / 10 min to 400 g / 10 min, 100 g / 10 min to 200 g / 10 min, 200 g / 10 min to 1,000 g / 10 min, 200 g / 10 min to 800 g / 10 min, 200 g / 10 min to 600 g / 10 min, 200 g / 10 min to 400 g / 10 min, 400 g / 10 min to 1,000 g / 10 min, 400 g / 10 min to 800 g / 10 min, 400 g / 10 min to 600 g / 10 min, 600 g / 10 min to 1,000 g / 10 min, 600 g / 10 min to 800 g / 10 min, or 800 g / 10 min to 1,000 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190 °C.

[0020] In embodiments, the tetrapolymer composition can have a storage modulus of 0.1 MPa to 100 MPa, 0.1 MPa to 75 MPa, 0.1 MPa to 50 MPa, 0.1 MPa to 25 MPa, 0.1 MPa to 1.0 MPa, 1.0 MPa to 100 MPa, 1.0 MPa to 75 MPa, 1.0 MPa to 50 MPa, 1.0 MPa to 25 MPa, 25 MPa to 100 MPa, 25 MPa to 75 MPa, 25 MPa to 50 MPa, 50 MPa to 100 MPa, 50 MPa to 75 MPa, or 75 MPa to 100 MPa. In other embodiments, the tetrapolymer composition can have a storage modulus of 1.0 MPa to 10 MPa, 1.0 MPa to 9.0 MPa, 1.0 MPa to 8.0 MPa, 1.0 MPa to 7.0 MPa, 1.0 MPa to 6.0 MPa, 1.0 MPa to 5.0 MPa, 1.0 MPa to 4.0 MPa, 1.0 MPa to 3.0 MPa, 1.0 MPa to 2.0 MPa, 2.0 MPa to 10.0 MPa, 2.0 MPa to 9.0 MPa, 2.0 MPa to 8.0 MPa, 2.0 MPa to 7.0 MPa, 2.0 MPa to 6.0 MPa, 2.0 MPa to 5.0 MPa, 2.0 MPa to 4.0 MPa, 2.0 MPa to 3.0 MPa, 3.0 MPa to 10.0 MPa, 3.0 MPa to 9.0 MPa, 3.0 MPa to 8.0 MPa, 3.0 MPa to 7.0 MPa, 3.0 MPa to 6.0 MPa, 3.0 MPa to 5.0 MPa, 3.0 MPa to 4.0 MPa, 4.0 MPa to 10.0 MPa, 4.0 MPa to 9.0 MPa, 4.0 MPa to 8.0 MPa, 4.0 MPa to 7.0 MPa, 4.0 MPa to 6.0 MPa, 4.0 MPa to 5.0 MPa, 5.0 MPa to 10.0 MPa, 5.0 MPa to 9.0 MPa, 5.0 MPa to 8.0 MPa, 5.0 MPa to 7.0 MPa, 5.0 MPa to 6.0 MPa, 6.0 MPa to 10.0 MPa, 6.0 MPa to 9.0 MPa, 6.0 MPa to 8.0 MPa, 6.0 MPa to 7.0 MPa, 7.0 MPa to 10.0 MPa, 7.0 MPa to 9.0 MPa, 7.0 MPa to 8.0 MPa, 8.0 MPa to 10.0 MPa, 8.0 MPa to 9.0 MPa, or 9.0 MPa to 9.5 MPa, when measured at 20°C according to ASTM D1708.

[0021] In embodiments, the quaternary copolymer composition can have a melting temperature of 30°C to 80°C, 30°C to 75°C, 30°C to 70°C, 30°C to 65°C, 30°C to 60°C, 30°C to 55°C, 30°C to 50°C, 30°C to 45°C, 30°C to 40°C, 30°C to 35°C, 35°C to 80°C, 35°C to 75°C, 35°C to 70°C, 35°C to 65°C, 35°C to 60°C, 35°C to 55°C, 35°C to 50°C, 35°C to 45°C, 35°C to 40°C, 40°C to 80°C, 40°C to 75°C, 40°C to 70°C, 40°C to 65°C, 40°C to 60°C, 40°C to 55°C, 40°C to 50°C, 40°C to 45°C, 45°C to 80°C, 45°C to 75°C, 45°C to 70°C, 45°C to 65°C, 45°C to 60°C, 45°C to 55°C, 45°C to 50°C, 50°C to 80°C, 50°C to 75°C, 50°C to 70°C, 50°C to 65°C, 50°C to 60°C, 50°C to 55°C, 55°C to 80°C, 55°C to 75°C, 55°C to 70°C, 55°C to 65°C, 55°C to 60°C, 60°C to 80°C, 60°C to 75°C, 60°C to 70°C, 60°C to 65°C, 65°C to 80°C, 65°C to 75°C, 65°C to 70°C, 70°C to 80°C, 70°C to 75°C, or 75°C to 80°C.

