THERMOFORMED ARTICLE, AND METHOD FOR THERMOFORMING IT

专利摘要:
thermoformed article formed from a porous polymeric sheet. A thermoformed article is provided which is formed from a polymeric sheet having a thickness of from about 0.1 to about 100 millimeters. the polymeric sheet contains a thermoplastic composition that includes a continuous phase, which includes a matrix polymer. a microinclusion additive and a nanoinclusion additive are dispersed within the continuous phase in the form of discrete domains, and a porous network is defined in the composition that includes a plurality of nanopores with an average transverse dimension of about 800 nanometers or less.
公开号:BR112016025073B1
申请号:R112016025073-7
申请日:2015-06-04
公开日:2022-01-04
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Brent M. Thompson；Duane L. Mcdonald
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

Fundamentals of the Invention
[001] Thermoforming is a common technique used to form three-dimensional items such as trays, cups, plates, refrigerator door linings and packages. In a typical thermoforming process, a thermoplastic sheet is initially heated to a temperature above the glass transition temperature so that it becomes malleable. The sheet is then molded into a thermoforming mold and cooled so that it retains the desired shape. Thereafter, the molded sheet is cut and trimmed to yield the final thermoformed article. One of the general requirements of a successful thermoforming process is the use of thermoplastic polymers (eg polyesters) that are capable of retaining a relatively high degree of melting force when heated. Unfortunately, polymers of this nature tend to be relatively expensive and can significantly increase the total cost of the thermoforming process. With this in mind, several attempts have been made to use gaseous blowing agents to create "foamed" sheet structures, thereby reducing the fiber density and, in turn, the polymer content. Unfortunately, the processability and tensile properties of the foamed structure are often compromised due to uncontrolled pore size and distribution.
[002] Thus, there is currently a need for an improved polymeric sheet for use in thermoforming processes that may have a reduced amount of polymers, but still have good properties. Summary of the Invention
[003] In accordance with an embodiment of the present invention, polymeric having a thickness of from about 0.1 to about 100 millimeters. The polymeric sheet contains a thermoplastic composition that includes a continuous phase, which includes a matrix polymer. A microinclusion additive and a nanoinclusion additive are dispersed within the continuous phase in the form of discrete domains, and a porous network is defined in the composition that includes a plurality of nanopores with an average transverse dimension of about 800 nanometers or less.
[4] According to another embodiment of the present invention, a method for thermoforming an article is disclosed. The method comprises heating a polymeric sheet, as described above, to a temperature above the glass transition temperature of the thermoplastic composition; feeding the heated polymeric sheet to a thermoforming mold; and molding the polymeric sheet into the mold.
[5] Other properties and aspects of the present invention will be discussed in more detail below. Brief Description of Figures
[6] A full and enlightening disclosure of the present invention, including its best mode, addressed to persons skilled in the art, is set out more particularly in the remainder of the specification, which makes reference to the accompanying figures, in which:
[7] Fig. 1 is a schematic illustration of an embodiment for forming the polymeric sheet of the present invention;
[8] Figs. 2-3 are SEM micrographs of the unstretched sheet of Example 7 (the sheet was cut parallel to the machine direction orientation);
[9] Figs. 4-5 are SEM micrographs of the stretched sheet of Example 7 (the sheet was cut parallel to the machine direction orientation);
[10] Figs. 6-7 are SEM micrographs of the unstretched sheet of Example 8, where the sheet was cut perpendicular to the machine direction in Fig. 6 and parallel to the machine direction in Fig. 7; and
[11] Figs. 8-9 are SEM micrographs of the stretched sheet of Example 8 (the sheet was cut parallel to the machine direction orientation).
[12] The repeated use of reference characters in the present specification and in the figures is intended to represent the same or similar features or elements of the invention. Detailed Description of Representative Modalities
[13] Detailed references will be made to various embodiments of the invention, with one or more examples described below. Each example is provided by way of explanation of the invention, without limitation of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations may be made to the present invention without departing from the scope or spirit of the invention. For example, features illustrated or described as part of one embodiment can be used in another embodiment to produce yet another embodiment. Thus, the present invention is intended to cover such modifications and variations as are within the scope of the appended claims and their equivalents.
[14] Generally speaking, the present invention is directed to a polymeric sheet for use in a thermoformed article. The thickness of the polymeric sheet generally ranges from about 0.1 to about 100 millimeters, in some embodiments from about 0.3 to about 60 millimeters, and in some embodiments from about 0.5 to about 20 millimeters. mm. Of course, the actual thickness can vary greatly depending on the desired application of the thermoformed article. For example, fine gauge thermoforming is primarily employed in the manufacture of disposable cups, containers, lids, trays, blisters, ladles and other products in the food, medical and general retail industries. In such cases, the thickness of the polymeric sheet can range from about 0.1 to about 2 millimeters, in some embodiments from about 0.2 to about 1.8 millimeters, and in some embodiments from 0.3 to about 1.8 millimeters. about 1.5 millimeters. On the other hand, heavy gauge thermoforming includes parts as diverse as vehicle door panels and panels, refrigerator linings, utility vehicle buckets and plastic pallets. In such cases, the thickness of the polymeric sheet can range from about 2 to about 100 millimeters, in some embodiments from about 3 to about 60 millimeters, and in some embodiments from about 4 to about 20 millimeters.
[15] Regardless of thickness, the polymeric sheet contains a thermoplastic composition, which includes a continuous phase that includes a matrix polymer (e.g. polyester) and also contains a nanoinclusion additive that is at least partially incompatible with the matrix polymer. , so that it becomes dispersed within the continuous phase, as nanoscale discrete phase domains. During stretching, when the composition is subjected to strain and elongation stress, the present inventors have discovered that these discrete nanoscale phase domains are capable of uniquely interacting to create a network of pores. Nominally, it is believed that elongation deformation can initiate zones of intensive localized shear and/or zones of stress intensity (e.g. normal stresses) near discrete phase domains as a result of stress concentrations arising from material mismatches. . These shear zones and/or stress intensity zones cause some initial debonding in the matrix adjacent to the domains. Once the initial pores are formed, the matrix located between domains can plastically deform to create internal stretched areas that locally narrow (or "bottle") and harden by deformation. This process enables pore formation through the volume of the composition which grows in the stretching direction, therefore leading to the formation of a porous network while molecular orientation leads to strain hardening which improves mechanical strength.
[16] Through the techniques described above, a unique porous network can be formed so that the average percentage volume occupied by pores within a given unit volume of composition can be from about 15% to about 80% per cm3, in some embodiments, from about 20% to about 70%, and in some embodiments, from about 30% to about 60% per cubic centimeter of the composition. With such a pore volume, the composition can have a relatively low density, such as about 1.4 grams per cubic centimeter ("g/cm3") or less, in some embodiments, about 1.2 g/cm3 or less, in some embodiments, from about 0.2 g/cm3 to about 0.83 and, in some embodiments, from about 0.1 g/cm3 to about 0.5 g/cm3 . A substantial portion of the pores in the pore network are also of "nanoscale" size ("nanopores"), such as those having an average transverse dimension of about 800 nanometers or less, in some embodiments, from about 1 to about 500 nanometers. nanometers, and in some embodiments from about 5 to about 400 nanometers, and in some embodiments from about 10 to about 100 nanometers. The term "cross-sectional dimension" generally refers to a characteristic dimension (e.g. width or diameter) of a pore that is substantially orthogonal to its major axis (e.g. length) and also normally orthogonal to the direction of stress. applied during stretching. Nanopores can also have an average axial dimension within the range of about 100 to about 5000 nanometers, in some embodiments from about 50 to about 2000 nanometers, and in some embodiments from about 100 to 1000 nanometers. The "axial dimension" is the dimension in the main axis direction (eg length), which is normally in the stretch direction. Such nanopores can, for example, constitute about 15% by volume or more, in some embodiments, about 20% by volume or more, in some embodiments, from about 30% by volume to 100% by volume, and in some modalities, from about 40% by volume to about 90% by volume of the total volume of pores in the composition.
[17] In addition to a reduced density, the nanoporous structure can also provide a variety of different additional benefits to the resulting polymeric sheet. For example, such a structure can help to restrict the flow of fluids through the sheet and is generally impermeable to fluids (e.g., liquid water), thus allowing the sheet to insulate a surface from water penetration. In this regard, the polymeric sheet may have a relatively high value of hydrostatic charge of about 50 centimeters ("cm") or more, in some embodiments, about 100 cm or more, in some embodiments, about 150 cm or more. more and, in some embodiments, from about 200 cm to about 1000 cm, as determined in accordance with ATTCC 127-2008. Other beneficial properties can also be achieved. For example, the resulting sheet can generally be permeable to water vapor. Sheet water vapor permeability can be characterized by its relatively high water vapor transmission rate (“WVTR”), which is the rate at which water vapor penetrates a sheet as measured in units of grams. per square meter for 24 hours (g/m2/24 hrs). For example, the polymeric sheet can exhibit a WVTR of about 300 g/m 2 -24 hours or more, in some embodiments, about 500 g/m 2 -24 hours or more, in some embodiments, about 1000 g/m 2 - 24 hours or more and, in some embodiments, from about 3,000 to about 15,000 g/m2-24 hours, as determined in accordance with ASTM E96/96M-12, Procedure B, or INDA Test Procedure IST-70.4 ( 01).
[18] Various embodiments of the present invention will now be described in more detail. I. Thermoplastic Composition A. Matrix Polymer
[19] As indicated above, the thermoplastic composition contains a continuous phase within which the microinclusion and nanoinclusion additives are dispersed. The continuous phase contains one or more matrix polymers, which typically constitute from about 60% by weight to about 99% by weight, in some embodiments, from about 75% by weight to about 98% by weight, and , in some embodiments, from about 80% by weight to about 95% by weight of the thermoplastic composition. The nature of the matrix polymer(s) used to form the continuous phase is not essential and any suitable polymer can be used, such as polyesters, polyolefins, styrene polymers, polyamides, etc. In certain embodiments, for example, polyesters can be used in the composition to form the polymer matrix. Any of a variety of polyesters can be generally employed, such as aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (e.g. polyethylene carbonate), copolymers of poly-3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3 - hydroxybutyrate-co-3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and aliphatic based polymers of succinate (e.g. polybutylene succinate, polybutylene adipate succinate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (e.g., polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene isophthalate adipate, polybutylene isophthalate adipate, etc.); aromatic polyesters (e.g. polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[20] In certain cases, the thermoplastic composition may contain at least one polyester that is rigid in nature and thus has a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be from about 0°C or greater, in some embodiments, from about 5°C to 100°C, in some embodiments, from about 30°C to about 100°C. from 80°C, and, in some embodiments, from about 50°C to about 75°C. The polyester may also have a melt temperature of from about 140°C to about 300°C, in some embodiments from about 150°C to about 250°C, and in some embodiments from about 160°C. C to about 220°C. The melting temperature can be determined by means of differential scanning calorimetry (DSC) in accordance with ASTM D-3417. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM E1640-09.
[21] A particularly suitable rigid polyester is polylactic acid, which can be derived generally from the monomer units of any isomer of lactic acid, such as levorotatory lactic acid ("L-lactic acid"), dextrorotatory lactic acid ("D-lactic acid"). lactic acid”), meso-lactic acid or combinations thereof. The monomer units can also be formed by anhydrides of any isomer of lactic acid, including L-lactide, D-lactide, meso-lactide or combinations thereof. Cyclic dimers of these lactic acids and/or lactides can also be used. Any known polymerization method, such as polycondensation or ring opening polymerization, can be used to polymerize lactic acid. A small amount of a chain extending agent (e.g., a diisocyanate compound, an epoxy compound, or acid anhydride) may also be employed. The polylactic acid can be a homopolymer or a copolymer, such as one that contains monomer units derived from L-lactic acid and monomer units derived from D-lactic acid. Although not required, the content ratio of one of the L-lactic acid-derived monomer units and the D-lactic acid-derived monomer unit is preferably about 85 mol% or more, in some embodiments, about 90 % by mol or more and, in other embodiments, about 95% by mol or more. Several polylactic acids, each with a different ratio between the monomer unit derived from L-lactic acid and the monomer unit derived from D-lactic acid, can be mixed in any random percentage. Of course, polylactic acid can be mixed with other types of polymers (eg polyolefins, polyesters, etc.).
[22] In a specific embodiment, polylactic acid has the following general structure:

