Polymer compositions and polymer plasticizers incorporating them

Abstract

The present disclosure provides embodiments of tetrapolymer compositions. In embodiments, the tetrapolymer composition may have the formula E / P / X / CO, which may include 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. The tetrapolymer composition may have a melt index, I2, of 10 to 1,000 g / 10 min, measured at 2.16 kg and 190°C according to ASTM 1238. Additionally, the present disclosure provides embodiments of polymer blends comprising the tetrapolymer composition and polyvinyl chloride.

Description

Technical Field

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

Background Art

[0002] Polyvinyl chloride (PVC) is one of the most commonly used polymers. PVC polymers are vinyl chloride polymers that can be further classified as "rigid" (unplasticized) PVC polymers or "flexible" (plasticized) PVC polymers depending on the degree of their rigidity. Thus, flexible PVC polymers are softer and more compliant to bending than rigid PVC polymers. Flexible PVC polymers are commonly used in applications such as insulation on electrical wires, household flooring, architectural applications such as roof flushing, and geomembrane applications.

Summary of the Invention

[0003] Conventionally, flexible PVC applications utilize PVC polymers that require plasticizers to soften the PVC sufficiently to be flexible and elastic. For example, phthalate-based liquid plasticizers are commonly used plasticizers for flexible PVC applications. However, due to the small molecular nature of phthalate-based liquid plasticizers, phthalate-based liquid plasticizers migrate from the PVC polymer over time, resulting in the degradation of the performance characteristics of the flexible PVC polymer.

[0004] To address the issue of migration, polymer plasticizers may be applied to replace phthalate-based plasticizers. However, as studies have shown, polymer plasticizers may have lower plasticization efficiency than conventional phthalate-based plasticizers. As a result, larger amounts of polymer plasticizers may be required to achieve the desired flexibility or elasticity in the overall PVC polymer formulation.

[0005] Therefore, there is a need for an alternative composition that exhibits improved plasticization efficiency compared to conventional polymer plasticizers when used as a plasticizer in PVC polymer formulations, and that possesses flexibility and elasticity.

[0006] Embodiments of this disclosure satisfy this need by providing compositions comprising tetrapolymers that can exhibit improved flexibility and elasticity compared to conventional polymer plasticizers. Therefore, when used in flexible PVC polymer formulations, the tetrapolymer compositions described herein can enable polymer formulations that maintain performance characteristics or have improved resistance to failure modes such as rutting or fatigue cracking at various temperature regimes.

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

[0008] According to at least one embodiment of the present disclosure, a polymer formulation that can be used in flexible PVC applications is provided. Embodiments of the polymer formulation may include polyvinyl chloride and a tetrapolymer composition having the formula E / P / X / CO, which may contain 25% to 90% by weight of ethylene (E), 0.1% to 5.0% by weight of propylene (P), 5% to 40% by weight of alkyl acrylate (X), and 3% to 30% by weight of carbon monoxide (CO). X can be n-butyl acrylate. The tetrapolymer composition may have a melt index of 10 to 1,000 g / 10 min, I2, when measured at 2.16 kg and 190°C according to ASTM 1238.

[0009] These embodiments and other embodiments will be described in more detail in the following embodiments for carrying out the invention. [Modes for carrying out the invention]

[0010] Herein, specific embodiments of this application are described. These embodiments are provided so as to demonstrate that this disclosure is detailed and complete and to fully convey the scope of the subject matter to those skilled in the art.

[0011] The term "polymer" refers to polymer compounds prepared by polymerizing monomers, whether of the same or different types. Therefore, the general term "polymer" typically includes the term "homopolymer," which refers to polymers prepared from only one type of monomer, and the term "copolymer," which refers to polymers prepared from two or more different types of monomers. As used herein, the term "interpolymer" refers to polymers prepared by polymerizing at least two different types of monomers. Therefore, 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 polymer" means a polymer containing units derived from more than 50 mol% of ethylene monomers. This includes ethylene homopolymers or copolymers (meaning units derived from two or more comonomers). Common forms of ethylene polymers known in the art include low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), ultra-low-density polyethylene (ULDPE), very low-density polyethylene (VLDPE), single-site catalyst linear low-density polyethylene (m-LLDPE) including both linear low-density resins and substantially linear low-density resins, medium-density polyethylene (MDPE), and high-density polyethylene (HDPE).

[0013] As used herein, the term “propylene-based polymer” refers to a polymer derived from propylene monomer that contains more than 50 mol% of units in its polymerized form. This includes propylene homopolymers, random copolymer polypropylenes, impact copolymer polypropylenes, propylene / α-olefin copolymers, and propylene / α-olefin copolymers.

[0014] Embodiments of polymer compositions as described herein will be referenced in detail. Embodiments of polymer compositions may include tetrapolymer compositions represented by the formula E / P / X / CO, comprising polymer units E, P, X, and CO. According to at least one embodiment of the present disclosure, the tetrapolymer composition may have the formula E / P / X / CO, comprising 25% to 90% by weight of ethylene (E), 0.1% to 5.0% by weight of propylene (P), 5% to 40% by weight of alkyl acrylate (X), and 3% to 30% by weight of carbon monoxide (CO). X can be n-butyl acrylate. The tetrapolymer composition may have a melt index of I2, ranging from 10 g / 10 min to 1,000 g / 10 min, when measured at 2.16 kg and 190°C according to ASTM 1238.