[0022] In embodiments, the quaternary copolymer composition can have a crystallization temperature of 20°C to 70°C, 20°C to 65°C, 20°C to 60°C, 20°C to 55°C, 20°C to 50°C, 20°C to 45°C, 20°C to 40°C, 20°C to 35°C, 20°C to 30°C, 20°C to 25°C, 25°C to 70°C, 25°C to 65°C, 25°C to 60°C, 25°C to 55°C, 25°C to 50°C, 25°C to 45°C, 25°C to 40°C, 25°C to 35°C, 25°C to 30°C, 30°C to 70°C, 30°C to 65°C, 30°C to 60°C, 30°C to 55°C, 30°C to 50°C, 30°C to 45°C, 30°C to 40°C, 30°C to 35°C, 35°C to 70°C, 35°C to 65°C, 35°C to 60°C, 35°C to 55°C, 35°C to 50°C, 35°C to 45°C, 35°C to 40°C, 40°C to 70°C, 40°C to 65°C, 40°C to 60°C, 40°C to 55°C, 40°C to 50°C, 40°C to 45°C, 45°C to 70°C, 45°C to 65°C, 45°C to 60°C, 45°C to 55°C, 45°C to 50°C, 50°C to 70°C, 50°C to 65°C, 50°C to 60°C, 50°C to 55°C, 55°C to 70°C, 55°C to 65°C, 55°C to 60°C, 60°C to 70°C, 60°C to 65°C, or 65°C to 70°C.

[0023] In embodiments, the tetrapolymer composition can have a heat of fusion of 10 J / g to 100 J / g, 10 J / g to 90 J / g, 10 J / g to 80 J / g, 10 J / g to 70 J / g, 10 J / g to 60 J / g, 10 J / g to 50 J / g, 10 J / g to 40 J / g, 10 J / g to 30 J / g, 10 J / g to 20 J / g, 20 J / g to 100 J / g, 20 J / g to 90 J / g, 20 J / g to 80 J / g, 20 J / g to 70 J / g, 20 J / g to 60 J / g, 20 J / g to 50 J / g, 20 J / g to 40 J / g, 20 J / g to 30 J / g, 30 J / g to 100 J / g, 30 J / g to 90 J / g, 30 J / g to 80 J / g, 30 J / g to 70 J / g, 30 J / g to 60 J / g, 30 J / g to 50 J / g, 30 J / g to 40 J / g, 40 J / g to 100 J / g, 40 J / g to 90 J / g, 40 J / g to 80 J / g, 40 J / g to 70 J / g, 40 J / g to 60 J / g, 40 J / g to 50 J / g, 50 J / g to 100 J / g, 50 J / g to 90 J / g, 50 J / g to 80 J / g, 50 J / g to 70 J / g, 50 J / g to 60 J / g, 60 J / g to 100 J / g, 60 J / g to 90 J / g, 60 J / g to 80 J / g, 60 J / g to 70 J / g, 70 J / g to 100 J / g, 70 J / g to 90 J / g, 70 J / g to 80 J / g, 80 J / g to 100 J / g, 80 J / g to 90 J / g, or 90 J / g to 100 J / g.

[0024] Embodiments of polymer formulations comprising the quaternary copolymer composition will now be described. In embodiments, the polymer formulations comprising the quaternary copolymer composition described herein can further comprise a halogen vinyl polymer. A halogen vinyl polymer is a homopolymer or copolymer of vinyl chloride or vinylidene chloride. In embodiments, the polymer formulations comprising the quaternary copolymer composition described herein can further comprise poly(vinyl chloride) (PVC). Poly(vinyl chloride) (PVC) can be further classified as a “rigid” PVC polymer or a “flexible” PVC polymer according to its stiffness. Flexible PVC polymers can have a modulus of less than 100,000 psi (690 MPa), and rigid PVC polymers can have a modulus of greater than 100,000 psi (690 MPa), for example between 100,000 psi and 1,000,000 psi (690 MPa and 6,900 MPa). The distinction between flexible and rigid PVC polymers can be primarily in the presence and amount of plasticizer in the resin. Flexible PVC polymers generally have improved processability, lower tensile strength, and higher elongation compared to rigid PVC polymers. In embodiments, the polymer formulations described herein comprising the quaternary copolymer composition and polyvinyl chloride can be classified as flexible PVC polymers. In some embodiments, the poly(vinyl chloride) polymer can have a K- value of 60 to 80, 60 to 75, 60 to 70, 60 to 65, 65 to 80, 65 to 75, 65 to 70, 70 to 80, 70 to 75, or 75 to 80.

[0025] In embodiments, the polymer formulation can comprise 40 wt% to 99 wt% polyvinyl chloride based on the total weight of the polymer formulation. In further embodiments, the polymer formulation can comprise 40 wt% to 95 wt%, 40 wt% to 90 wt%, 40 wt% to 80 wt%, 40 wt% to 70 wt%, 40 wt% to 60 wt%, 40 wt% to 50 wt%, 50 wt% to 99 wt%, 50 wt% to 90 wt%, 50 wt% to 80 wt%, 50 wt% to 70 wt%, 50 wt% to 60 wt%, 60 wt% to 99 wt%, 60 wt% to 90 wt%, 60 wt% to 80 wt%, 60 wt% to 70 wt%, 70 wt% to 99 wt%, 70 wt% to 90 wt%, 70 wt% to 80 wt%, 80 wt% to 99 wt%, 80 wt% to 90 wt%, and 90 wt% to 99 wt%.