[23] A specific example of a suitable polylactic acid polymer that can be used in the present invention is commercially available from Biomer, Inc. of Krailling, Germany under the name BIOMER™ L9000. Other suitable polylactic acid polymers are commercially available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA™). Still other suitable polylactic acids may be described in U.S. Patent No. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458.
[24] Polylactic acid typically has a number average molecular weight (“Mn”) that ranges from about 40,000 to about 180,000 grams per mole, in some embodiments from about 50,000 to about 160,000 grams per mole, and in some embodiments from about 50,000 to about 160,000 grams per mole. in some embodiments, from about 80,000 to about 120,000 grams per mole. Likewise, the polymer typically also has a weight average molecular weight ("Mw") that ranges from about 80,000 to about 250,000 grams per mole, in some embodiments from about 100,000 to about 200,000 grams per mole, and in some embodiments from about 100,000 to about 200,000 grams per mole. in some embodiments, from about 110,000 to about 160,000 grams per mole. The ratio of weight average molecular weight to number average molecular weight ("Mw/Mn"), i.e. the "polydispersity index", is also relatively low. For example, the polydispersity index typically ranges from about 1.0 to about 3.0, in some embodiments from about 1.1 to about 2.0, and in some embodiments from about 1.2 at about 1.8. The weight average and weight average molecular weight numbers can be determined by methods known to those skilled in the art.
[25] Polylactic acid can also have an apparent viscosity of from about 50 to about 600 Pascal-seconds (Pa2s), in some embodiments from about 100 to about 500 Pa2s, and in some embodiments from about 200 to about 400 Pa2s, as determined at a temperature of 190°C and a shear rate of 1000 sec -1 . The melt flow rate of polylactic acid (on a dry basis) can also range from about 0.1 to about 40 grams per 10 minutes, in some embodiments from about 0.2 to about 20 grams per 10 minutes. and, in some embodiments, from about 0.3 to about 15 grams per 10 minutes, determined at a load of 2160 grams and at 190°C.
[26] Some types of pure polyester (e.g. polylactic acid) can absorb water from the environment such that it has a moisture content of about 500 to 600 parts per million (“ppm”) or even higher, based on weight. of the initial polylactic acid. Moisture content can be determined in various ways as is known in the art, such as in accordance with ASTM D 7191-05, as described below. Since the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes desired to dry the polyester prior to blending. In most embodiments, for example, it is desired that the polyester have a moisture content of about 300 parts per million ("ppm") or less, in some embodiments, of about 200 ppm or less, in some embodiments, of about 1 to about 100 ppm, prior to mixing with the microinclusion and nanoinclusion additives. Drying of the polyester can occur, for example, at a temperature of from about 50°C to about 100°C and, in some embodiments, from about 70°C to about 80°C. B. Microinclusion Additive
[27] As used herein, the term "micro-inclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material capable of being dispersed within the polymer matrix in the form of discrete domains of microscale size. For example, prior to drawing, domains may have an average cross-sectional dimension from about 0.05 μm to about 30 μm, in some embodiments from about 0.1 μm to about 25 μm, in some embodiments , from about 0.5 μm to about 20 μm and, in some embodiments, from about 1 μm to about 10 μm. The term "cross-sectional dimension" generally refers to a characteristic dimension (e.g., width or diameter) of a domain that is substantially orthogonal to its principal axis (e.g., length) and also substantially orthogonal to the direction of stress. applied during stretching. While normally formed from the microinclusion additive, it should be understood that the microscale domains may also be formed from a combination of the microinclusion and nanoinclusion additives and/or other components of the composition.
[28] The microinclusion additive is generally polymeric in nature and has a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. Typically, the microinclusion polymer may be generally immiscible with the matrix polymer. In this way, the additive can be better spread out as discrete phase domains within a continuous phase of the matrix polymer. Discrete domains are able to absorb energy from an external force, which increases the stiffness and overall strength of the resulting material. Domains can have many different shapes, such as elliptical, spherical, cylindrical, plate-shaped, tubular, etc. In one embodiment, for example, the domains have a very elliptical shape. The physical dimension of an individual domain is normally small enough to minimize the propagation of cracks through the composition upon application of an external stress, but large enough to initiate microscopic plastic deformation and allow for zones of shear and/or shear intensity. tension around or at the particle inclusions.
[29] Although the polymers may be immiscible, the microinclusion additive may nevertheless be selected for having a solubility parameter that is relatively similar to that of the matrix polymer. This can improve the interfacial compatibility and physical interaction of the discrete and continuous phase boundaries and thus reduce the likelihood of composite breakdown. In this regard, the ratio of the solubility parameter for the matrix polymer to that of the additive is typically from about 0.5 to about 1.5, and in some embodiments from about 0.8 to about 1. two. For example, the polymeric microinclusion additive may have a solubility parameter of from about 15 to about 30 MJoules1/2/m3/2 and, in some embodiments, from about 18 to about 22 MJoules1/2/m3/2 , while polylactic acid can have a solubility parameter of about 20.5 MJoules1/2/m3/2. The term “solubility parameter”, as used in this document, refers to the “Hildebrand Solubility Parameter”, which is the square root of the cohesive energy density and is calculated according to the following equation:
where: Δ Hv = heat of vaporization R = Ideal gas constant T = Temperature Vm = Molecular volume
[30] Hildebrand solubility parameters for various polymers are also available from the Solubility Handbook of Plastics, by Wyeych (2004), which is incorporated herein by reference.
[31] The microinclusion additive may also have a certain melt flow rate (or viscosity) to ensure that the discrete domains and resulting pores can be properly maintained. For example, if the melt flow rate of the additive is too high, it tends to flow and disperse uncontrollably through the continuous phase. This results in lamellar or plate-like domains or co-continuous phase structures that are difficult to maintain and also likely to crack prematurely. On the other hand, if the melt flow rate of the additive is too low, it will tend to clump together and form very large elliptical domains, which are difficult to disperse during mixing. This may cause uneven distribution of the additive throughout the continuous phase. In this regard, the present inventors have found that the ratio of the melt flow rate of the microinclusion additive to the melt flow rate of the matrix polymer is normally from about 0.2 to about 8, in some embodiments, of from about 0.5 to about 6 and, in some embodiments, from about 1 to about 5. The microinclusion additive may, for example, have a melt flow rate of from about 0.1 to about 250 grams per 10 minutes, in some embodiments from about 0.5 to about 200 grams per 10 minutes, and in some embodiments from about 5 to about 150 grams per 10 minutes, determined at a load of 2160 grams and the 190°C.
[32] In addition to the properties noted above, the mechanical characteristics of the microinclusion additive can also be selected to achieve the desired porous network. For example, when a mixture of matrix polymer and microinclusion additive is applied with an external force, stress concentrations (e.g. including normal or shear stress) and shear and/or plastic producing zones may be initiated around and in the discrete phase domains as a result of stress concentrations arising from a difference in the elastic modulus of the additive and matrix polymer. Higher stress concentrations promote more intense localized plastic flow in the domains, which allows them to become significantly elongated when stresses are applied. Such elongated domains allow the composition to exhibit a more flexible and softer behavior than the matrix polymer, such as when the matrix is a rigid polyester resin. To improve stress concentrations, the microinclusion additive can be selected to have a relatively low Young's modulus of elasticity compared to the matrix polymer. For example, the ratio of the elastic modulus of the matrix polymer to that of the additive is typically from about 1 to about 250, in some embodiments from about 2 to about 100, and in some embodiments from about 2 to about 50. The modulus of elasticity of the microinclusion additive can, for example, range from about 2 to about 1000 megapascals (MPa), in some embodiments from about 5 to about 500 MPa, and in some modalities, from about 10 to about 200 MPa. On the other hand, the modulus of elasticity of polylactic acid, for example, is normally from about 800 MPa to about 3000 MPa.
[33] While a wide variety of microinclusion additives may be employed, especially suitable examples of such additives may include synthetic polymers such as polyolefins (eg, polyethylene, polypropylene, polybutylene, etc.); styrene copolymers (e.g., styrene-butadiene-styrene, styrene-isoprene-styrene, styrene-ethylene-propylene-styrene, styrene-ethylene-butadiene-styrene, etc.); polytetrafluoroethylenes; polyesters (eg recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (e.g. poly(ethylene vinyl acetate), polyvinyl chloride acetate, etc.); polyvinyl alcohols (e.g. polyvinyl alcohol, poly(ethylene vinyl alcohol), etc.); polyvinyl butyral; acrylic resins (e.g. polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (e.g. nylon); polyvinyl chlorides; polyvinylidene chlorides; polystyrenes; polyurethanes, etc. Suitable polyolefins may, for example, include ethylene polymers (e.g., low density polyethylene ("LDPE"), high density polyethylene ("HDPE"), linear low density polyethylene ("LLDPE"), etc.) , propylene homopolymers (e.g. syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[34] In one embodiment, the polymer is a propylene polymer, such as homopolypropylene or a propylene copolymer. The propylene polymer may, for example, be formed of a substantially isotactic polypropylene homopolymer or a copolymer containing an amount equal to or less than about 10% of the other monomer, i.e., at least about 90% by weight of the propylene. Such homopolymers may have a melting point of from about 160°C to about 170°C.
[35] In yet another embodiment, the polyolefin may be a copolymer of ethylene or propylene with another α-olefin, such as a C3-C20 α-olefin or a C3-C12 α-olefin. Specific examples of suitable α-olefins include 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1- pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1- dodecene; and styrene. Particularly desired α-olefin comonomers are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can range from about 60 mol % to about 99 mol %, in some embodiments from about 80 mol % to about 98.5 mol %, and in some embodiments from about 80 mol % to about 98.5 mol %. in some embodiments, from about 87% by mol to about 97.5% by mol. The α-olefin content can range from about 1 mol% to about 40 mol%, in some embodiments from about 1.5 mol% to about 15 mol%, and, in some embodiments, from about 2.5% by mol to about 13% by mol.
[36] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers available under the designation EXACT™ from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available under the names ENGAGE™, AFFINITY™, DOWLEX™ (LLDPE) and ATTANE™ (ULDPE) from the Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patent No. 4,937,299 to Ewen et al.; 5,218,071 to Tsutsui et al.; 5,272,236 to Lai, et al.; and 5,278,272 to Lai, et al. Suitable propylene copolymers are also commercially available under the names VISTAMAXX™ from ExxonMobil Chemical Co. of Houston, Texas; FINA™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER™ available from Mitsui Petrochemical Industries; and VERSIFY™, available from Dow Chemical Co. of Midland, Michigan. Suitable polypropylene homopolymers may include polypropylene from Exxon Mobil 3155, resins from Exxon Mobil Achieve™, and resin from Total M3661 PP. Other examples of suitable propylene polymers are described in U.S. Patent Nos. 6,500,563 to Datta et al.; 5,539,056 to Yang et al.; and 5,596,052 to Resconi et al.
[37] A wide variety of known techniques can be generally employed to form olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordination catalyst (eg Ziegler-Natta). Preferably, the olefin polymer is formed by a single-site coordination catalyst, such as a metallocene catalyst. Such a catalyst system produces ethylene copolymers, in which the comonomer is randomly distributed within a molecular chain and evenly distributed among different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent No. 5,571,619 to McAlpin et al.; 5,322,728 to Davis et al.; 5,472,775 to Obijeski et al.; 5,272,236 to Lai et al.; and 6,090,325 to Wheat, et al. Examples of metallocene catalysts include bis(n-butylcyclopentadienyl)titanium dichloride, bis(n-butylcyclopentadienyl)zirconium dichloride, bis(cyclopentadienyl)scandium chloride, bis(indenyl)zirconium dichloride, bis(methylcyclopentadienyl)titanium dichloride, dichloride bis(methylcyclopentadienyl)zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl(cyclopentadienyl,-1-fluorenyl) zirconium dichloride, molybdocene dichloride, nickelocene, niobocene dichloride, ruthenocene, titanocene dichloride, hydrated zirconocene, zirconocene dichloride, and so on. Polymers made using metallocene catalysts typically have a narrow molecular weight range. For example, metallocene-catalyzed polymers can have polydispersity numbers (Mw/Mn) below 4, controlled distribution of short chain branching, and controlled isotacticity.
[38] Regardless of the materials employed, the relative percentage of the microinclusion additive in the thermoplastic composition is selected to achieve the desired properties without significantly affecting the basic properties of the composition. For example, the microinclusion additive is normally employed in an amount of from about 1% by weight to about 30% by weight, in some embodiments, from about 2% by weight to about 25% by weight, and in some embodiments from about 5% by weight to about 20% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymer(s)). The concentration of the microinclusion additive in the entire thermoplastic composition can be from about 0.1% by weight to about 30% by weight, in some embodiments, from about 0.5% by weight to about 25% by weight, and , in some embodiments, from about 1% by weight to about 20% by weight. C. Nanoinclusion Additive
[39] As used herein, the term "nanoinclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material that is capable of being dispersed within the polymer matrix in the form of discrete domains of a nanoscale size. For example, before stretching, domains may have an average cross-sectional dimension of about 1 to about 500 nanometers, in some embodiments from about 2 to about 400 nanometers, and in some embodiments from about 5 to about 400 nanometers. of 300 nanometers. It should also be understood that nanoscale domains may also be formed from a combination of microinclusion and nanoinclusion additives and/or other components of the composition. For example, the nanoinclusion additive is typically employed in an amount of from about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight, and , in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymer(s)). The concentration of the nanoinclusion additive in the entire thermoplastic composition can be from about 0.01% by weight to about 15% by weight, in some embodiments, from about 0.05% by weight to about 10% by weight. and, in some embodiments, from about 0.3% by weight to about 6% by weight of the thermoplastic composition.
[40] The nanoinclusion additive may be polymeric in nature and have a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. To enhance its ability to become dispersed in the nanoscale domains, the nanoinclusion additive can also be selected from materials that are generally compatible with the matrix polymer and the microinclusion additive. This can be particularly useful when the matrix polymer or microinclusion additive has a polar moiety, such as a polyester. An example of such a nanoinclusion additive is a functionalized polyolefin. The polar compound can, for example, be provided by one or more functional groups, and the nonpolar component can be provided by an olefin. The olefin compound of the nanoinclusion additive may generally be formed from any branched or linear α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer as described above.
[41] The functional group of the nanoinclusion additive can be any group, segment and/or molecular block that provides a polar component to the molecule and is not compatible with the matrix polymer. Examples of non-polyolefin compatible segment and/or molecular blocks may include acrylates, styrenes, polyesters, polyamides, etc. The functional group may be ionic in nature and comprise charged metal ions. Especially suitable functional groups are maleic anhydride, maleic acid, fumaric acid, maleimide, maleic acid hydrazide, a reaction product of maleic anhydride and diamine, methylnadic anhydride, dichloromaleic anhydride, maleic acid amide, and the like. Maleic anhydride modified polyolefins are especially suitable for use in the present invention. These modified polyolefins are typically formed by grafting maleic anhydride onto a polymeric backbone material. These maleated polyolefins are available from EI du Pont de Nemours and Company under the name Fusabond®, such as P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified ethylene vinyl acetate), A series (chemically modified ethylene acrylate copolymers or terpolymers) or N series (chemically modified ethylene-propylene, ethylene-propylene diene monomer ("EPDM") or ethylene-octene). Alternatively, maleated polyolefins are also available from Chemtura Corp. under the designation of Polybond® and Eastman Chemical Company under the designation of Eastman series G.