[0015] In embodiments, E may be a polymer unit -(CH2CH2)- derived from an ethylene monomer. The tetrapolymer composition is based on the total weight of the tetrapolymer and is available in the following ranges: 25%-90% by weight, 25%-80% by weight, 25%-70% by weight, 25%-60% by weight, 25%-50% by weight, 25%-40% by weight, 25%-30% by weight, 30%-90% by weight, 30%-80% by weight, 30%-70% by weight, 30%-60% by weight, and 30%-50% by weight from It may contain E in the following proportions: 30% to 40% by weight, 40% to 90% by weight, 40% to 80% by weight, 40% to 70% by weight, 40% to 60% by weight, 40% to 50% by weight, 50% to 90% by weight, 50% to 80% by weight, 50% to 70% by weight, 50% to 60% by weight, 60% to 90% by weight, 60% to 80% by weight, 60% to 70% by weight, 70% to 90% by weight, 70% to 80% by weight, or 80% to 90% by weight.

[0016] In embodiments, P may be a polymer unit derived from a propylene monomer. The tetrapolymer composition may contain P in amounts of 0.1% to 5% by weight, 0.1% to 4% by weight, 0.1% to 3% by weight, 0.1% to 2% by weight, 0.1% to 1% by weight, 0.1% to 0.5% by weight, 0.5% to 5% by weight, 0.5% to 4% by weight, 0.5% to 3% by weight, 0.5% to 2% by weight, 0.5% to 1% by weight, 1% to 5% by weight, 1% to 4% by weight, 1% to 3% by weight, 1% to 2% by weight, 2% to 5% by weight, 2% to 4% by weight, 2% to 3% by weight, 3% to 5% by weight, or 4% to 5% by weight.

[0017] In some embodiments, X may be a polymer unit containing an alkyl acrylate. In further embodiments, X can be a polymer unit of the n-butyl acrylate monomer. Tetrapolymer compositions are based on the total weight of tetrapolymer and include 5% to 40% by weight, 5% to 35% by weight, 5% to 30% by weight, 5% to 25% by weight, 5% to 20% by weight, 5% to 15% by weight, 5% to 10% by weight, 10% to 40% by weight, 10% to 35% by weight, 10% to 30% by weight, 10% to 25% by weight, 10% to 20% by weight, 10% to 15% by weight, and 15% by weight. It may contain X in amounts of ~40% by weight, 15%~35% by weight, 15%~30% by weight, 15%~25% by weight, 15%~20% by weight, 20%~40% by weight, 20%~35% by weight, 20%~30% by weight, 20%~25% by weight, 25%~40% by weight, 25%~35% by weight, 25%~30% by weight, 30%~40% by weight, 30%~35% by weight, or 35%~40% by weight.

[0018] In embodiments, CO may be polymer units derived from a carbon monoxide-containing comonomer. The tetrapolymer composition may contain 3% to 30% by weight, 3% to 25% by weight, 3% to 20% by weight, 3% to 15% by weight, 3% to 10% by weight, 3% to 5% by weight, 5% to 30% by weight, 5% to 25% by weight, 5% to 20% by weight, 5% to 15% by weight, 5% to 10% by weight, 10% to 30% by weight, 10% to 25% by weight, 10% to 20% by weight, 10% to 15% by weight, 15% to 30% by weight, 15% to 25% by weight, 15% to 20% by weight, 20% to 30% by weight, 20% to 25% by weight, 25% to 30% by weight, or 25% to 30% by weight of CO.

[0019] In this embodiment, the tetrapolymer composition, when measured at 2.16 kg and 190°C according to ASTM 1238, yields 10 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, and 10 g / 10 min to 100 g / 10 min. minutes, 10g / 10 minutes to 50g / 10 minutes, 50g / 10 minutes to 1,000g / 10 minutes, 50g / 10 minutes to 800g / 10 minutes, 50g / 10 minutes to 600g / 10 minutes, 50g / 10 minutes to 400g / 10 minutes, 50g / 10 minutes to 200g / 10 minutes, 50g / 10 minutes to 100g / 10 minutes, 100g / 10 minutes to 1,000g / 10 minutes , 100g / 10 minutes~800g / 10 minutes, 100g / 10 minutes~600g / 10 minutes, 100g / 10 minutes~400g / 10 minutes, 100g / 10 minutes~200g / 1 0 minutes, 200g / 10 minutes ~ 1,000g / 10 minutes, 200g / 10 minutes ~ 800g / 10 minutes, 200g / 10 minutes ~ 600g / 10 minutes, 200g / 10 minutes ~ 400 It may have a melt index of I2 for 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.

[0020] In some embodiments, the tetrapolymer composition may 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 may have a storage modulus of ASTM When measured at 20°C according to D1708, the following pressure ranges were observed: 1.0MPa~10MPa, 1.0MPa~9.0MPa, 1.0MPa~8.0MPa, 1.0MPa~7.0MPa, 1.0MPa~6.0MPa, 1.0MPa~5.0MPa, 1.0MPa~4.0MPa, 1.0MPa~3.0MPa, 1.0MPa~2.0MPa, 2.0MPa~10.0MPa, 2.0MPa~9.0MPa, 2.0MPa~8.0MPa, 2.0MPa~7.0MPa, 2.0MPa~6.0MPa, 2.0MPa~5.0MPa, 2.0MPa~4.0MPa, 2.0MPa~3.0MPa, 3.0MPa~10.0MPa, 3.0MPa~9.0MPa, 3.0MPa~8.0MPa, 3.0MPa~7.0MPa, and 3.0MPa. ~6.0MPa, 3.0MPa~5.0MPa, 3.0MPa~4.0MPa, 4.0MPa~10.0MPa, 4.0MPa~9.0MPa, 4.0MPa~8.0MPa, 4 .0MPa~7.0MPa, 4.0MPa~6.0MPa, 4.0MPa~5.0MPa, 5.0MPa~10.0MPa, 5.0MPa~9.0MPa, 5.0MPa~8.0M Pa, 5.0MPa~7.0MPa, 5.0MPa~6.0MPa, 6.0MPa~10.0MPa, 6.0MPa~9.0MPa, 6.0MPa~8.0MPa, 6.0MPa~ 7.0MPa, 7.0MPa~10.0MPa, 7.0MPa~9.0MPa, 7.0MPa~8.0MPa, 8.0MPa~10.0MPa, 8.0MPa~9.0MPa, or It can have a storage modulus of elasticity from 9.0 MPa to 9.5 MPa.