[0026] In such embodiments, the polymer formulation can include from 1 wt% to 60 wt%, from 1 wt% to 50 wt%, from 1 wt% to 40 wt%, from 1 wt% to 30 wt%, 1 wt%, from 1 wt% to 20 wt%, from 1 wt% to 10 wt%, from 10 wt% to 60 wt%, from 10 wt% to 50 wt%, from 10 wt% to 40 wt%, from 10 wt% to 30 wt%, 10 wt%, from 10 wt% to 20 wt%, from 20 wt% to 60 wt%, from 20 wt% to 50 wt%, from 20 wt% to 40 wt%, from 20 wt% to 30 wt%, from 30 wt% to 60 wt%, from 30 wt% to 50 wt%, from 30 wt% to 40 wt%, from 40 wt% to 60 wt%, from 40 wt% to 50 wt%, or from 50 wt% to 60 wt% of the tetrad copolymer, based on the total weight of the polymer formulation.

[0027] Without being bound by theory, it is believed that the tetrad copolymer compositions described herein can be effective plasticizers when mixed with polyvinyl chloride to produce a polymer formulation. The tetrad copolymer compositions can have improved plasticizing efficiency when compared to other polymer compositions that can be mixed with polyvinyl chloride, calculated according to the methods described subsequently herein. Thus, the polymer formulations of embodiments comprising the described tetrad copolymer compositions can exhibit improved processability, lower tensile strength, and higher elongation, as compared to conventional flexible PVC polymers comprising other plasticizers. Furthermore, because the tetrad copolymer compositions can have improved plasticizing efficiency, the polymer formulations described herein can require relatively less plasticizer as compared to conventional flexible PVC polymers utilizing other conventional polymer plasticizers. As used herein, the plasticizing efficiency of the tetrad copolymer compositions can be calculated relative to the plasticizing efficiency of diisodecyl phthalate (DIDP), which is a conventional phthalate plasticizer. In embodiments, the tetrad copolymer compositions can have a plasticizing efficiency greater than 0.14, greater than 0.16, greater than 0.18, or greater than 0.20 relative to DIDP.

[0028] In further embodiments, the polymer formulation can also include other materials present to alter the properties of the polyvinyl chloride. These one or more optional components can include, but are not limited to, polystyrene, styrene copolymers, polyolefins (including homopolymers and copolymers comprising polyethylene and / or polypropylene and other ethylene / alpha-olefin copolymers), polyacrylic resins, polymers comprising butadiene such as acrylonitrile butadiene styrene terpolymer (ABS) and methacrylate butadiene styrene terpolymer (MBS), and chlorinated polyethylene (CPE) resins, and the like. These one or more optional components can also include DIDP, epoxidized soybean oil (ESO), stearic acid, and stabilizers known in the art. Such stabilizers can include barium / zinc stabilizers and 1076 stabilizer (commercially available from BASF).

[0029] In embodiments, the polymer formulation can comprise 1 to 40 weight percent, 1 to 30 weight percent, 1 weight percent, 1 to 20 weight percent, 1 to 10 weight percent, 10 to 50 weight percent, 10 to 40 weight percent, 10 to 30 weight percent, 10 weight percent, 10 to 20 weight percent, 20 to 50 weight percent, 20 to 40 weight percent, 20 to 30 weight percent, 30 to 50 weight percent, 30 to 40 weight percent, or 40 to 50 weight percent of one or more optional components, based on the total weight of the polymer formulation.

[0030] To produce the polymer formulation, the tetrad copolymer composition can be blended with the polyvinyl chloride and optionally one or more additional components. In further embodiments, the one or more optional components and the polyvinyl chloride can be dry mixed separately from the tetrad copolymer. In embodiments, the one or more optional components can be dry mixed with the polyvinyl chloride in a "Henschel-type" high speed agitator. The dry mix of the one or more optional components and the polyvinyl chloride can then be loaded into a polymer compounding device. In embodiments, the compounding device can be a Haake mixer, a co-rotating twin screw extruder, a counter-rotating twin screw extruder, or a conical mixer. The Haake temperature can be set to a melt temperature of 100°C to 200°C, 100°C to 180°C, 100°C to 160°C, 100°C to 140°C, 100°C to 120°C, 120°C to 200°C, 120°C to 180°C, 120°C to 160°C, 120°C to 140°C, 140°C to 200°C, 140°C to 180°C, 140°C to 160°C, 160°C to 200°C, 160°C to 180°C, or 180°C to 200°C. When the dry mix of the one or more optional components and the polyvinyl chloride is loaded into the Haake mixer, the melt temperature can drop. When the temperature of the Haake mixer comes back up to the desired melt temperature, the tetrad copolymer composition can be added to the Haake mixer. While mixing, the melt torque can be monitored to check for fusion of the PVC compound to determine if the fusion peak has been reached. As used herein, the fusion peak means the peak in the torque curve generated via software from the measured torque after the initial loading of the PVC dry mix. The fusion peak can be directly observed from the change in torque. In some embodiments, once the fusion peak has been reached, the Haake mixer can continue mixing for an additional time to ensure the desired melt mixing. For example, the Haake mixer can continue mixing for an additional 1 minute to 60 minutes, 1 minute to 30 minutes, 1 minute to 10 minutes, 1 minute to 5 minutes, 5 minutes to 60 minutes, 5 minutes to 30 minutes, 5 minutes to 10 minutes, 10 minutes to 60 minutes, 10 minutes to 30 minutes, or 30 minutes to 60 minutes. Once the tetrad copolymer, polyvinyl chloride, and optionally one or more additional components have been sufficiently melt mixed, the polymer formulation can be produced.