[42] In certain embodiments, the nanoinclusion additive may also be reactive. An example of such a reactive nanoinclusion additive is a polyepoxide that contains, on average, at least two oxirane rings per molecule. Without intending to be bound by theory, it is believed that these polyepoxide molecules can induce a reaction of the matrix polymer (e.g. polyester) under certain conditions, thereby improving their melt strength without significantly reducing the melt temperature. glass transition. The reaction may involve chain extension, side chain branching, grafting, copolymer formation, etc. Chain extension, for example, can occur through a variety of different reactive pathways. For example, the modifier may allow a nucleophilic reaction to ring opening through a terminal carboxyl group of a polyester (esterification) or through a hydroxyl group (etherification). Oxazoline side reactions can occur to form steramide moieties. Through these reactions, the molecular weight of the matrix polymer can be increased to counteract degradation frequently during the melting process. While it is desirable to induce a reaction with the matrix polymer as described above, the present inventors have found that too much reaction can cause crosslinking between the polymer backbones. If this crosslinking was allowed to proceed to a significant extent, the resulting polymer blend could become brittle and difficult to process into a material with the desired strength and elongation properties.
[43] In this regard, the present inventors have found that polyepoxides with a relatively low epoxy functionality are particularly effective, which can be quantified by "epoxy equivalent weight". The epoxy equivalent weight reflects the amount of resin that contains one molecule of an epoxy group, and can be calculated by dividing the number average molecular weight of the modifier by the number of epoxy groups in the molecule. The polyepoxide of the present invention typically has a number average molecular weight of from about 7,500 to about 250,000 grams per mole, in some embodiments from about 15,000 to about 150,000 grams per mole, and in some embodiments from about 20,000 to about 20,000 to about 150,000 grams per mole. about 100,000 grams per mole, with a polydispersity index ranging from 2.5 to 7. The polyepoxide may contain less than 50, in some embodiments 5 to 45, and in some embodiments 15 to 40 epoxy groups. In turn, the epoxy equivalent weight may be less than about 15,000 grams per mole, in some embodiments, from about 200 to about 10,000 grams per mole, and in some embodiments, from about 500 to about 7,000 grams. per mole
[44] The polyepoxide can be a linear or branched (eg random, graft, block, etc.) homopolymer or copolymer containing terminal epoxy groups, skeletal oxirane units, and/or pendant epoxy groups. The monomers used to form these polyepoxides can vary. In a specific embodiment, for example, the polyepoxide contains at least one epoxy-functional (meth)acrylic monomeric component. As used herein, the term "(meth)acrylic" includes acrylic and methacrylic monomers, as well as their salts or esters, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth)acrylic monomers may include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate and glycidyl isoconate.
[45] Polyepoxide normally has a relatively high molecular weight, as indicated above, so that it can not only result in chain extension, but also achieve the desired blend morphology. The resulting melt flow rate of the polymer is thus typically within a range of about 10 to about 200 grams for 10 minutes, in some embodiments, from about 40 to about 150 grams for 10 minutes, and in some embodiments, from about 40 to about 150 grams for 10 minutes. in some embodiments, from about 60 to about 120 grams for 10 minutes, determined at a load of 2160 grams and at a temperature of 190°C.
[46] If desired, additional monomers can also be employed in the polyepoxide to help achieve the desired molecular weight. These monomers can vary and include, for example, ester monomers, (meth)acrylic monomers, olefin monomers, amide monomers, etc. In one embodiment, for example, the polyepoxide includes at least one linear or branched α-olefin monomer, such as those having 2 to 20 carbon atoms and preferably 2 to 8 carbon atoms. Specific examples include ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. Particularly desired α-olefin comonomers are ethylene and propylene.
[47] Another suitable monomer may include a (meth)acrylic monomer that is not epoxy-functional. Examples of such (meth)acrylic monomers may include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-acrylate. -butyl, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, acrylate methylcyclohexyl, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, i-butyl methacrylate, methacrylate of n-amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, crotyl methacrylate, cyclohexyl methacrylate , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, etc., good as a comb inactions of the same.
[48] In a particularly desirable embodiment of the present invention, the polyepoxide is a terpolymer formed of an epoxy-functional (meth)acrylic monomeric component, an α-olefin monomeric component, and a non-epoxy-functional (meth)acrylic monomeric component. . For example, the polyepoxide can be poly(ethylene-co-methylacrylate-co-glycidyl) methacrylate, which has the following structure:
where x, y and z are 1 or greater.
[49] The epoxy-functional monomer can be made into a polymer using a variety of known techniques. For example, a monomer containing polar functional groups can be grafted onto the backbone of a polymer to form a graft copolymer. Such grafting techniques are well known in the art and described, for example, in U.S. Patent No. 5,179,164. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer to form a block or random copolymer using known free radical polymerization techniques, such as high pressure reactions, Ziegler-Natta catalyst reaction systems, reaction with single-site catalyst (eg metallocene), etc.
[50] The relative portion of the monomeric component(s) can be selected to strike a balance between epoxy reactivity and melt flow rate. More specifically, a high epoxy monomer content can result in good reactivity with the matrix polymer, but too high a content can reduce the melt flow rate such that the polyepoxide negatively affects the melt strength of the epoxy blend. polymer. Thus, in most embodiments, the epoxy-functional (meth)acrylic monomer(s) constitute(s) from about 1% by weight to about 25% by weight, in some embodiments, from about 2% by weight to about 20% by weight and, in some embodiments, from about 4% by weight to about 15% by weight of the copolymer. The α-olefin monomer(s) may also comprise from about 55% by weight to about 95% by weight, in some embodiments, from about 60% by weight to about 90% by weight. weight and, in some embodiments, from about 65% by weight to about 85% by weight of the copolymer. When employed, other monomeric components (e.g., non-epoxy-functional (meth)acrylic monomers) may constitute from about 5% by weight to about 35% by weight, in some embodiments, from about 8% by weight to about from 30% by weight and, in some embodiments, from about 10% by weight to about 25% by weight of the copolymer. A specific example of a suitable polyepoxide that can be used in the present invention is commercially available from Arkema under the name LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a melt flow rate of 70 to 100 g/10 min and has a glycidyl methacrylate monomer content of 7 wt. of methyl from 13% by weight to 17% by weight, and an ethylene monomer content from 72% by weight to 80% by weight. Another suitable polyepoxide is commercially available from DuPont under the name ELVALOY® PTW, which is a terpolymer of ethylene, butyl acrylate, and glycidyl methacrylate and has a melt flow rate of 12 g/10 min.
[51] In addition to controlling the type and relative content of the monomers used to form the polyepoxide, the overall weight percentage can also be controlled to achieve desired benefits. For example, if the level of modification is too low, the desired increase in melt strength and mechanical properties may not be achieved. The present inventors have also discovered, however, that if the level of modification is too high, processing may be restricted due to strong molecular interactions (eg, cross-linking) and physical network formation by the epoxy-functional groups. Thus, the polyepoxide is normally employed in an amount of from about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, in some embodiments. from about 0.5% by weight to about 5% by weight and, in some embodiments, from about 1% by weight to about 3% by weight, based on the weight of the matrix polymer employed in the composition. The polyepoxide can also constitute from about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.05% by weight to about 8% by weight, in some embodiments, from about 0 .1% by weight to about 5% by weight, and in some embodiments, from about 0.5% by weight to about 3% by weight, based on the total weight of the composition.
[52] Other reaction nanoinclusion additives can also be employed in the present invention, such as oxazoline functionalized polymers, cyanide functionalized polymers, etc. When employed, these reactive nanoinclusion additives can be used within the concentrations indicated above for the polyepoxide. In a specific embodiment, an oxazoline-grafted polyolefin may be employed, i.e., a polyolefin grafted with a monomer containing an oxazoline ring. The oxazoline may include a 2-oxazoline, such as 2-vinyl-2-oxazoline (e.g. 2-isopropenyl-2-oxazoline), 2-graxo-alkyl-2-oxazoline (e.g. obtainable from oleic acid ethanolamine , linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and/or arachidonic acid) and combinations thereof. In another embodiment, the oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, ricin-2-oxazoline and combinations thereof, for example. In yet another embodiment, the oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[53] Nanofillers can also be used, such as carbon black, carbon nanotubes, carbon nanofibers, nanoclays, metallic nanoparticles, nanosilica, nanoalumina, etc. Nanoclays are especially suitable. The term "nanoclay" generally refers to nanoparticles of a clay material (a naturally occurring mineral, an organically modified mineral, or a synthetic nanomaterial), which typically have a platelet structure. Examples of nanoclays include, for example, montmorillonite (2:1 layered smectite clay structure), bentonite (aluminum phyllosilicate formed primarily by montmorillonite), kaolinite (1:1 aluminosilicate having a lamellar structure and of the empirical formula Al2Si2O5(OH) 4), Haloisite (1:1 aluminosilicate having a tubular structure and empirical formula Al2Si2O5(OH)4), etc. An example of a suitable nanoclay is Cloisite®, which is a montmorillonite nanoclay and is commercially available from Southern Clay Products, Inc. Other examples of synthetic nanoclays include, but are not limited to, a mixed metal hydroxide nanoclay, hydroxide nanoclay double layered (e.g. sepiocite), laponite, hectorite, saponite, indomite, etc.
[54] If desired, the nanoclay can contain a surface treatment to help improve compatibility with the matrix polymer (eg polyester). The surface treatment can be organic or inorganic. In one embodiment, an organic surface treatment is employed which is obtained by the reaction of an organic cation with the clay. Suitable organic cations may include, for example, organoquaternary ammonium compounds which are capable of exchanging cations with clay, such as dimethyl-bis[hydrogenated tallow]ammonium chloride (2M2HT), benzyl methyl bis[hydrogenated tallow]ammonium chloride ( MB2HT), methyl tris chloride [hydrogenated tallow alkyl] (M3HT), etc. Examples of commercially available organic nanoclays may include, for example, Dellite® 43B (Laviosa Chimica of Livorno, Italy), which is a montmorillonite clay modified with dimethyl tallow benzyl hydrogenated ammonium salt. Other examples include Cloisite® 25A and Cloisite® 30B (Southern Clay Products) and Nanofil 919 (Süd Chemie). If desired, the nanofiller can be blended with a carrier resin to form a masterbatch that enhances the additive's compatibility with the other polymers in the composition. Particularly suitable carrier resins include, for example, polyesters (e.g. polylactic acid, polyethylene terephthalate, etc.); polyolefins (e.g. ethylene polymers, propylene polymers, etc.); and so on, as described in more detail above.
[55] In certain embodiments of the present invention, various nanoinclusion additives may be employed in combination. For example, a first nanoinclusion additive (e.g., polyepoxide) may be dispersed in the form of domains with an average cross-sectional dimension of about 50 to about 500 nanometers, in some embodiments, from about 60 to about 400 nanometers, and, in some embodiments, from about 80 to about 300 nanometers. A second nanoinclusion additive (e.g. nanofiller) can also be dispersed in the form of domains that are smaller than the first nanoinclusion additive, such as those with an average cross-sectional dimension of about 1 to about 50 nanometers, in some embodiments, from about 2 to about 45 nanometers, and in some embodiments from about 5 to about 40 nanometers. When employed, the first and/or second nanoinclusion additives typically constitute from about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight. weight, and, in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymer(s)). The concentration of the first and/or second nanoinclusion additives in the entire thermoplastic composition can be from about 0.01% by weight to about 15% by weight, in some embodiments, from about 0.05% by weight to about 10 % by weight, and in some embodiments, from about 0.1% by weight to about 8% by weight of the thermoplastic composition. D. Other Components
[56] A wide variety of ingredients can be used in the composition for several different reasons. For example, in a specific embodiment, an interphase modifier may also be employed in the thermoplastic composition to help reduce the degree of friction and connectivity between the microinclusion additive and the matrix polymer and thereby increase the degree and uniformity of debonding. . In this way, the pores can be distributed more evenly throughout the composition. The modifier can be in liquid or semi-solid form at room temperature (eg, 25°C) so that it has a relatively low viscosity, allowing it to be more easily incorporated into the thermoplastic composition and migrate more easily to polymer surfaces. In this regard, the kinematic viscosity of the interphase modifier is typically from about 0.7 to about 200 centistokes ("cs"), in some embodiments from about 1 to about 100 cs, and in some embodiments from about 100 cs. 1.5 at about 80 cs, determined at 40°C. Furthermore, the interphase modifier is also normally hydrophobic so that it has an affinity for the microinclusion additive, resulting, for example, in a change in the interfacial tension between the matrix polymer and the additive. By reducing the physical forces at the interfaces between the matrix polymer and the microinclusion additive, it is believed that the low viscosity, hydrophobic nature of the modifier can help facilitate debonding. As used herein, the term "hydrophobic" typically refers to a material that has a contact angle of water and air of about 40° or more, and in some cases of about 60° or more. In contrast, the term “hydrophilic” typically refers to a material that has a contact angle of water and air of less than about 40°. A suitable test for measuring contact angle is ASTM D5725-99 (2008).
[57] Suitable low viscosity, hydrophobic interphase modifiers may include, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), alkane diols (e.g. 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1 ,3-cyclobutanediol, etc.), amine oxides (e.g. octyldimethylamine oxide), fatty acid esters, fatty acid amides (e.g. oleamide, erucamide, stearamide, ethylene bis(stearamide), etc.), mineral and vegetable oils, and so on. A particularly suitable liquid or semi-solid is polyether polyol, such as that commercially available under the name Pluriol® WI from BASF Corp. Another suitable modifier is a partially renewable ester, such as that commercially available under the Hallstar name HALLGREEN® IM.
[58] When employed, the interphase modifier can comprise from about 0.1% by weight to about 20% by weight, in some embodiments, from about 0.5% by weight to about 15% by weight, and , in some embodiments, from about 1% by weight to about 10% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymer(s)). The concentration of the interphase modifiers in the entire thermoplastic composition can be from about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 15% by weight, and , in some embodiments, from about 0.5% by weight to about 10% by weight.
[59] When employed in the amounts noted above, the interphase modifier will have a characteristic that allows it to easily migrate to the interfacial surface of polymers and facilitate debonding without impairing the overall melting properties of the thermoplastic composition. For example, the interphase modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. On the contrary, the present inventors have discovered that the glass transition temperature of the thermoplastic composition can be substantially equal to that of the initial matrix polymer. In this regard, the ratio of the glass temperature of the composition to that of the matrix polymer is normally from about 0.7 to about 1.3 in some embodiments, from about 0.8 to about 1.2, and, in some embodiments, from about 0.9 to about 1.1. The thermoplastic composition may, for example, have a glass transition temperature from about 35°C to about 80°C, in some embodiments from about 40°C to about 80°C, and in other embodiments, from about 40°C to about 80°C. from about 50°C to about 65°C. The melt flow rate of the thermoplastic composition can also be similar to that of the matrix polymer. For example, the melt flow rate of the composition (on a dry basis) can be from about 0.1 to about 40 grams per 10 minutes, in some embodiments from about 0.2 to about 20 ranges per 10 minutes. minutes and, in some embodiments, from about 0.3 to about 15 grams per 10 minutes, determined at a load of 2160 grams and at a temperature of 190°C.
[60] Compatibility agents can also be used to improve interfacial adhesion and reduce the interfacial tension between the domain and the matrix, thus allowing the formation of smaller domains during mixing. Examples of suitable compatibilizers may include, for example, epoxy functionalized copolymers or chemical moieties of maleic anhydride. An example of a maleic anhydride compatibilizer is polypropylene-grafted maleic anhydride, which is commercially available from Arkema under the names Orevac™ 18750 and Orevac™ CA 100. When employed, the compatibilizers can constitute from about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, and, in some embodiments, from about 0.5% by weight to about 5% by weight weight of the thermoplastic composition, based on the weight of the continuous phase matrix.