[0021] In this embodiment, the tetrapolymer composition is suitable for temperatures 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, and 40°C to 45°C. It may have a melting temperature of 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 65°C, 60°C to 80°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, or 75°C to 80°C.

[0022] In the embodiment, the tetrapolymer composition is used at 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, 30°C to 50°C, 30°C to 45°C, and 30°C to 40°C. It may have crystallization temperatures of 30℃~35℃, 35℃~70℃, 35℃~65℃, 35℃~60℃, 35℃~55℃, 35℃~50℃, 35℃~45℃, 35℃~40℃, 40℃~70℃, 40℃~65℃, 40℃~60℃, 40℃~55℃, 40℃~50℃, 40℃~45℃, 45℃~70℃, 45℃~65℃, 45℃~60℃, 45℃~55℃, 45℃~50℃, 50℃~70℃, 50℃~65℃, 50℃~60℃, 50℃~55℃, 55℃~70℃, 55℃~65℃, 55℃~60℃, 60℃~70℃, 60℃~65℃, or from 65℃~70℃.

[0023] In this embodiment, the tetrapolymer composition is 10J / g to 100J / g, 10J / g to 90J / g, 10J / g to 80J / g, 10J / g to 70J / g, 10J / g to 60J / g, 10J / g to 50J / g, 10J / g to 40J / g, 10J / g to 30J / g, 10J / g to 20J / g, 20J / g to 100J / g, 20J / g~90J / g, 20J / g~80J / g, 20J / g~70J / g, 20J / g~60J / g, 20J / g~50J / g, 20J / g~40J / g, 20J / g~30J / g, 30J / g~100J / g, 30J / g~90J / g, 30J / g~80J / g, 30J / g~70J / g, 30J / g~60J / g, 30J / g~50J / g, 30J / g~40J / g, 40J / g~100J / g, 40J / g~90J / g, 40J / g~80J / g, 40J / g~70J / g, 40 J / g~60J / g, 40J / g~50J / g, 50J / g~100J / g, 50J / g~90J / g, 50J / g~80J / g, 50J / g~70J / g, 50 It may have a heat of fusion of J / g~60J / g, 60J / g~100J / g, 60J / g~90J / g, 60J / g~80J / g, 60J / g~70J / g, 70J / g~100J / g, 70J / g~90J / g, 70J / g~80J / g, 80J / g~100J / g, 80J / g~90J / g, or 90J / g~100J / g.

[0024] Next, embodiments of the polymer blend containing the tetrapolymer composition will be described. In an embodiment, the polymer blend containing the tetrapolymer composition described herein may further contain a vinyl halide polymer. The vinyl halide polymer is a homopolymer or copolymer of vinyl chloride or vinylidene dichloride. In an embodiment, the polymer blend containing the tetrapolymer composition described herein may further contain poly(vinyl chloride) (PVC). Poly(vinyl chloride) polymers can be further classified as "rigid" PVC polymers or "flexible" PVC polymers depending on the degree of their rigidity. Flexible PVC polymers may have a modulus of elasticity of less than 100,000 psi (690 MPa), and rigid PVC polymers may have a modulus of elasticity of greater than 100,000 psi (690 MPa), for example, 100,000 psi to 1,000,000 psi (690 MPa to 6,900 MPa). Flexible PVC polymers can be distinguished from rigid PVC polymers mainly by the presence and amount of plasticizers in the resin. Flexible PVC polymers typically have better processability, lower tensile strength, and higher elongation than rigid PVC polymers. In an embodiment, the polymer blend described herein containing the tetrapolymer composition and polyvinyl chloride can be classified as a flexible PVC polymer. In these embodiments, the poly(vinyl chloride) polymer may have a K value of 60 - 80, 60 - 75, 60 - 70, 60 - 65, 65 - 80, 65 - 75, 65 - 70, 70 - 80, 70 - 75, or 75 - 80.

[0025] In an embodiment, the polymer formulation may include 40% to 99% by weight of polyvinyl chloride based on the total weight of the polymer formulation. In a further embodiment, the polymer formulation may include 40% to 95%, 40% to 90%, 40% to 80%, 40% to 70%, 40% to 60%, 40% to 50%, 50% to 99%, 50% to 90%, 50% to 80%, 50% to 70%, 50% to 60%, 60% to 99%, 60% to 90%, 60% to 80%, 60% to 70%, 70% to 99%, 70% to 90%, 70% to 80%, 80% to 99%, 80% to 90%, and 90% to 99%.

[0026] In the above embodiment, the polymer formulation may include 1% to 60%, 1% to 50%, 1% to 40%, 1% to 30%, 1%, 1% to 20%, 1% to 10%, 10% to 60%, 10% to 50%, 10% to 40%, 10% to 30%, 10%, 10% to 20%, 20% to 60%, 20% to 50%, 20% to 40%, 20% to 30%, 30% to 60%, 30% to 50%, 30% to 40%, 40% to 60%, 40% to 50%, or 50% to 60% by weight of a tetrapolymer based on the total weight of the polymer formulation.