[0031] In embodiments comprising the formation of plasticized PVC using a co-rotating twin-screw extruder, a gravimetric feeder can be used to feed the dry blend powder and the tetrapolymer pellets into the feed hopper of the extruder. The extruder can be equipped with two rotating screws, a powder conveying section, a melting and fusion section, and multiple mixing sections separated by melt conveying sections. As the mixture of dry blend powder and tetrapolymer pellets flows through the extruder, the powder and pellets melt and mix to produce a homogenized melt. A die plate can be attached to the end of the extruder through which the polymer melt flows as a continuous strand. A rotating knife can be used to cut the continuous strand to produce plasticized PVC pellets. In embodiments, the melting and mixing sections of the extruder can be set at a temperature of 140 °C to 200 °C. In embodiments, the temperature of the melt exiting the die plate can be 170 °C to 210 °C. To test whether the PVC powder is fully plasticized, the PVC pellets can be pressed into a film in a compression molder and analyzed using a photo scanner in transmission mode. When full and satisfactory plasticization is achieved, the image will yield a white area percentage of < 5%.

[0032] In one or more additional embodiments, the polymer formulations described herein can be shaped into articles. Articles comprising the polymer formulations described herein can be used in flexible PVC applications, including roofing materials and geomembrane applications. The articles can include films and plaques comprising the polymer formulations described herein.

[0033] Test Methods

[0034] Density

[0035] Samples for density measurement are prepared according to ASTM D4703. The measurement is made according to ASTM D792 Method B within one hour after the sample is extruded. The value is reported in units of grams per cubic centimeter (g / cm3). 3

[0036] Melt Index

[0037] Melt index, I2, is measured according to ASTM D-1238 at 190 °C and 2.16 kg. The value is reported in units of g / 10 min.

[0038] Dynamic Mechanical Spectroscopy (DMS)

[0039] ​Viscosity measurements were made by TA Instruments ARES in a parallel plate. The samples were compression molded at 190 °C under a pressure of 25,000 pounds for 6.5 minutes in air, after which the plaque was allowed to cool on the lab bench. The thickness of the plate was about 3 mm. Constant temperature frequency sweep measurements were made on an ARES strain controlled parallel plate rheometer (TA Instruments) equipped with 25 mm parallel plates under a nitrogen purge. For each measurement, the rheometer was thermally equilibrated for at least 30 minutes before the gap was zeroed. The sample was placed on the plate and allowed to melt at 180 °C for five minutes. The plates were then closed to 2 mm, the sample was trimmed, and then the test was started. The method was additionally programmed with a five minute delay to allow for temperature equilibration. The experiment was run at 180 °C over a frequency range of 0.1 rad / s - 500 rad / s at five points per decade interval. The strain amplitude was constant at 5%. The stress response was analyzed in terms of amplitude and phase, from which the storage modulus (G'), loss modulus (G"), complex modulus (G*), dynamic complex viscosity (η*), and tan(δ) or loss tangent were calculated. Additionally, thin plaques of about 3 mm - 4 mm thickness were prepared to measure the loss tangent (ratio of loss modulus to storage modulus) as a function of temperature from -100 °C to 80 °C.

[0040] Tensile Properties

[0041] Tensile strength, tensile modulus, and elongation at break were measured according to ASTM D1708. To test these properties, microtensile bars of 2 mm thickness were punched from compression molded plaques.

[0042] Glass Transition Temperature (Tg)

[0043] Glass transition temperature (Tg) was measured from the loss tangent peak temperature of the DMS analysis described herein.

[0044] Differential Scanning Calorimetry (DSC)

[0045] Differential scanning calorimetry (DSC) can be used to measure the melting, crystallization, heat of fusion, and glass transition behavior of polymers over a wide range of temperatures. For example, a TA Instruments Q1000 DSC, equipped with a refrigerated cooling system (RCS) and an autosampler was used to perform this analysis. During testing, a nitrogen purge gas flow of 50 ml / min was used. Each sample was melt pressed into a thin film at about 175 °C; the molten sample was then air-cooled to room temperature (about 25 °C). A 3-10 mg, 6 mm diameter specimen was extracted from the cooled polymer, weighed, placed in a light aluminum pan (ca 50 mg), and crimped shut. The analysis was then performed to determine its thermal properties.

[0046] The thermal behavior of the sample is determined by ramping the sample temperature up and down to create a heat flow versus temperature curve. First, the sample is rapidly heated to 120°C and held isothermal for 3 minutes in order to remove its thermal history. Next, the sample is cooled to -50°C at a 10°C / minute cooling rate and held isothermal at -50°C for 3 minutes. The sample is then heated to 120°C (this is the "second heat" ramp) at a 10°C / minute heating rate. The cooling and second heating curves are recorded. The cooling curve is analyzed by setting a baseline from the beginning of crystallization to -20°C. The heating curve is analyzed by setting a baseline from -20°C to the end of melting. The values determined are the extrapolated onset of melting, Tm, and the extrapolated onset of crystallization, Tc. The heat of fusion (Hf), also known as the melting enthalpy, and the peak melting temperature are reported from the second heat curve. The peak crystallization temperature is determined from the cooling curve.