[61] Other suitable materials that can also be used in the thermoplastic composition, such as catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (e.g. calcium carbonate, etc.), particulate compounds, and other materials added to increase the processability and mechanical properties of the thermoplastic composition. However, a beneficial aspect of the present invention is that good properties can be provided without the need for various conventional additives such as blowing agents (e.g. chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, supercritical carbon dioxide, nitrogen, etc.) and plasticizers (eg solid or semi-solid polyethylene glycol). Indeed, the thermoplastic composition may generally be free of blowing agents and/or plasticizers. For example, the blowing agents and/or plasticizers can be present in an amount of not more than about 1% by weight, in some embodiments, not more than about 0.5% by weight, and, in some embodiments, of about 0.001% by weight to about 0.2% by weight of the thermoplastic composition. Furthermore, due to the stress bleaching properties, as described in more detail below, the resulting composition can achieve an opaque color (e.g. white) without the need for conventional pigments such as titanium dioxide. In certain embodiments, for example, the pigments may be present in an amount of not more than about 1% by weight, in some embodiments, not more than about 0.5% by weight, and in some embodiments, of about 0.001 % by weight to about 0.2% by weight of the thermoplastic composition. II. Mixture
[62] To form the thermoplastic composition, the components are typically mixed using one or a variety of known techniques. In one embodiment, for example, the components may be provided separately or in combination. For example, the components may first be dry blended to form an essentially homogeneous dry blend, and may be supplied simultaneously or sequentially to a melt processing device which dispersively blends the materials. Batch and/or continuous melt processing techniques may be employed. For example, a mixer/kneader, Banbury mixer, Farrel continuous mixer, single screw extruder, twin screw extruder, rolling mills, etc. can be used to mix and melt materials. Particularly suitable melt processing devices may be a co-rotating twin screw extruder (e.g. ZSK-30 extruder available from Werner & Pfleiderer Corporation of Ramsey, New Jersey or a USALAB 16 Thermo Prism™ extruder available from Thermo Electron Corp. , Stone, England). These extruders can include feed and vent ports and provide high-intensity distributive and dispersive mixing. For example, the components can be fed into the same feed ports as the twin screw extruder and melt blended to form a substantially homogeneous melt mixture. If desired, other additives can also be injected into the polymer melt and/or introduced separately into the extruder at a different point along its length.
[63] Regardless of the specific processing technique chosen, the melt-blended composition typically contains nanoscale domains of the nanoinclusion additive and, optionally, microscalar domains of the microinclusion additive. The degree of shear/pressure and heat can be controlled to ensure sufficient dispersion, but not so high as to negatively reduce the size of the domains so that they are unable to achieve the desired properties. For example, mixing generally occurs at a temperature from about 180°C to about 300°C, in some embodiments from about 185°C to about 250°C, and in some embodiments from about 190°C. °C to about 240 °C. Likewise, the apparent shear rate during processing can range from about 10 seconds-1 to about 3000 seconds-1, in some embodiments from about 50 seconds-1 to about 2000 seconds-1, and, in some embodiments, from about 100 seconds-1 to about 1200 seconds-1. The apparent shear rate can be equal to 4Q/R3, where Q is the volumetric flow rate (“m3/s”) of the polymer melt and R is the radius (“m”) of the capillary (e.g. extruder) through which the molten polymer flows. Of course, other variables, such as residence time during melt processing, which is inversely proportional to the production rate, can also be controlled to achieve the desired degree of homogeneity.
[64] To achieve the desired shear conditions (e.g. rate, dwell time, shear rate, melt processing temperature, etc.), the speed of the extruder screw(s) can be selected with a certain range. Generally, an increase in product temperature is observed with increasing screw speed due to the additional input of mechanical energy into the system. For example, the screw speed can range from about 50 to about 600 revolutions per minute ("rpm"), in some embodiments from about 70 to about 500 rpm, and in some embodiments from about 100 rpm. at about 300 rpm. This can result in a temperature high enough to disperse the nanoinclusion additive without adversely affecting the size of the resulting domains. The melt shear rate and, in turn, the degree to which the additives are dispersed, can also be increased when using one or more distributive and/or dispersive mixing elements within the mixing section of the extruder. Among the single screw distributive mixers are, for example, Saxon, Dulmage, Cavity Transfer mixers, etc. Likewise, suitable dispersive mixers may include bubble ring, Leroy/Maddock, CRD, etc. mixers. As is known in the art, mixing can be further improved by using pins on the cylinder that create a bend reorienting the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin (VIP) mixers. III. Leaf Formation
[65] Any known technique can be used to form a sheet from the composition, including blowing, casting, flat extrusion, etc. In one embodiment, the sheet may be formed by a blowing process in which a gas (e.g., air) is used to expand a bubble of the extruded polymer mixture through an annular mold. The bubble is then broken up and collected flat. Blowing processes are described, for example, in US Patent Nos. 3,354,506 to Raley; 3,650,649 to Schippers; and 3,801,429 to Schrenk et al., as well as US Patent Application Publication Nos. 2005/0245162 to McCormack, et al. and 2003/0068951 to Boggs, et al. In yet another embodiment, however, the sheet is formed using a die-casting technique.
[66] Referring to Fig. 1, for example, an embodiment of a method for forming a molded sheet is shown. In this embodiment, raw materials (not shown) are fed to extruder 80 from a hopper 40 and then cast on a casting roll 90 to form a single layer precursor sheet 10a. If a multilayer sheet is to be produced, the various layers are co-extruded together on the casting roll 90. The casting roll 90 can optionally be provided with embossing elements to give the sheet a pattern. Typically, the casting roll 90 is maintained at a temperature sufficient to solidify and cool the sheet 10a as it is formed, such as from about 20 to 60°C. If desired, a vacuum box can be positioned adjacent the casting roll 90 to help keep the precursor sheet 10a close to the surface of the roll 90. Additionally, air jets or electrostatic tweezers can help force the precursor sheet 10a against the surface. of the casting roll 90 as it moves around a rotating roll. Air jets are devices known in the art that direct a flow of air at a very high flow rate in order to secure the edges of the sheet.
[67] Once melted, the sheet 10a can then be optionally oriented in one or more directions to further improve the uniformity of the sheet. The sheet can be immediately reheated to a temperature below the melting point of one or more polymers in the sheet, but high enough to allow the composition to be drawn or stretched. In the case of sequential orientation, the “softened” sheet is pulled by rollers that rotate at different rotation speeds, such that the sheet is stretched to the desired stretch rate in the longitudinal direction (machine direction). This "uniaxially" oriented sheet may then optionally be laminated to form a fibrous web. Furthermore, the uniaxially oriented sheet can also be oriented cross-machine to form a "biaxially oriented" sheet. For example, the sheet can be secured at its side edges by chain clamps and transported to a tensioning oven. In the tension oven, the sheet can be reheated and pulled cross-machine at a desired stretch rate by spaced-apart chain clamps on their forward course.
[68] Referring again to Fig. 1, for example, a method for forming a uniaxially oriented sheet is shown. As illustrated, the precursor sheet 10a is directed to an orientation unit 100 or machine direction orientator ("MDO"), such as those available from Marshall and Willams, Co. of Providence, Rhode Island. The MDO has a variety of stretching cylinders (such as 5 to 8), which progressively stretch and thin the sheet in the machine direction, which is the direction the sheet travels through the process as shown in Fig. 1. Although the MDO 100 is illustrated with eight rolls, it should be understood that the number of rolls may be higher or lower depending on the desired stretch level and the degrees of stretch between each roll. The sheet can be stretched in a single or multiple discrete stretch operation. It should be noted that some of the cylinders in an MDO device may not be operating at progressively higher speeds. If desired, some of the MDO 100 rollers can function as preheat rollers. If present, these first rolls heat the sheet 10a above ambient temperature (eg, 125°F). The faster progressive speeds of adjacent cylinders in the MDO act to stretch sheet 10a. The rate at which the stretch cylinders rotate determines the amount of stretch of the sheet and the final weight of the sheet.
[69] The resulting sheet 10b can then be rolled up and stored on a take-up reel 60. Although not shown here, several additional possible processing and/or finishing steps known in the art, such as cutting, curing, perforating, printing images or laminating the sheets with other layers (e.g. films, non-woven batting materials) can be performed without departing from the spirit and scope of the invention.
[70] The polymeric sheet of the present invention may be mono- or multi-layered (e.g., from 2 to 20 layers and, in some embodiments, from 3 to 10 layers). For example, a multilayer sheet may contain at least one core layer which is positioned adjacent to at least one outer layer. The outer layers are often used for heat sealing or printing. In one embodiment, for example, it may be desirable to apply a first and second outer layer, interspersed by the core layer. The core layer(s) typically constitute a substantial part of the weight of the sheet, such as from about 50% by weight to about 99% by weight, in some embodiments, from about 55% by weight. to about 90% by weight and, in some embodiments, from about 60% by weight to about 85% by weight of the sheet. The outer layer(s) may similarly constitute from about 1% by weight to about 50% by weight, in some embodiments, from about 10% by weight to about 45% by weight and, in some embodiments, from about 15% by weight to about 40% by weight of the sheet.
[71] The thermoplastic composition of the present invention can be used in any layer of the sheet, including core layer and/or outer layer. In one embodiment, for example, the core layer is formed from the composition of the present invention and the outer layers are formed from the composition or an additional polymeric material. Similarly, in other possible embodiments, one or more outer layers are formed from the composition of the present invention and the core layer is formed from an additional polymeric material. When used, the additional material may include any type of polymer, such as polyolefins (e.g., polyethylene, polypropylene, etc.), polyesters, polyamides, styrenic copolymers, polyurethanes, polyvinyl acetate, polyvinyl alcohol, etc.
[72] Regardless of the specific way it is formed, the sheet can be extracted to form the desired porous network. If desired, the sheet can be stripped in-line as it is being formed. Alternatively, the sheet may be extracted in its solid state after being formed, before or after thermoformed into the desired shape. By "solid state" extraction, it is generally meant that the composition is maintained at a temperature below the melting temperature of the matrix polymer. Among other things, this helps to ensure that the polymer chains are not altered to such a degree that the porous network becomes unstable. For example, the sheet can be extracted at a temperature of from about 0°C to about 50°C, in some embodiments from about 15°C to about 40°C, and in some embodiments from about 20°C. °C to about 30 °C. It may optionally be at least about 10°C, in some embodiments at least about 20°C, and in some embodiments at least about 30°C below the glass transition temperature of the component with the highest glass transition temperature (eg matrix polymer). In certain embodiments, for example, extraction may occur at temperatures from about -50°C to about 150°C, in some embodiments, from about -40°C to about 100°C, in some embodiments , from about -20°C to about 50°C.
[73] Extraction can occur in a single or multi-phase phase and use any of a variety of different techniques. In one embodiment, for example, the sheet may be extracted prior to being thermoformed, with a machine direction advisor (“MDO”), as well as using the unit 100 shown in Fig. 1. To extract the sheet in the manner described above , it is generally preferable that the MDO rollers are not heated. However, if desired, one or more cylinders may be heated slightly to facilitate the extraction process, as long as the temperature of the composition remains below the ranges determined above. The sheet is normally drawn (e.g., machine direction) to a stretch ratio of about 1.1 to about 3.5, in some embodiments, from about 1.2 to about 3.0, and, in some embodiments, from about 1.2 to about 3.0. in other embodiments, from about 1.3 to about 2.5. The “extraction ratio” can be determined by dividing the length of the extracted leaf by its length before extraction. The pull rate can also be varied to help achieve desired properties, such as within the range of about 5% to about 1500% per minute of strain, in some embodiments from about 20% to about 1000% per minute. minute of strain, and, in some embodiments, from about 25% to about 850% per minute of strain. Although the sheet is typically extracted without the application of external heat (e.g. heated rollers), this heat can optionally be used to improve processability, reduce extraction force, increase extraction rates and improve uniformity.
[74] Extracting in the manner described above can result in the formation of pores that have a "nanoscale" dimension ("nanopores"), as described above. Micropores can also be formed around and in the microscale domains during stretching to have an average transverse dimension of about 0.5 to about 30 micrometers, in some embodiments from about 1 to about 20 micrometers, and, in some embodiments, from about 2 micrometers to about 15 micrometers. The micropores and/or nanopores can be of any regular or irregular shape, such as spherical, elongated, etc. In certain cases, the axial dimension of the micropores and/or nanopores may be greater than the cross-sectional dimension so the aspect ratio (the ratio of the axial dimension to the cross-sectional dimension) is from about 1 to about 30 , in some embodiments, from about 1.1 to about 15, and, in some embodiments, from about 1.2 to about 5. The "axial dimension" is the dimension along the principal axis (e.g., length), which is normally in the stretch direction.
[75] The present inventors have also found that pores (eg, micropores, nanopores, or both) can be distributed substantially homogeneously throughout the composition. For example, pores can be distributed in columns that are oriented in a direction generally perpendicular to the direction in which the stress is applied. These columns can generally be parallel to each other across the width of the composition. Without intending to impose theoretical limitations, it is believed that the presence of this network of evenly distributed voids can result in good mechanical properties (eg energy dissipation under load and impact force). There is a stark contrast to conventional techniques for creating pores that involve the use of blowing agents, which tends to result in uncontrolled pore distribution and poor mechanical properties. Notably, the formation of the porous network by the process described above does not necessarily result in a substantial change in the transverse size (eg, width) of the material. In other words, the material is not substantially narrowed, which can allow the material to retain a greater degree of strength properties. For example, the width may be decreased by an amount not more than about 20% and, in some embodiments, not more than about 15%. Likewise, the thickness may be decreased by an amount not more than 10% and, in some embodiments, not more than 5%.
[76] In addition to forming a porous network, stretching can also significantly increase the axial dimension of the microscale domains so that they have a generally linear, elongated shape. For example, elongated microscale domains can have an average axial dimension that is about 10% or more, in some embodiments, from about 20% to about 500%, and, in some embodiments, from about 50% to about 500%. about 250% greater than the axial dimension of the domains before stretching. The axial dimension after stretching can, for example, range from about 0.5 to about 250 micrometers, in some embodiments from about 1 to about 100 micrometers, in some embodiments from about 2 to about 50 micrometers. micrometers, and in some embodiments from about 5 to about 25 micrometers. Microscale domains can also be relatively thin and thus have a small cross-sectional dimension. For example, the transverse dimension can be from about 0.05 to about 50 micrometers, in some embodiments from about 0.2 to about 10 micrometers, and in some embodiments from about 0.5 to about 10 micrometers. of 5 micrometers. This can result in an aspect ratio for the microscale domains (the ratio of the axial dimension to the cross-sectional dimension) of from 2 to about 150, in some embodiments, from about 3 to about 100, and , in some embodiments, from about 4 to about 50.
[77] As a result of the porous and elongated structure of the domain, the present inventors have found that the resulting composition can expand uniformly in volume when stretched lengthwise, which is reflected by a low "Poisson coefficient", as determined accordingly. with the following equation:

[78] where Etransverse is the transverse strain of the material and Elongitudinal is the longitudinal strain of the material. More specifically, the material's Poisson ratio can be approximately 0 or even negative. For example, the Poisson ratio can be from about 0.1 or less, in some embodiments from about 0.08 or less, and from about -0.1 to 0.04 in some embodiments. When Poisson's ratio is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When Poisson's ratio is negative, the transverse or lateral dimensions of the material also expand when the material is stretched lengthwise. Materials with a negative Poisson's ratio may thus exhibit an increase in width when stretched in the longitudinal direction, which can result in greater energy absorption in the crosswise direction.
[79] In addition to having a porous structure, which results in a reduction in density and polymer content, the polymeric sheet is also able to maintain good mechanical properties during use. For example, the sheet may be relatively pliable. A parameter indicative of the sheet's ductility is the percentage of its elongation at its breaking point, as determined by the stress-strain curve, as obtained in accordance with ASTM D638-10 at 23°C. For example, the percentage elongation at machine direction sheet break ("MD") can be about 10% or more, in some embodiments, about 50% or more, in some embodiments, about 80% or more. more and, in other modalities, from about 100% to about 600%. Likewise, the percentage of elongation at break of the sheet in the transverse direction ("CD") can be about 15% or more, in some embodiments, about 40% or more, in some embodiments, about 70% or more. more and, in other modalities, from about 100% to about 400%. Another parameter indicative of ductility is the modulus of elasticity of the sheet, which is equal to the ratio of resistance stress to elastic deformation and is determined from the slope of the stress-strain curve. For example, the sheet typically exhibits an MD and/or CD modulus of elasticity of about 2500 Megapascals ("MPa") or less, in some embodiments, about 2200 MPa or less, in some embodiments, from about 50 MPa to about 2000 MPa and, in some embodiments, from about 100 MPa to about 1000 MPa. The modulus of elasticity can be determined in accordance with ASTM D638-10 at 23°C.
[80] Although the sheet is ductile, it can still be relatively strong. A parameter indicative of the relative strength of the sheet is its maximum tensile strength, which is equal to the maximum stress obtained on a stress-strain curve as obtained in accordance with ASTM D638-10. For example, the sheet may exhibit a maximum MD and/or CD tension of about 5 to about 65 MPa, in some embodiments, from about 10 to about 60 MPa, and in other embodiments, from about 20 MPa to about 60 MPa. about 55 MPa. The sheet may also exhibit an MD and/or CD voltage drop from about 5 MPa to about 60 MPa, in some embodiments from about 10 MPa to about 50 MPa, and in some embodiments from about 20 MPa at about 45 MPa. Maximum voltage and breakdown voltage can be determined in accordance with ASTM D638-10 at 23°C.
[81] If desired, the polymeric material of the present invention may be subjected to one or more additional processing steps, before and/or after extraction. Examples of such processes include, for example, notch roll drawing, embossing, coating, etc. In certain embodiments, the sheet may also be annealed to help ensure maintenance of the desired shape. Annealing normally occurs at temperatures above the glass transition temperature of the polymer matrix, such as temperatures from about 40°C to about 120°C; in some embodiments, from about 50°C to about 100°C and, in other embodiments, from about 70°C to about 90°C. The polymeric sheet may also be surface treated using any of several known techniques to improve its properties. For example, high energy beams (e.g. plasma, x-rays, electron beam, etc.) can be used to eliminate or reduce any skin layers, to change surface polarity, porosity, topography, to weaken a layer of skin. surface, etc. If desired, this surface treatment can be used before and/or after stretching the thermoplastic compound. IV. Thermoformed article
[82] Regardless of its particular shape, the polymeric sheet can be thermoformed into a wide variety of different three-dimensional articles. Thermoforming generally involves heating the polymeric sheet to a certain temperature, shaping the sheet into a mold and then optionally trimming the article to create the desired article. The particular forming technique is not critical, and any of a variety of conventional processes may be employed in the present invention. Suitable techniques may include, for example, vacuum forming, assisting plug forming, curtain forming, press forming, etc. For example, the sheet may be fed to a heating device (eg, convection oven, resistance heater, infrared heater, etc.) which heats to a temperature sufficient to cause the polymer to deform or stretch. This temperature is generally above the glass transition temperature of the composition, still at or below the melting temperature. For example, the thermoforming temperature can be from about 30°C or more below, in some embodiments from about 40°C or more, and in some embodiments from about 45°C to about 80°C below the temperature. melting temperature of the composition. In certain embodiments, for example, the sheet may be heated to a temperature from about 30°C to about 150°C, in some embodiments from about 50°C to about 130°C, and in some embodiments, from about 50°C to about 130°C. from about 60°C to about 120°C. Once heated, the polymeric sheet can then be fed into a mold where a force (e.g. suction force) is placed against the sheet to make it conform to the contours of the mold. The mold cavity imparts the shape of the article to the polymeric sheet and can also cool the material to a temperature significantly below the melting point so that it solidifies properly to maintain its shape after removal from the mold.
[83] Various types of articles can be thermoformed in accordance with the present invention. The resulting article may, for example, be a food, medical, or general retail industry product such as a package, cup, tube, bucket, jar, box, container, lid, tray (e.g. for an article of food), blister, ladle, bottle, pocket, appliance part (eg refrigerator lining), pallet, etc.; auto or aircraft part, such as a vehicle dashboard, door panel, utility vehicle base, etc.; and so on.
[84] The present invention can be better understood with reference to the following examples. Melting Flow Rate Test Methods:
[85] Melt flow rate (“MFR”) is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825 inch in diameter) when subjected to a load of 2160 grams at 10 minutes, normally at 190°C, 210°C or 230°C. Unless otherwise noted, melt flow rate is measured according to ASTM test method D1239 with a Tinius Olsen Extrusion Plastometer. Thermal Properties:
[86] The glass transition temperature (Tg) can be determined by dynamic-mechanical analysis (DMA) according to ASTM E1640-09. A TA Instruments Q800 instrument can be used. Experimental runs can be run in stress/stress geometry, in a temperature sweep mode in the range of -120°C to 150°C with a heating rate of 3°C/min. The force amplitude frequency can be kept constant (2 Hz) during the test. Three (3) independent samples can be tested to obtain an average glass transition temperature, which is defined by the peak value of the tangent curve δ, where the tangent δ is defined as the ratio of the loss modulus to the loss modulus. storage (tangent δ = E”/E').
[87] The melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimeter may be a DSC Q100 differential scanning calorimeter, which can be prepared with a liquid nitrogen cooling accessory and a UNIVERSAL ANALYSIS 2000 analysis software program (version 4.6.6), both available from TA Instruments Inc. of New Castle, Delaware. To avoid direct handling of samples, tweezers and other tools can be used. Samples can be placed on an aluminum plate and weighed to an accuracy of 0.01 milligram on an analytical balance. A lid can be placed over the material sample in the dish. Normally, resin pellets can be placed directly on the weighing pan.
[88] The differential scanning calorimeter can be calibrated using an indium metal standard and a baseline correction can be made as described in the differential scanning calorimeter operating manual. The material sample can be placed in the test chamber of the differential scanning calorimeter for testing, and an empty plate can be used as a reference. All tests can be performed with 55 cubic centimeters per minute nitrogen purge (industrial grade) in the test chamber. For resin grain samples, the heating and cooling program is a 2-cycle test, which began with chamber equilibration at -30°C, followed by a first heating period at a rate of 10°C per minute. to a temperature of 200 °C, followed by an equilibration of the sample at 200 °C for 3 minutes, followed by a first cooling period of 10 °C per minute to a temperature of -30 °C, followed by equilibration of the sample at -30 °C for 3 minutes, followed by a second heating period at a rate of 10 °C per minute to a temperature of 200 °C. For resin grain samples, the heating and cooling program is a 1-cycle test, which began with chamber equilibration at -25°C, followed by a first heating period at a rate of 10°C per minute. to a temperature of 200 °C, followed by an equilibration of the sample at 200 °C for 3 minutes, followed by a first cooling period of 10 °C per minute to a temperature of -30 °C. All tests can be performed with 55 cubic centimeters per minute nitrogen purge (industrial grade) in the test chamber.
[89] Results can be evaluated using the UNIVERSAL ANALYSIS 2000 analysis software program, which identifies and quantifies the glass transition temperature (Tg) of inflection, endothermic and exothermic peaks, and areas under peaks on DSC plots. . The glass transition temperature can be identified as the region of the graph line where a sharp change in slope has occurred, and the melting temperature can be determined using an automatic inflection calculation. Elastic Properties:
[90] Sheets can be tested for elastic properties (maximum stress, modulus, strain at break, and energy per volume at break) on an MTS Synergie 200 elastic frame. The test was performed in accordance with ASTM D638-10 (approx. of 23°C). Specimens can be cut into a 3.0 mm central width canine bone shape prior to testing. Canine bone shaped specimens can be held in place using forceps on the MTS Synergie 200 device with 18.0 mm gauge length. Samples can be stretched at a pull speed of 5.0 in/min until breakage occurs. Five samples can be tested for each sheet, either in the machine direction (MD) or in the transverse direction (CD). A computer program (e.g. TestWorks 4) can be used to collect data during the test and generate a stress versus strain curve from which various properties can be determined, including modulus, maximum stress, elongation, and energy at break. Expansion Ratio, Density and Percent Pore Volume:
[91] To determine the expansion ratio, the density and the percentage pore volume, the width (Wi) and thickness (Ti) of the sample were initially measured before stretching. The length (Li) before stretching could also be determined by measuring the distance between two marks on a surface of the sample. Consequently, the sample could be stretched to initiate the formation of voids. The width (Wf), thickness (Tf) and length (Lf) of the sample could then be measured to the nearest 0.01 mm using a Digimatic Compass (Mitutoyo Corporation). The volume (Vi) before stretching could be calculated by Wi x Ti x Li = Vi. The volume (Vf) after stretching could be calculated by Wf x Tf x Lf = Vf. The expansion ratio (Φ) could be calculated by Φ = Vf/Vi; the density (Pf) was calculated by: Pf = Pi/Φ, where Pi is the density of the precursor material; and the percentage pore volume (% Vv) could be calculated by: %Vv = (1 - 1/ Φ) x 100. Moisture content:
[92] Moisture content can be determined using an Arizona Instruments Computrac Vapor Pro moisture analyzer (Model #3100) substantially in accordance with ASTM D 7191-05, which is incorporated in its entirety herein by reference for all purposes. . The test temperature (§X2.1.2) can be 130°C, the sample size (§X2.1.1) can be 2 to 4 grams, and the vial purge time (§X2.1.4) can be of 30 seconds. In addition, the final criteria (§X2.1.3) can be set to a "prediction" mode, which means that the test ends when the internally programmed criteria (which mathematically calculate the moisture content parameter) are met. EXAMPLE 1
[93] The ability to form a polymeric sheet for use in a thermoformed article has been demonstrated. Initially, a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of a microinclusion additive, 1.4% by weight of a nanoinclusion additive was demonstrated. , and 3.8% by weight of an interfacial modifier. The microinclusion additive was Vistamaxx™ 2120 (ExxonMobil), which is a polyolefin/elastomer copolymer with a melt flow rate of 29 g/10 min (190°C, 2160 g) and a density of 0.866 g/cm3 . The nanoinclusion additive was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema) with a melt flow rate of 5-6 g/10 min (190°C/2160 g), a glycidyl methacrylate content of 7 to 11% by weight, methyl acrylate content of 13 to 17% by weight, and ethylene content of 72 to 80% by weight, the internal interfacial modifier was WI 285 PLURIOL® Lubricant from BASF, which is a polyalkylene glycol functional fluid. The polymers were fed into a co-rotating twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) to produce compounds which were manufactured by Werner and Pfleiderer Corporation of Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1-14, from the hopper to the mold. The first barrel zone #1 received the resins through a gravimetric feeder at a total flow rate of 15 pounds per hour. PLURIOL® WI285 was added via injection pump in barrel #2. The mold used to extrude the resin had 3 mold openings (6 millimeters in diameter) that were 4 millimeters apart. After forming, the extruded resin was cooled on a fan cooled conveyor belt and formed into pellets by a Conair pelletizer. The extruder screw speed was 200 revolutions per minute (“rpm”). The pellets were then bulk fed to a signal screw extruder heated to a temperature of 212°C where the molten mixture was exited through a 4.5 inch slit mold and stretched to a sheet thickness ranging from 0.54 at 0.58 mm. EXAMPLE 2
[94] The sheet produced in Example 1 was cut to a length of 6" and then stripped to 100% elongation using an MTS 820 hydraulic tension frame in spring mode at 50 mm/min. EXAMPLE 3
[95] The sheet produced in Example 1 was cut to a length of 6" and then stripped to 150% elongation using an MTS 820 hydraulic tension frame in spring mode at 50 mm/min. EXAMPLE 4
[96] The sheet produced in Example 1 was cut to a length of 6" and then stripped to 200% elongation using an MTS 820 hydraulic tension frame in spring mode at 50 mm/min. EXAMPLE 5
[97] Pellets were formed as described in Example 1 and then bulk fed into a Rheomix 252 single screw extruder with an L/D ratio of 25:1 and heated to a temperature of 212°C, where the molten mixture exited through from a 6 inch Haake casting mold and extracted in the machine direction to a longitudinal strain of 160% at a tensile rate of 50 mm/min (strain rate of 67%/min) through the MTS Synergie 200 elastic frame with calipers at a caliber distance of 75 mm. EXAMPLE 6
[98] The sheets were formed as described in Example 5, except that the sheet was also stretched in the counter-machine direction at 100% strain at a pull rate of 50 mm/min (strain rate 100%/min ) with calipers at a gauge distance of 50 mm. Various properties of the sheets of Examples 5-6 were tested as described above. The results are shown in Tables 1 and 2. Table 1: Sheet Properties
Table 2: Elastic properties
EXAMPLE 7
[99] Pellets were formed as described in Example 1 and then bulk fed to a signal screw extruder heated to a temperature of 212°C, whereupon the molten mixture was exited through a 4 .5 inches and extracted in the machine direction to about 100% to initiate cavitation and void formation. Leaf morphology was analyzed by scanning electron microscopy (SEM) before and after stretching. The results are shown in Figs. 2-5. As shown in Figs. 2-3, the microinclusion additive was initially dispersed in domains with an axial (machine direction) size of about 2 to about 30 micrometers and a transverse (machine direction) dimension of about 1 to about 30 micrometers. 3 micrometers, whereas the nanoinclusion additive was initially dispersed as spherical or spheroidal domains having an axial size of about 100 to about 300 nanometers. Figs. 4-5 show the sheet after stretching. As indicated, pores formed around the microinclusion and nanoinclusion additives. The micropores formed around the microinclusion additive were generally elongated and slit-like in shape, with a wide size distribution ranging from about 2 to about 20 micrometers in the axial direction. The nanopores associated with the nanoinclusion additive are generally between about 50 and about 500 nanometers in size. EXAMPLE 8
[100] The composite pellets of Example 7 were dry blended with another nanoinclusion additive, which was a halloysite clay masterbatch (MacroComp MNH-731-36, MacroM) containing 22% by weight of a styrenic copolymer modified nanoclay. and 78% by weight polypropylene (Exxon Mobil 3155). The mixing ratio was 90% by weight of the pellets and 10% by weight of the clay masterbatch, which provided a total clay content of 2.2%. The dry mixture was then bulk fed to a signal screw extruder heated to a temperature of 212°C, where the molten mixture was exited through a 4.5 inch wide slot mold and drawn in the machine direction to approx. 100% to initiate cavitation and void formation. Leaf morphology was analyzed by scanning electron microscopy (SEM) before and after stretching. The results are shown in Figs. 6-9. As shown in Figs. 6-7, some of the nanoclay particles (visible as brighter regions) became dispersed in the form of very small domains - that is, axial dimension ranging from about 50 to about 300 nanometers. The masterbatch itself also formed domains of a microscale size (axial dimension from about 1 to about 5 micrometers). Also, the microinclusion additive (Vistamaxx™) formed elongated domains, while the nanoinclusion additives (Lotader®, visible as ultrafine dark spots and nanoclay masterbatch, visible as clear platelets) formed spheroidal domains. The stretched sheet is shown in Figs. 8-9. As structured, the cavitated structure is more open and demonstrates a wide range of pore sizes. In addition to the highly elongated micropores formed by the microinclusions (Vistamaxx™), the nanoclay masterbatch inclusions formed more open spheroidal micropores with an axial size of about 10 microns or less, and a transverse size of about 2 microns. Spherical nanopores are also formed by nanoinclusion additives (Lotader® and nanoclay particles). Various elastic properties (machine sense) of the sheets of Example 7 and 8 were also tested. The results are provided below.