[0027] While not bound by theory, the tetrapolymer compositions described herein are considered to be efficient plasticizers when combined with polyvinyl chloride to produce polymer formulations. The tetrapolymer compositions may have improved plasticization efficiencies, calculated according to the methods described later herein, compared to other polymer compositions that can be combined with polyvinyl chloride. Therefore, polymer formulations including embodiments of the tetrapolymer compositions described herein may exhibit improved processability, lower tensile strength, and higher elongation than conventional flexible PVC polymers containing other plasticizers. Furthermore, because the tetrapolymer compositions may have improved plasticization efficiencies, the polymer formulations described herein may require relatively less plasticizer than conventional flexible PVC polymers utilizing other conventional polymer plasticizers. The plasticization efficiency of the tetrapolymer compositions used herein can be calculated as the plasticization efficiency relative to the conventional phthalate plasticizer diisodecylphthalate (DIDP). In embodiments, the tetrapolymer compositions may have plasticization efficiencies 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 may further include other materials present to modify the properties of polyvinyl chloride. These one or more optional components may include, but are not limited to, polystyrene, styrene copolymers, polyolefins including homo and copolymers containing polyethylene and / or polypropylene, and other ethylene / α-olefin copolymers, polyacrylic resins, butadiene-containing polymers such as acrylonitrile butadiene styrene terpolymer (ABS) and methacrylate butadiene styrene terpolymer (MBS), and chlorinated polyethylene (CPE) resins. These one or more optional components may further include DIDP, epoxidized soybean oil (ESO), stearic acid, and stabilizers known in the art. Such stabilizers may include barium / zinc stabilizers and Irganox® 1076 stabilizer (commercially available from BASF).

[0029] In some embodiments, the polymer formulation may contain one or more optional components based on the total weight of the polymer formulation, in the following proportions: 1% to 40% by weight, 1% to 30% by weight, 1% or more by weight, 1% to 20% by weight, 1% to 10% by weight, 10% to 50% by weight, 10% to 40% by weight, 10% to 30% by weight, 10% or more by weight, 10% to 20% by weight, 20% to 50% by weight, 20% to 40% by weight, 20% to 30% by weight, 30% to 50% by weight, 30% to 40% by weight, or 40% to 50% by weight.

[0030] To produce polymer formulations, the tetrapolymer composition may be blended with polyvinyl chloride and optionally one or more additional components. In further embodiments, one or more optional components and polyvinyl chloride may be dry-mixed separately from the tetrapolymer. In embodiments, one or more optional components and polyvinyl chloride may be dry-mixed in a "Henschel" type high-speed mixer. The dry blend of one or more optional components and polyvinyl chloride may then be introduced into a polymer mixing apparatus. In embodiments, the mixing apparatus may be a Haake mixer, a co-rotating twin-screw extruder, a counter-rotating twin-screw extruder, or a conical mixer. The temperature of the Haake mixer can be set to a melting 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 a dry blend of one or more optional components with polyvinyl chloride is added to the Haake mixer, the melting temperature may decrease. Once the temperature of the Haake mixer has risen to the desired melting temperature, the tetrapolymer composition can be added to the Haake mixer. During mixing, the melting torque can be monitored to check the melting of the PVC compound and determine whether the melting peak has been reached. As used herein, the melting peak refers to the peak in the torque curve generated via software from the torque measured after the initial loading of the PVC dry blend. The melting peak can be observed directly from the torque change. In some embodiments, once the melting peak is reached, the Haake mixer may continue mixing for an additional time to ensure the desired melted mixture. For example, the Haake mixer may continue mixing for a further 1 to 60 minutes, 1 to 30 minutes, 1 to 10 minutes, 1 to 5 minutes, 5 to 60 minutes, 5 to 30 minutes, 5 to 10 minutes, 10 to 60 minutes, 10 to 30 minutes, or 30 to 60 minutes. The polymer formulation can be produced after the tetrapolymer, polyvinyl chloride, and one or more optional additional components have been sufficiently melted and mixed.

[0031] In embodiments involving the formation of plasticized PVC using a co-rotating twin-screw extruder, dry blend powder and tetrapolymer pellets may be fed into the extruder's feed hopper using a weight feeder. The extruder may comprise multiple mixing sections separated by two rotating screws, a powder conveying section, a melting and dissolving section, and a molten material conveying section. As the mixture of dry blend powder and tetrapolymer pellets flows through the extruder, the powder and pellets melt and mix to produce a homogeneous molten material. A die plate may be attached to the end of the extruder through which the polymer molten material flows as a continuous strand. The continuous strand can be cut using a rotating knife to produce plasticized PVC pellets. In embodiments, the melting and dissolving section of the extruder may be set to a temperature of 140°C to 200°C. In embodiments, the temperature of the molten material exiting the die plate may be 170°C to 210°C. To test whether the PVC powder is completely plasticized, the PVC pellets can be pressed into a thin film using a compression molder and analyzed using a photoscanner in transmission mode. After complete and satisfactory plasticization, the image will have a white area percentage of less than 5%.

[0032] In one or more further embodiments, the polymer formulations described herein may be formed into articles. Articles containing the polymer formulations described herein may be used in flexible PVC applications, including roofing and geomembrane applications. Articles may include films and plaques containing the polymer formulations described herein.