[0047] The melting point, Tm, is determined from the DSC heating curve by first drawing a baseline between the beginning and end of the melting transition. A tangent line is then drawn to the data on the low temperature side of the melting peak. The point at which this tangent line intersects the baseline is the extrapolated onset of melting (Tm). This is as described by Bernhard Wunderlich, The Basis of Thermal Analysis, in Thermal Characterization of Polymeric Materials 92, 277-278 (Edith A. Turi, ed., 2d ed. 1997).

[0048] The crystallization temperature, Tc, is determined from the DSC cooling curve as above, except that a tangent line is drawn on the high temperature side of the crystallization peak. The point at which this tangent line intersects the baseline is the extrapolated onset of crystallization temperature (Tc).

[0049] Examples

[0050] The following examples illustrate features of the present disclosure, but are not intended to limit the scope of the present disclosure. The following experiments analyze the performance of embodiments of the polymer compositions described herein.

[0051] Example 1 : Sample 1

[0052] To prepare Sample 1, a mixture of ethylene (E), n-butyl acrylate (nBA), carbon monoxide (CO), and propylene was added to a 545 milliliter (mL) stirred autoclave. Organic peroxide (tert-butyl peroxy isooctanoate) was added to the mixture as a 1-3 wt% solution in odorless mineral spirits as a polymerization initiator, and the mixture was subjected to approximately 27,000 psi (1,898 kg / cm2) pressure at 150°C for 2 hours. The resulting polymer was recovered and dried. 2The reactor temperature was set to a target temperature of 205 °C. Under the polymerization conditions shown in Table 1, a tetrapolymer was continuously synthesized and subsequently converted into pellet form by melt extrusion. The conditions listed in Table 1 are averages over the time span in which Sample 1 was collected. The "autoclave-prepared" experimental reactor tetrapolymer thus formed was found to have the properties shown in Table 2.

[0053] Table 1. Polymerization Conditions for Sample 1 .

[0054] Sample 1 Reactor Pressure (psi) 27,000 Reactor Temperature (°C) 204.9 Ethylene Feed Rate (lb / hr) 24.96 nBA Feed Rate (lb / hr) 1.7 CO Feed Rate (lb / hr) 0.71 Acetone Feed Rate (lb / hr) --- Propylene Feed Rate (lb / hr) 2.08 Initiator Solution wt % 3 Initiator Solution Feed Rate (cc / hr) 30.18 Reactor Conversion (%) 11.40％

[0055] The properties of Sample 1 are provided in Table 2 below, where nBA represents n-butyl acrylate; CO represents carbon monoxide; P represents propylene; the weight percentages of nBA, CO, and P are based on the total weight of Sample 1; and the melt index is measured according to ASTM D-1238 at 190 °C and 2.16 kg.

[0056] Table 2: Properties of Sample 1 .

[0057]

[0058] Example 2: Comparative Sample A

[0059] To prepare Sample 1, a mixture of ethylene (E), n-butyl acrylate (nBA), carbon monoxide (CO), and acetone was added to a 545 milliliter (mL) stirred autoclave. An organic peroxide (tert-butyl peroxyisooctanoate) was added to the mixture as a polymerization initiator in the form of a 1-3 wt% solution in odorless mineral spirits, the mixture was subjected to a set pressure of approximately 27,000 psi (1,898 kg / cm 2 The reactor temperature was set to a target temperature of 205 °C. Under the polymerization conditions shown in Table 3, a terpolymer was continuously synthesized and subsequently converted into pellet form by melt extrusion. The conditions listed in Table 2 are averages over the time span in which Comparative Sample A was collected. The "autoclave-prepared" experimental reactor terpolymer thus formed was found to have the properties shown in Table 3.

[0060] Table 3. Polymerization Conditions for Comparative Sample A .

[0061] Comparative Sample A Reactor Pressure (psi) 27,000 Reactor Temperature (°C) 205 Ethylene Feed Rate (lb / hr) 25 nBA Feed Rate (lb / hr) 1.7 CO Feed Rate (lb / hr) 0.68 Acetone Feed Rate (lb / hr) 2.21 Propylene Feed Rate (lb / hr) --- Initiator Solution wt % 1 Initiator Solution Feed Rate (cc / hr) 33.25 Reactor Conversion (%) 12.30％

[0062] The properties of Comparative Sample A are provided in Table 4 below, where nBA represents n-butyl acrylate; CO represents carbon monoxide; P represents propylene; the weight percentages of nBA, CO, and P are based on the total weight of Comparative Sample A; the melt index is measured according to ASTM D-1238 at 190 °C and 2.16 kg.

[0063] Table 4: Properties of Sample 1 .

[0064]

[0065] Example 3: Comparison of Sample 1 to Comparative Sample A

[0066] In Example 3, Sample 1 was compared to Comparative Sample A by analyzing the melt index, molecular weight, molecular weight distribution, glass transition temperature (Tg) (DSC), glass transition temperature (determined from the peak in the loss tangent), melting temperature, crystallization temperature, heat of fusion, and storage modulus at 20 °C, which are subsequently provided in Table 5. These properties were measured according to the test methods described herein. To determine the glass transition temperature (determined from the peak in the loss tangent), a plot of Tan(5) versus temperature was drawn, and the peak temperature is provided in the table below.