[101] As shown, the addition of the nanoclay filler resulted in a slight increase in tensile strength and a significant increase in elongation at break. EXAMPLE 9
[102] The ability to form a polymeric sheet for use in a thermoformed article has been demonstrated. Initially, a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of a microinclusion additive, 1.4% by weight of a nanoinclusion additive was demonstrated. , and 3.8% by weight of an interfacial modifier. The microinclusion additive was Vistamaxx™ 2120 (ExxonMobil). The nanoinclusion additive was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema) and the internal interfacial modifier was PLURIOL® WI 285. The polymers were fed into a twin screw extruder. The extruder had 10 zones, numbered sequentially from 1-10, from the hopper to the mold. The first barrel zone #1 received the resins through a gravimetric feeder at a total flow rate of 500 pounds per hour. PLURIOL® WI285 was added via injection pump in barrel #4. The extrusion temperature started at 50°C in zone 1 and was increased to 220°C in zones 2-8. Zones 9 and 10 were set at a temperature of 265°C to facilitate pelleting. The mold used to expel the resin had 24 mold openings. The extruded resin was cut into pellets using an underwater pelletizing system operating at 4250 revolutions per minute (Gala Industries, Eagle Rock, Virginia). The extruder screw speed was 360 revolutions per minute ("rpm"). The pellets were then bulk fed to a 3.5 inch signal screw extruder heated to a temperature of 205°C, where the molten mixture was exited through a 91.5 cm wide slit mold and extracted at a sheet thickness of 0.38 mm. EXAMPLE 10
[103] A sheet was formed as described in Example 9 and then extracted uniaxially using a Machine Steering Guideline (Windmoller & Holscher, Lengerich, Germany). The sheet was extracted at a ratio of 1.56X (based on winder speed divided by MDO feed roller speed). Pressure was applied in two zones, at a temperature of 43°C. EXAMPLE 11
[104] The sheets from Examples 9 and 10 were then thermoformed in various molds using a Formech 450 vacuum molding unit. The heater output and dwell time were controlled directly on the Formech Unit and the Sheet temperature and measured using a handheld non-contact infrared thermometer. Thermoforming conditions are given in the table below.