[0033] Test method

[0034] density

[0035] Samples for density measurement are prepared according to ASTM D4703. Measurements are taken during a 1-hour sample press according to ASTM D792, Method B. The value is expressed in grams per cubic centimeter (g / cm³). 3 It is reported in units of )

[0036] Melt Index

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

[0038] Dynamic Mechanical Spectroscopy (DMS)

[0039] Viscosity measurements were performed using a parallel plate rheometer (ARES) from TA Instruments. The sample was compressed in air at 190°C and 25,000 pounds of pressure for 6.5 minutes, and then the plaque was cooled on a workbench. The plaque thickness was approximately 3 mm. Constant temperature-frequency sweep measurements were performed under nitrogen purging using an ARES strain-controlled parallel plate rheometer (TA Instruments) equipped with a 25 mm parallel plate. For each measurement, the rheometer was thermally equilibrated for at least 30 minutes before the gap was reduced to zero. The sample was placed on the plate and melted at 180°C for 5 minutes. The plate was then closed to 2 mm, the sample was trimmed, and then the test was initiated. This method incorporated an additional 5-minute delay to allow for thermal equilibrium. This experiment was performed at 180°C, at 5 points per 10x interval, over a frequency range of 0.1–500 radians / second. The strain amplitude was constant at 5%. The stress response was analyzed with respect to amplitude and phase, and from this, the storage modulus (G'), loss modulus (G''), complex modulus (G*), dynamic complex viscosity (η*), and tan(δ) or tandelta were calculated. In addition, thin plaques with a thickness of approximately 3-4 mm were prepared from the sample, and the tandelta (ratio of loss modulus to storage modulus) versus temperature was measured from -100 to 80°C.

[0040] Tensile properties

[0041] Tensile strength, tensile modulus, and elongation at fracture were measured according to ASTM D1708. To test these properties, minute tensile bars were punched out from a compression-molded plaque with a thickness of 2 mm.

[0042] Glass transition temperature (Tg)

[0043] The glass transition temperature (Tg) is measured from the tan delta 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, this analysis is performed using a TA Instruments Q1000DSC equipped with an RCS (refrigerated cooling system) and an autosampler. A nitrogen purge gas flow rate of 50 mL / min is used during the test. Each sample is melted and compressed into a thin film at approximately 175°C, and then the molten sample is air-cooled to room temperature (approximately 25°C). Test specimens of 3–10 mg, 6 mm in diameter are extracted from the cooled polymer, weighed, placed in a lightweight aluminum pan (approximately 50 mg), and pressed shut. Analysis is then performed to determine its thermal properties.

[0046] The thermal behavior of the sample is determined by raising and lowering the sample temperature to create a heat-flux-temperature profile. First, to remove its thermal history, the sample is rapidly heated to 120°C and held isothermally for 3 minutes. Next, the sample is cooled to -50°C at a cooling rate of 10°C / min and held isothermally at -50°C for 3 minutes. Then, the sample is heated to 120°C at a heating rate of 10°C / min (this is the "second heating" gradient). The cooling curve and the second heating curve are recorded. The cooling curve is analyzed by setting the baseline endpoint from the start of crystallization to -20°C. The thermal curve is analyzed by setting the baseline endpoint from -20°C to the end of melting. The values ​​obtained are the extrapolated melting start point Tm and the extrapolated crystallization start point Tc. The heat of fusion (Hf) (also known as enthalpy of fusion) and peak melting temperature are reported from the second heating curve. The peak crystallization temperature is determined from the cooling curve.

[0047] The melting point Tm is first determined from the DSC heating curve by drawing a baseline between the start and end of the melting transition. Next, a tangent line is drawn to the data on the lower temperature side of the melting peak. The point where this line intersects the baseline is the extrapolated melting start point (Tm). This is as described in 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 can be determined from the DSC cooling curve as described above, except that the tangent is drawn on the high-temperature side of the crystallization peak. The point where this tangent intersects the baseline is the extrapolated crystallization start point (Tc).

[0049] Examples

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

[0051] Example 1: Sample 1

[0052] To prepare Sample 1, a 545 ml (mL) stirred autoclave was filled with a mixture of ethylene (E), n-butyl acrylate (nBA), carbon monoxide (CO), and propylene. An organic peroxide (t-butyl peroctoate) was added to the mixture as a polymerization initiator in a solution of 1% to 3% by weight in odorless mineral spirits, and this mixture was heated to approximately 27,000 psi (1,898 kg / cm³). 2The reactor was subjected to the set pressure. The reactor temperature was set to a target temperature of 205°C. Tetrapolymers were continuously synthesized under the polymerization conditions shown in Table 1, and then converted into pellet form by melt extrusion. The conditions listed in Table 1 are averages over the length of time that sample 1 was collected. The experimental reactor tetrapolymers thus formed "autoclave-produced" were found to have the characteristics described in Table 2. [Table 1]

[0053] The properties of Sample 1 are shown in Table 2 below. Here, nBA represents n-butyl acrylate, CO represents carbon monoxide, and 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 at 190°C and 2.16 kg according to ASTM D-1238. [Table 2]

[0054] Example 2: Comparative Sample A

[0055] To prepare Sample 1, a 545 ml (mL) stirred autoclave was filled with a mixture of ethylene (E), n-butyl acrylate (nBA), carbon monoxide (CO), and acetone. An organic peroxide (t-butyl peroctoate) was added to the mixture as a polymerization initiator at a concentration of 1% to 3% by weight in odorless mineral spirits, and this mixture was heated to approximately 27,000 psi (1,898 kg / cm³). 2 The reactor was subjected to the set pressure. The reactor temperature was set to a target temperature of 205°C. Tetrapolymers were continuously synthesized under the polymerization conditions shown in Table 3, and then converted into pellet form by melt extrusion. The conditions listed in Table 2 are the average over the length of time that comparative sample A was collected. The experimental reactor terpolymer thus formed "autoclave-produced" was found to have the characteristics described in Table 3. [Table 3]

[0056] The properties of comparative sample A are shown in Table 4 below. Here, nBA represents n-butyl acrylate, CO represents carbon monoxide, and P represents propylene. The weight percentages of nBA, CO, and P are based on the total weight of comparative sample A, and the melt index is measured at 190°C and 2.16 kg according to ASTM D-1238. [Table 4]