[0067] Table 5. Comparison of Sample 1 to Comparative Sample A .

[0068]

[0069] As shown in Table 5, Sample 1 exhibited a lower melting temperature, crystallization temperature, and heat of fusion when compared to Comparative Sample A. Additionally, Sample 1 exhibited a lower storage modulus at temperatures above -50 °C. Lower storage modulus and thermal properties are desirable for plasticized PVC applications because of the need for flexibility in handling, operation, and installation of the finished product.

[0070] Example 4: Sample PVC-1

[0071] In Example 4, a PVC formulation, referred to as Sample PVC-1, was prepared that included polyvinyl chloride and Sample 1 of Example 1 described above. The materials used to produce Sample PVC-1 were polyvinyl chloride having a K value of 70 (purchased from Formosa Plastics Corporation); diisodecyl phthalate (DIDP) (purchased from ExxonMobil); barium / zinc stabilizer (purchased from Galata Chemicals); epoxidized soybean oil (ESO) (purchased from Galata Chemicals); titanium dioxide (purchased from Chemours); stearic acid (purchased from Sigma-Aldrich); and 1076 stabilizer (purchased from BASF). The amounts of each component in Sample PVC-1 are subsequently provided in Table 6.

[0072] Table 6. Composition of Samples PVC-1 and PVC-2 .

[0073]

[0074] To produce samples PVC-1 and PVC-2, all components except for the Sample 1 composition were dry blended in a “Henschel-type” high speed mixer. The dry blend was then loaded into a Haake mixer (Sample 1 composition). The Haake temperature was set at 170 °C, and once the PVC dry blend was added, the melt temperature dropped. Once the melt temperature came back up to 170 °C, the Sample 1 composition was then slowly added to the Haake mixer. The melt torque was closely monitored to check for fusion of the PVC compound. Once the fusion peak was determined to have been reached according to the method described herein, the Haake mixer was kept running for an additional 10 minutes to ensure good melt mixing. Then, each of samples PVC-1 and PVC-2 were removed from the Haake and hot pressed into 2 nm-4 nm plaques at 185 °C for various characterizations.

[0075] Example 5: Sample PVC-1a

[0076] In Example 5, a PVC formulation similar to PVC-1 and referred to as sample PVC-1a was prepared using an alternative method compared to Example 4. In particular, sample PVC-1a included a dry powder of polyvinyl chloride having the same composition as the polyvinyl chloride of Example 4 and a tetrapolymer pellet having the same composition as sample 1 of Example 1 described above. The PVC dry blend powder and the tetrapolymer pellets were fed into a 26 mm Coperion co-rotating twin-screw extruder with 11 barrels, a total length / diameter ratio of 44. The extruder had a relatively high intensity screw design with a length / diameter ratio of 4.8 for one melt section and about 4.8 and about 3.4 for two mixing sections, respectively. The PVC dry blend powder was fed using a KTRON gravity powder feeder and the tetrapolymer pellets were fed using a KTRON gravity pellet feeder. The extruder was equipped with a die having four 3.1 mm die holes. The continuous polymer strand was cut into pellets. The third extruder barrel to the eleventh extruder barrel were set at a temperature of 160 °C, the second barrel was set at 80 °C, and no heat was applied to the feed barrels.

[0077] Table 7 below shows the processing parameters for the extrusion method used to obtain sample PVC-1a and the percent white area of the resulting film. The process described in Example 5 resulted in complete and satisfactory plasticization of the PVC powder as evidenced by the percent white area of 0.47%.

[0078] Table 7. Processing Parameters for Extrusion Process to Obtain Sample PVC-1A

[0079] Throughput Rate (lb / hr) 35 Extruder Screw Speed (rpm) 300 Melt Temperature (°C) 198 Specific Energy Input (kW-hr / kg) 0.248 White Area Percentage (%) 0.47

[0080] The 4 g of the resulting pellets were compression molded into a film using a Carver press at a pressure of 10,000 psi and a temperature of 180 °C for 3 min. The film was cooled to room temperature while the pressure was maintained at 10,000 psi, and then it was removed from the press.

[0081] The resulting PVC film was scanned using an Epson Perfection photo scanner in reflectance mode, with an image size of 22 mm x 22 mm, a resolution of 4800 dpi, and saved with 8-bit grayscale. The resulting image was then opened in Image J software and requested twice to obtain Image Copy 1 and Image Copy 2. A Gaussian Blur was applied to Image Copy 2 sigma (radius) 40. Image Copy 2 was subtracted from Image Copy 1 using the Image Calculator. A non-sharpening mask was applied to the resulting image with a radius (sigma) of 2 pixels and a mask weight of 0.80. A threshold was then applied with a default grayscale level of 56. The subsequent step was dilation, followed by the application of a median filter with a radius of 2 pixels. The white area percentage was analyzed in the 25 pm 3 to infinity pm 3 range. The output of the white area percentage was then tabulated using Microsoft Excel.