EXAMPLE 12
[105] A mixture of materials that contained 91.75% by weight of polypropylene (Total Petrochemicals 3762), 7.5% by weight of polylactic acid (NatureWorks Ingeo 6251D) and 0.75% by weight of a polyepoxide modifier ( Arkema Lotader AX8900). This blend was melt blended through a twin screw extruder at 220°C to form a homogeneous polymer blend. The molten polymer mixture was then extruded through a multifilament mold, quenched by water, and cut into a pellet by an underwater pelletizing system, such as those available from Gala Industries of Eagle Rock, Virginia. The composite pellet was then fed into a HAAKE Rheomex single screw extruder (24:1 length to diameter ratio) with a molten sheet die. The pellets were melted in the extruder at a temperature of 200°C and extruded through an 8 inch wide film mold onto a casting roll at a temperature of 25°C. A stretching force was applied to the cast film to reduce the thickness to approximately 0.18 to 0.2 mm. EXAMPLE 13
[106] The sheet material of Example 12 was stretched at room temperature using an MTS 810 elastic frame at a rate of 50 millimeters per minute. The samples were stretched to 200% elongation. At this level, the material is narrowed and reduced in thickness to 0.076 mm, resulting in a 20% reduction in width.
[107] The sheets from Examples 12 and 13 were then thermoformed in various molds using a Formech 450 vacuum molding unit. The heater output and dwell time were controlled directly on the Formech Unit and the Sheet temperature and measured using a handheld non-contact infrared thermometer. Thermoforming conditions are given in the table below. Heater Output Sheet(%) Interrupt Time (sec) Heater Temperature
EXAMPLE 14
[108] A sheet was formed as described in Example 12, except that a lower melt strength force was used to create a film with a thickness of 0.25 to 0.28 mm. EXAMPLE 15
[109] The sheet of Example 14 was stretched at room temperature using an MTS 810 elastic frame at a rate of 50 millimeters per minute. The samples were stretched to 200% elongation. At this level, the material is narrowed and reduced in thickness to 0.114 mm, which resulted in a 20% reduction in width. EXAMPLE 16
[110] The sheets from Examples 14 and 15 were then thermoformed in various molds using a Formech 450 vacuum molding unit. The heater output and dwell time were directly controlled on the Formech Unit and the Sheet temperature and measured using a handheld non-contact infrared thermometer. Thermoforming conditions are given in the table below.
EXAMPLE 17
[111] The sheet from Example 9 was uniaxially extracted using a Machine Steering Guideline (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.5x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 43°C. EXAMPLE 18
[112] A sheet was formed as described in Example 9, except that the casting roll speed was increased to reduce the sheet thickness to 0.30 mm. EXAMPLE 19
[113] The sheet from Example 18 was uniaxially extracted using a Machine Steering Guideline (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.5x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 20
[114] The sheet of Example 18 was uniaxially extracted using a Machine Steering Guidance Line (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.75x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 21
[115] The sheet from Example 18 was uniaxially extracted using a Machine Steering Guidance Line (Windmoller & Holscher, Lengerich, Germany) and at an aspect ratio of 2.0x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 22
[116] A sheet was formed as described in Example 9, except that the polymer yield through the single-screw extruder was reduced and the casting roll line speed was increased to create a sheet with a thickness of 0.25 mm EXAMPLE 23
[117] The sheet of Example 22 was uniaxially extracted using a Machine Steering Guidance Line (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.5x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 24
[118] The sheet of Example 22 was uniaxially extracted using a Machine Steering Guidance Line (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.75x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 25
[119] The sheet from Example 22 was uniaxially extracted using a Machine Steering Guideline (Windmoller & Holscher, Lengerich, Germany) and at an aspect ratio of 2.0x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 26
[120] A sheet was formed as described in Example 9, except that the polymer yield through the single screw extruder was further reduced and the casting roll line speed was increased to create a sheet with a thickness of 0 .20 mm. EXAMPLE 27
[121] The sheet from Example 26 was uniaxially extracted using a Machine Steering Guideline (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.5x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 28
[122] The sheet of Example 26 was extracted uniaxially using a Machine Steering Guidance Line (Windmoller & Holscher, Lengerich, Germany) and at an aspect ratio of 17.5x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 29
[123] The sheet of Example 26 was extracted uniaxially using a Machine Steering Guideline (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 2.0x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C. EXAMPLE 30
[124] A sheet was formed as described in Example 9, except that the polymer yield through the single screw extruder was increased and the casting roll line speed was decreased to create a sheet with a thickness of 0.76 mm EXAMPLE 31
[125] The sheet of Example 30 was uniaxially extracted using a Machine Steering Guidance Line (Windmoller & Holscher, Lengerich, Germany) and at a ratio of 1.5x (based on winder speed divided by feed roll speed). MDO). Pressure was applied in two zones, at a temperature of 46°C.
[126] The following table represents thermoforming data for non-porous sheet material from Examples 9, 18, 20 and 22. All samples were produced in a thermoforming unit using an oven with an infrared heater to heat the sheet material. before training. Sheet temperature is controlled by setting the heater unit output from 0 to 100% and keeping sheet material in the oven for a set time. The first uses a single sheet of material of the indicated thickness. The sheet temperature was measured using single-use temperature indicator adhesives in a range of 60 to 82°C, 88 to 110°C and 116 to 138°C. Sheet Thickness (mm) Interruption Time (seconds) Heater Setting (%) Temperature (°C)