[0057] Example 3: Comparison of Sample 1 and Comparative Sample A

[0058] In Example 3, Sample 1 and Comparative Sample A were compared by analyzing their melt index, molecular weight, molecular weight distribution, glass transition temperature (Tg) (DSC), glass transition temperature (from the tan delta peak), melting temperature, crystallization temperature, heat of fusion, and storage modulus at 20°C, which are shown in Table 5. These properties were measured according to the test methods described herein. To determine the glass transition temperature (from the tan delta peak), a Tan(δ) vs. temperature plot was drawn, and the peak temperatures are shown in the table below. [Table 5]

[0059] As shown in Table 5, compared to comparative sample A, sample 1 exhibited lower melting temperature, crystallization temperature, and heat of fusion. In addition, sample 1 showed a lower storage modulus at temperatures above -50°C. Since flexibility is required for processing, handling, and installation of the finished product, a low storage modulus and thermal properties are desirable for plasticized PVC applications.

[0060] Example 4: Sample PVC-1

[0061] In Example 4, a PVC compound (referred to as Sample PVC-1) containing polyvinyl chloride and Sample 1 from Example 1 was prepared. The materials used to produce Sample PVC-1 were polyvinyl chloride with a K value of 70 (supplied by Formosa Plastics Corporation), diisodecyl phthalate (DIDP) (supplied by ExxonMobil), barium / zinc stabilizer (supplied by Galata Chemicals), epoxidized soybean oil (ESO) (supplied by Galata Chemicals), titanium dioxide (supplied by Chemors), stearic acid (supplied by Sigma-Aldrich), and Irganox® 1076 stabilizer (supplied by BASF). The amounts of each component in Sample PVC-1 are shown in Table 6. [Table 6]

[0062] To prepare samples PVC-1 and PVC-2, all components except for the composition of sample 1 were dry-mixed in a "Henschel" high-speed mixer. The dry blend was then loaded into a Haake mixer (composition of sample 1). The Haake temperature was set to 170°C, and once the PVC dry blend was added, the melting temperature decreased. Once the melting temperature rose back to 170°C, the composition of sample 1 was then slowly added to the Haake mixer. The melting torque was closely monitored to check the melting of the PVC compound. Once the melting peak, as determined according to the method described herein, was reached, the Haake mixer was run for a further 10 minutes to ensure good melt mixing. Next, samples PVC-1 and PVC-2 were removed from the Haake and hot-pressed at 185°C to form 2-4 nm plaques for various characterizations.

[0063] Example 5: Sample PVC-1a

[0064] In Example 5, similar to PVC-1, a PVC compound called Sample PVC-1a was prepared using a different method than in Example 4. Specifically, Sample PVC-1a contained polyvinyl chloride dry powder having the same composition as polyvinyl chloride in Example 4 and tetrapolymer pellets having the same composition as Sample 1 in Example 1. The PVC dry blend powder and tetrapolymer pellets were fed into a 26 mm Coperion co-rotating twin-screw extruder with 11 barrels having a total length / diameter ratio of 44. The extruder had a relatively high-strength screw design with one molten section of 4.8 length / diameter and two mixed sections of approximately 4.8 length / diameter and approximately 3.4 length / diameter, respectively. The PVC dry blend powder was fed using a KTRON gravimetric powder feeder, and the tetrapolymer pellets were fed using a KTRON gravimetric pellet feeder. The extruder was equipped with a die having four 3.1 mm die holes. Continuous polymer strands were cut into pellets. Extruder barrels 3 through 11 were set to 160°C, barrel 2 was set to 80°C, and no heat was applied to the supply barrel.

[0065] Table 7 below shows the processing parameters for the extrusion process to obtain sample PVC-1a and the percentage of white area of ​​the resulting film. As evidenced by the percentage of white area of ​​0.47%, the treatment described in Example 5 resulted in complete and satisfactory plasticization of the PVC powder. [Table 7]

[0066] The 4g pellet obtained was compressed into a thin film using a Carber press at a pressure of 10,000 psi and a temperature of 180°C for 3 minutes. The film was then cooled to room temperature while maintaining the pressure of 10,000 psi, and then removed from the press.

[0067] The obtained PVC film was scanned using an Epson Perfection Photo Scanner in reflection mode at 4800 dips with an image size of 22mm x 22mm, and saved in 8-bit grayscale. The resulting image was then opened in ImageJ software and duplicated twice to obtain image copy 1 and image copy 2. Gaussian blur was applied to image copy 2 sigma (radius) at 40 pixels. Image copy 2 was subtracted from image copy 1 using an image calculator. An unsharp mask was applied to the resulting 2-pixel mask weight radius (sigma) image. Next, a threshold of default gray level 56 was applied. As a next step, the image was expanded, and then a median filter with a radius of 2 pixels was applied. The particle size was 25 μm. 3 From infinity to μm 3 The size range was analyzed. Then, using Microsoft Excel, the output of the percentage of white area was compiled into a table.