[0082] Example 6 - Comparative Sample PVC-A

[0083] In Example 6, a composition referred to as Comparative Sample PVC-A was prepared that included polyvinyl chloride and Sample 1 of Example 1 described above. The materials used to produce Sample PVC-1 were polyvinyl chloride with a K value of 70 (purchased from Formosa Plastics Corporation); diisodecyl phthalate (DIDP) (purchased from ExxonMobil); barium / zinc stabilizer (purchased from Galata Chemicals); epoxidized soybean oil (ESO) (purchased from Galata Chemicals); titanium dioxide (purchased from Chemours); stearic acid (purchased from Sigma-Aldrich); and 1076 stabilizer (purchased from BASF). The amounts of each component in Sample PVC-1 are provided subsequently in Table 8.

[0084] Table 8. Composition of Comparative Samples PVC-A, PVC-B, and PVC-C .

[0085]

[0086] To produce comparative samples PVC-A, PVC-B, and PVC-C, all components except for Sample 1 composition were dry blended in a “Henschel-type” high speed mixer. The dry blend was then loaded into a Haake mixer (Sample 1 composition). The Haake temperature was set at 170 °C, and once the PVC dry blend was added, the melt temperature dropped. Once the melt temperature came back up to 170 °C, the Sample 1 composition was then slowly added into the Haake mixer. The melt torque was closely monitored to check for fusion of the PVC compound. Once the fusion peak was determined to be reached according to the method described herein, the Haake mixer was kept running for an additional 10 minutes to ensure good melt mixing. Then, each of samples PVC-1 and PVC-2 were removed from the Haake and hot pressed into plaques with a thickness between 2 mm - 4 mm at 185 °C for various characterizations.

[0087] Example 7: Comparison of Sample PVC-1 to Comparative Sample PVC-A

[0088] In Example 7, the mechanical properties and plasticization efficiency of samples PVC-1 and PVC-2 were compared to comparative samples PVC-A, PVC-B, and PVC-C. As provided in Examples 4 and 6 above, samples PVC-1 and PVC-2 included Sample 1 composition from Example 1 (E-P-nBA-CO (58%-2%-30%-10%)). Additionally, PVC-1 included DIDP. Comparative samples PVC-A and PVC-B included Comparative Sample A composition from Example 2 (E-nBA-CO (60%-30%-10%)). Additionally, PVC-A included DIDP. Comparative sample PVC-C included only DIDP, neither Sample 1 composition from Example 1 nor Sample A composition from Example 2.

[0089] The mechanical properties of samples PVC-1 and PVC-2 and comparative samples PVC-A, PVC-B, and PVC-C were measured according to the test methods provided herein. Tensile strength, tensile modulus, and elongation at break were measured according to ASTM D1708. To test the samples, micro tensile bars were punched from compression molded plaques made from the sample compositions. The compression molded plaques had a thickness of 1.5 mm.

[0090] The viscosity and DMA properties of samples PVC-1 and PVC-2 and comparative samples PVC-A, PVC-B, and PVC-C were measured according to the test methods provided herein. Viscosity measurements were made by TA Instruments ARES in a parallel plate configuration. The samples were tested at 180 °C with a strain of 5%, and the frequency was scanned from 0.1 rad / s to 500 rad / s. Additionally, plaques with a thickness of about 3 mm - 4 mm were prepared to measure the relationship of the tangent of the loss angle (ratio of the loss modulus to the storage modulus) to temperature from -100 °C to 80 °C.

[0091] The mechanical properties of samples PVC-1 and PVC-2 and comparative samples PVC-A, PVC-B, and PVC-C are then provided in Table 9.

[0092] Table 9. Mechanical Properties of Samples PVC-1 and PVC-2 to Comparative Samples PVC-A, PVC-B, and PVC-C .

[0093] Modulus (MPa) Tensile Strength (MPa) Elongation at Break (%) Sample PVC-1 18.1 12.7 348.3 Sample PVC-2 47.9 16.2 314.1 Comparative Sample PVC-A 29.1 13.7 310.9 Comparative Sample PVC-B 106.1 14.2 251.6 Comparative Sample PVC-C 13.4 18.0 380.4

[0094] As shown in Table 9, it was observed that sample PVC-1 exhibited results comparable to sample containing only DIDP, comparative sample PVC-C. In addition, sample PVC-1 and comparative sample PVC-A exhibited tensile strength and elongation at break comparable thereto, but sample PVC-1 exhibited a lower modulus. In addition, sample PVC-2 and comparative sample PVC-B exhibited tensile strength comparable thereto, but sample PVC-1 exhibited a lower modulus. As previously described in this disclosure, for some flexible PVC applications, such as roofing material applications, a lower modulus is desirable as it indicates higher softness and flexibility.