[0068] Example 6: Comparative sample PVC-A

[0069] In Example 6, a composition called comparative sample PVC-A was prepared containing polyvinyl chloride and sample 1 from Example 1 described above. The materials used to produce sample PVC-1 were polyvinyl chloride with a K value of 70 (supplied by Formosa Plastics Corporation), diisodecyl phthalate (DIDP) (supplied by ExxonMobil), barium / zinc stabilizer (supplied by Galata Chemicals), epoxidized soybean oil (ESO) (supplied by Galata Chemicals), titanium dioxide (supplied by Chemors), stearic acid (supplied by Sigma-Aldrich), and Irganox® 1076 stabilizer (supplied by BASF). The amounts of each component in sample PVC-1 are shown in Table 8. [Table 8]

[0070] To prepare comparative samples PVC-A, PVC-B, and PVC-C, all components except for the composition of Sample 1 were dry-mixed in a "Henschel-type" high-speed mixer. The dry blend was then loaded into a Haake mixer (composition of Sample 1). The Haake temperature was set to 170°C, and once the PVC dry blend was added, the melting temperature decreased. Once the melting temperature rose back to 170°C, the composition of Sample 1 was then slowly added to the Haake mixer. The melting torque was closely monitored to check the melting of the PVC compound. Once the melting peak, as determined according to the method described herein, was reached, the Haake mixer was continued to run for another 10 minutes to ensure good melt mixing. Next, samples PVC-1 and PVC-2 were removed from the Haake and hot-pressed at 185°C to form plaques 2–4 mm thick for various characterizations.

[0071] Example 7: Comparison of Sample PVC-1 with Comparative Sample PVC-A

[0072] In Example 7, the mechanical properties and plasticization efficiency were compared for samples PVC-1 and PVC-2, as well as comparative samples PVC-A, PVC-B, and PVC-C. As provided in Examples 4 and 6 above, samples PVC-1 and PVC-2 contained the composition of sample 1 from Example 1 (EP-nBA-CO (58%-2%-30%-10%)). Furthermore, PVC-1 contained DIDP. Comparative samples PVC-A and PVC-B contained the composition of comparative sample A from Example 2 (E-nBA-CO (60%-30%-10%)). Furthermore, PVC-A contained DIDP. Comparative sample PVC-C contained only DIDP and did not contain the composition of sample 1 from Example 1 or the composition of sample A from Example 2.

[0073] The mechanical properties of samples PVC-1 and PVC-2 were measured, along with comparative samples PVC-A, PVC-B, and PVC-C, 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, microtensile bars were punched out from compression-molded plaques prepared from the sample compositions. The compression-molded plaques had a thickness of 1.5 mm.

[0074] The viscosity and DMA characteristics of samples PVC-1 and PVC-2 were measured together with comparative samples PVC-A, PVC-B, and PVC-C according to the test methods provided herein. Viscosity measurements were performed using a parallel-plate configuration TA instrument ARES. Samples were tested at 180°C with a 5% strain, and the frequency sweep was set to 0.1 to 500 radians / second. Plaques with a thickness of 3 to 4 mm were prepared from the samples, and the tandelta (ratio of loss modulus to storage modulus) versus temperature was measured from -100 to 80°C.

[0075] The mechanical properties of samples PVC-1 and PVC-2, as well as comparative samples PVC-A, PVC-B, and PVC-C, are shown in Table 9 below. [Table 9]

[0076] As shown in Table 9, sample PVC-1 was observed to show results comparable to comparative sample PVC-C, which was a DIDP-only sample. Furthermore, while sample PVC-1 and comparative sample PVC-A showed equivalent tensile strength and elongation at break, sample PVC-1 showed a lower modulus of elasticity. In addition, while sample PVC-2 and comparative sample PVC-B showed equivalent tensile strength, sample PVC-1 showed a lower modulus of elasticity. As previously stated in this disclosure, for some flexible PVC applications such as roofing, a lower modulus of elasticity is desirable because it results in greater flexibility and pliability.

[0077] The following formulas were used to calculate the elastic moduli of PVC-1 and PVC-A, respectively.

[0078] Regarding sample PVC-1:

number

[0079] Regarding comparative sample PVC-A:

number

[0080] The modulus of elasticity of sample 1 and comparative sample A was determined based on DMA data from Example 3 above. Using the above formula, the modulus of elasticity of polyvinyl chloride with a K value of 70 (supplied by Formosa Plastics Corporation) and other additives not included in comparative sample A or sample 1 were calculated inversely using the modulus of elasticity of the entire sample PVC-A or sample PVC-1 (measured by tensile testing). According to the formulation, the polyvinyl chloride with a K value of 70 (supplied by Formosa Plastics Corporation) in sample PVC-1 and sample PVC-A is known to be the same as that of other additives not included in comparative sample A or sample 1. Therefore, assuming that the modulus of elasticity of polyvinyl chloride with a K value of 70 in PVC-1 with other additives is equal to the modulus of elasticity of polyvinyl chloride with a K value of 70 in PVC-A with other additives, the modulus of elasticity of PVC-1 and comparative PVC-A could be calculated and compared with the actual measured values. [Table 10]

[0081] As shown in Table 10, it was concluded that the calculated modulus of elasticity of sample PVC-1 was higher than the actually measured value. This indicates that the low modulus of elasticity of sample PVC-1 is not simply due to the low modulus of sample 1 (of Example 1 above), which may further mean that sample 1 has improved plasticization efficiency in PVC, resulting in a lower modulus of elasticity for the overall PVC composition.

[0082] Furthermore, sample PVC-1 was observed to exhibit a lower Tg and a broader Tg peak compared to comparative sample PVC-A. While not theoretically bound, a lower glass transition temperature may contribute to the lower elastic modulus of sample PVC-1. Moreover, the lower Tg of sample PVC-1 may further indicate that sample 1 contributed to the improved plasticization efficiency in PVC.

[0083] To demonstrate that Sample 1 (of Example 1) showed improved plasticization efficiency in PVC compared to Comparative Sample A (of Example 2), the plasticization efficiency (PE) of Sample 1 and Comparative Sample A with respect to DIDP was calculated based on the following formula.

number

[0084] Table 11 shows the plasticization efficiency for DIDP calculated based on the above formula, as well as the measured elastic modulus of comparative sample PVC-C and sample PVC-B or comparative sample PVC-B. [Table 11]

[0085] It will be apparent that modifications and changes are possible without departing from the scope of this disclosure as defined in the attached claims. More specifically, certain aspects of this disclosure are identified herein as preferred or particularly advantageous, but this disclosure is intended not to be limited to these aspects. The present specification includes the following embodiments. Section 1: A tetrapolymer composition, It has the formula E / P / X / CO, During the ceremony, E contains 25% to 90% by weight of ethylene. P contains 0.1% to 5.0% by weight of propylene. X contains 5% to 40% by weight of alkyl acrylate. CO contains 3% to 30% by weight of carbon monoxide. The tetrapolymer composition has a melt index of I2, measured at 2.16 kg and 190°C according to ASTM 1238, between 10 and 1,000 g / 10 min. Section 2: The tetrapolymer composition according to item 1, wherein the tetrapolymer composition has a melt index of I2, ranging from 10 g / 10 min to 800 g / 10 min, when measured at 2.16 kg and 190°C according to ASTM 1238. Section 3: The tetrapolymer composition according to item 1 or 2, wherein the tetrapolymer composition has a melt index of I2, measured at 2.16 kg and 190°C according to ASTM 1238, between 50 g / 10 min and 600 g / 10 min. Section 4: The tetrapolymer composition according to any one of claims 1 to 3, wherein the tetrapolymer contains 1% to 4% by weight of P based on the total weight of the tetrapolymer. Section 5: The tetrapolymer composition according to any one of claims 1 to 4, wherein the tetrapolymer contains 10% to 40% by weight of X based on the total weight of the tetrapolymer. Item 6: The tetrapolymer composition according to any one of claims 1 to 5, wherein the tetrapolymer contains 5% to 20% by weight of CO based on the total weight of the tetrapolymer. Section 7: The tetrapolymer composition according to any one of claims 1 to 6, wherein the tetrapolymer composition has a storage modulus of 0.1 MPa to 100 MPa when measured at 20°C. Section 8: The tetrapolymer composition according to any one of claims 1 to 7, wherein the tetrapolymer composition has a melting temperature of 30°C to 80°C. Section 9: The tetrapolymer composition according to any one of claims 1 to 8, wherein the tetrapolymer composition has a crystallization temperature of 20°C to 70°C. Section 10: The tetrapolymer composition according to any one of claims 1 to 9, wherein the tetrapolymer composition has a heat of fusion of 10 J / g to 100 J / g. Section 11: The tetrapolymer composition according to any one of claims 1 to 10, wherein the tetrapolymer composition has a storage modulus of 1.0 MPa to 4.5 MPa when measured at 20°C. Section 12: A polymer compound comprising the tetrapolymer composition described in any one of items 1 to 11, and further comprising polyvinyl chloride. Section 13: The polymer formulation according to claim 12, comprising 1% to 60% by weight of the tetrapolymer based on the total weight of the polymer formulation. Section 14: The polymer formulation according to item 12 or 13, comprising 40% to 99% by weight of the polyvinyl chloride based on the total weight of the polymer formulation. Section 15: An article containing a polymer compound as described in any one of paragraphs 12 to 14.

Claims

1. A tetrapolymer composition, Having formula E / P / X / CO, The tetrapolymer is determined based on the total weight of the tetrapolymer. It contains 25% to 90% by weight of ethylene (E), Contains 0.1% to 5.0% by weight of propylene (P), Containing 5% to 40% by weight of n-butyl acrylate (X), Contains 3% to 30% by weight of carbon monoxide (CO), When the tetrapolymer composition was measured at 2.16 kg and 190°C according to ASTM 1238, it had a melt index of 10 to 1,000 g / 10 min, I ２ A tetrapolymer composition having the following characteristics.

2. When the tetrapolymer composition was measured at 2.16 kg and 190°C according to ASTM 1238, it had a melt index of 10 g / 10 min to 800 g / 10 min, I ２ A tetrapolymer composition according to claim 1, having the following characteristics.

3. When the tetrapolymer composition was measured at 2.16 kg and 190°C according to ASTM 1238, it had a melt index of 50 g / 10 min to 600 g / 10 min, I ２ A tetrapolymer composition according to claim 1 or 2, having the following characteristics.

4. The tetrapolymer composition according to any one of claims 1 to 3, wherein the tetrapolymer contains 1% to 4% by weight of P based on the total weight of the tetrapolymer.

5. The tetrapolymer composition according to any one of claims 1 to 4, wherein the tetrapolymer composition has a storage modulus of 0.1 MPa to 100 MPa when measured at 20°C.

6. The tetrapolymer composition according to any one of claims 1 to 5, wherein the tetrapolymer composition has a melting temperature of 30°C to 80°C.

7. The tetrapolymer composition according to any one of claims 1 to 6, wherein the tetrapolymer composition has a crystallization temperature of 20°C to 70°C.

8. The tetrapolymer composition according to any one of claims 1 to 7, wherein the tetrapolymer composition has a heat of fusion of 10 J / g to 100 J / g.

9. The tetrapolymer composition according to any one of claims 1 to 8, wherein the tetrapolymer composition has a storage modulus of 1.0 MPa to 4.5 MPa when measured at 20°C.

10. A polymer compound comprising the tetrapolymer composition according to any one of claims 1 to 9, further comprising polyvinyl chloride.

11. The polymer formulation according to claim 10, comprising 1% to 60% by weight of the tetrapolymer based on the total weight of the polymer formulation.

12. The polymer compound according to claim 10 or 11, comprising 40% to 99% by weight of the polyvinyl chloride based on the total weight of the polymer compound.

13. An article comprising a polymer compound according to any one of claims 10 to 12.

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