[0095] To calculate the modulus of each sample in PVC-1 and PVC-A, the following equation was used:

[0096] For sample PVC-1:

[0097] log 10 (modulus of overall sample PVC-1) = log 10 (modulus of sample 1) x (wt% of sample 1 used in PVC-1) + log 10 (modulus of PVC and other additives in PVC-1) * (wt% of PVC and other additives in PVC-1)

[0098] For comparative sample PVC-A:

[0099] log 10 (modulus of overall sample PVC-A) = log 10 (modulus of sample 2) x (wt% of sample 2 used in PVC-A) + log 10 (modulus of PVC

[0100] and other additives in PVC-A) * (wt% of PVC

[0101] and other additives in PVC-A)

[0102] The modulus of Sample 1 and Comparative Sample A is based on the DMA data from Example 3 above. Using the above equation, the modulus of polyvinyl chloride having a K value of 70 (purchased from Formosa Plastics Corporation) and the other additives of Bulk Sample PVC-A or Bulk Sample PVC-1, respectively, were back-calculated using the modulus (measured by tensile testing) of Bulk Sample PVC-A or Bulk Sample PVC-1. From this formulation, it is known that the polyvinyl chloride having a K value of 70 (purchased from Formosa Plastics Corporation) and the other additives (not including Comparative Sample A or Sample 1) are the same in Sample PVC-1 and Sample PVC-A. Therefore, assuming that the modulus of the polyvinyl chloride having a K value of 70 and the other additives in PVC-1 is equal to the modulus of the polyvinyl chloride having a K value of 70 and the other additives in PVC-A, the modulus of PVC-1 and Comparative PVC-A can be calculated and compared to the actual measured values.

[0103] Table 10. Mechanical Properties of Sample PVC-1 to Comparative Sample PVC-A .

[0104]

[0105]

[0106] As shown in Table 10, it was concluded that the calculated modulus of Sample PVC-1 was higher than its actual measured value. This indicates that the low modulus of Sample PVC-1 is not only from the lower modulus of Sample 1 (of Example 1 above), it can further imply that Sample 1 has improved plasticization efficiency of PVC, resulting in a lower modulus of the overall PVC formulation.

[0107] Further, it was observed that Sample PVC-1 exhibited a lower Tg and a broader Tg peak when compared to Comparative Sample PVC-A. Without being bound by theory, the lower glass transition temperature can contribute to Sample PVC-1 exhibiting a lower modulus. Further, the lower Tg of Sample PVC-1 can further illustrate that Sample 1 helps improve the plasticization efficiency of PVC.

[0108] To demonstrate that Sample 1 (of Example 1 above) exhibits improved plasticization efficiency of PVC compared to Comparative Sample A (of Example 2 above), the plasticization efficiency (PE) of Sample 1 and Comparative Sample A relative to DIDP was calculated based on the following equation:

[0109] PE of Sample 1 = (Modulus of PVC-C) / (Modulus of PVC-2)

[0110] PE of Comparative Sample A = (Modulus of PVC-C) / (Modulus of PVC-B)

[0111] The calculated plasticizing efficiency relative to DIDP based on the above equations and the measured modulus of comparative sample PVC-C and sample PVC-B or comparative sample PVC-B are provided in Table 11.

[0112] Table 11. Plasticization Efficiency of Sample 1 to Comparative Sample A Table 11. Plasticization Efficiency of Sample 1 to Comparative Sample A .

[0113]

[0114] It will be readily apparent that modifications and variations of the present disclosure can be made in light of the above teachings. It is therefore to be understood that this disclosure may not be limited to the specific aspects disclosed hereinabove, and other modifications and variations may be apparent to those skilled in the art upon reading this disclosure.

Claims

1. A tetrapolymer composition comprising: Formula E / P / X / CO; wherein: the tetrapolymer composition comprises 25 wt% to 90 wt% ethylene E, 0.1 wt% to 5.0 wt% propylene P, 5 wt% to 40 wt% n-butyl acrylate X, and 3 wt% to 30 wt% carbon monoxide CO, and wherein the tetrapolymer composition has a melt index I2 of 10 g / 10 min to 800 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190 °C.

2. The tetrapolymer composition of claim 1, wherein the tetrapolymer composition has a melt index I2 of 50 g / 10 min to 600 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190 °C.

3. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition has a melt index I2 of 200 g / 10 min to 400 g / 10 min when measured according to ASTM 1238 at 2.16 kg and 190 °C.

4. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition comprises 1 wt% to 4 wt% P based on the total weight of the tetrapolymer composition.

5. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition comprises 10 wt% to 40 wt% X based on the total weight of the tetrapolymer composition.

6. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition comprises 5 wt% to 20 wt% CO based on the total weight of the tetrapolymer composition.

7. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition has a storage modulus of 0.1 MPa to 100 MPa when measured at 20 °C.

8. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition has a melting temperature of 30 °C to 80 °C.

9. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition has a crystallization temperature of 20 °C to 70 °C.

10. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition has a heat of fusion of 10 J / g to 100 J / g.

11. The tetrapolymer composition of claim 1 or 2, wherein the tetrapolymer composition has a storage modulus of 1.0 MPa to 4.5 MPa when measured at 20 °C.

12. A polymer formulation comprising the tetrapolymer composition of any one of claims 1-11 and further comprising polyvinyl chloride.

13. The polymer formulation of claim 12, comprising 1 wt% to 60 wt% of the tetrapolymer based on the total weight of the polymer formulation. ​ 14. The polymer formulation of claim 12 or 13, comprising 40 to 99 weight percent of the polyvinyl chloride, based on the total weight of the polymer formulation.

15. An article comprising the polymer formulation of any one of claims 12 to 14.

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