[127] While the invention has been described in detail with respect to its specific embodiments, it will be appreciated that those skilled in the art, after gaining an understanding of the foregoing, can readily devise alterations, variations, and equivalents of such embodiments. In that sense, the scope of the present invention should be evaluated as that of the appended claims and any equivalents thereto.

权利要求:
Claims (15)
[0001]
1. Thermoformed article which is formed from a polymeric sheet having a thickness of 0.1 to 100 millimeters, wherein the polymeric sheet contains - a thermoplastic composition which includes a continuous phase which includes a matrix polymer, - a microinclusion which has a melt flow rate of 0.1 to 250 grams for 10 minutes, determined at a load of 2160 grams and at 190°C, and - a nanoinclusion additive which has a melt flow rate of 10 to 200 grams for 10 minutes, determined at a load of 2160 grams and at 190°C dispersed within the continuous phase in the form of discrete domains, CHARACTERIZED by the fact that the polymeric sheet is extracted at a temperature lower than the glass transition temperature of the matrix polymer before being supplied to the thermoformed mold, and wherein a porous network is defined in the composition that includes a plurality of nanopores having an average transverse dimension of 800 nanometers or less, wherein the microinclusion additive is present. present in an amount of from 1% by weight to 20% by weight based on the weight of the thermoplastic composition and the nanoinclusion additive is present in an amount of from 0.01% by weight to 15% by weight based on the weight of the thermoplastic composition .
[0002]
2. Thermoformed article according to claim 1, CHARACTERIZED by the fact that the nanopores have an average transverse dimension of 1 to 500 nanometers and, preferably, from 5 to 400 nanometers and/or an average axial dimension of 100 to 5000 nanometers, preferably from 50 to 2000 nanometers and more preferably from 100 to 1000 nanometers; and/or the total pore volume of the composition is from 15% to 80%, preferably from 20% to 70%, and most preferably from 30% to 60% per cubic centimeter, and/or the nanopores comprise 15% by volume or more, preferably 20% by volume or more, and most preferably from 40% by volume to 90% by volume of the total pore of the composition.
[0003]
3. Thermoformed article according to claim 1, CHARACTERIZED in that the matrix polymer includes a polyester or polyolefin, wherein the polyester preferably includes polylactic acid or polyethylene terephthalate; and/or the microinclusion additive includes a polyolefin, such as a propylene homopolymer, α-olefin/propylene copolymer, or a combination thereof; and/or wherein the nanoinclusion additive is a functionalized polyolefin, such as a polyepoxide.
[0004]
4. Thermoformed article according to claim 1, CHARACTERIZED in that: the continuous phase constitutes from 75% by weight to 98% by weight and, more preferably, from 80% by weight to 95% by weight of the composition thermoplastic; the microinclusion additive constitutes from 2% by weight to 20% by weight and more preferably from 5% by weight to 20% by weight of the composition, based on the weight of the continuous phase; and/or the nanoinclusion additive constitutes from 0.05% by weight to 15% by weight, preferably from 0.1% by weight to 10% by weight and more preferably from 0.5% by weight to 5 % by weight of the composition, based on the weight of the continuous phase.
[0005]
5. Thermoformed article according to claim 1, CHARACTERIZED in that the thermoplastic composition further comprises an interphase modifier, such as a silicone, silicone-polyether copolymer, aliphatic polyester, aromatic polyester, alkylene glycol, alkane diol, amine, fatty acid ester, or a combination thereof, wherein the interphase modifier constitutes from 0.1% by weight to 20% by weight of the composition based on the weight of the continuous phase.
[0006]
6. Thermoformed article, according to claim 1, CHARACTERIZED by the fact that the composition is free of gaseous blowing agents.
[0007]
7. Thermoformed article, according to claim 1, CHARACTERIZED by the fact that the porous network also includes micropores having an average transverse dimension of 0.5 to 30 micrometers and/or an aspect ratio of 1 to 30.
[0008]
8. Thermoformed article, according to claim 1, CHARACTERIZED by the fact that the porous network is homogeneously distributed throughout the composition, and/or the nanopores are distributed in parallel columns.
[0009]
9. Thermoformed article according to claim 1, CHARACTERIZED by the fact that the microscale domains have an average transverse dimension of 0.5 micrometers to 250 micrometers.
[0010]
10. Thermoformed article according to claim 1, CHARACTERIZED in that the sheet is multilayered and contains a core layer and at least one outer layer, wherein the core layer, outer layer, or both, contains the thermoplastic composition.
[0011]
11. Thermoformed article, according to claim 1, CHARACTERIZED by the fact that the sheet has a thickness of 0.4 to 60 millimeters and, preferably, from 0.5 to 20 millimeters.
[0012]
12. Method for thermoforming the article, as defined in any one of the preceding claims, the method CHARACTERIZING in that it comprises: heating the polymeric sheet to a temperature above the glass transition temperature of the thermoplastic composition; supplying the heated polymeric sheet to a thermoforming mold; and casting the polymeric sheet into the mold, wherein the polymeric sheet is stripped before being supplied to the thermoforming mold.
[0013]
13. Method, according to claim 12, CHARACTERIZED by the fact that the polymeric sheet is extracted at a temperature that is lower than the glass transition temperature of the matrix polymer.
[0014]
14. Method, according to claim 12, CHARACTERIZED by the fact that the leaf is extracted at an extraction rate of 1.1 to 3.5; or wherein the sheet is extracted at a temperature of at least 10°C below the glass transition temperature of the matrix polymer; or wherein the sheet is heated to a temperature of from 30°C to 150°C, preferably from 50°C to 130°C, and most preferably from 60°C to 120°C.
[0015]
15. Method, according to claim 12, CHARACTERIZED by the fact that the sheet is cut after being molded.

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同族专利:

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公开号 | 公开日

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US10286593B2|2019-05-14|

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RU2016148475A3|2018-06-09|

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JP2017522399A|2017-08-10|

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EP3152038A1|2017-04-12|

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MX2016015249A|2017-05-25|

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EP3152038A4|2018-01-17|

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AU2015269616B2|2019-06-20|

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AU2015269616A1|2016-12-22|

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EP3152038B1|2020-05-06|

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BR112016025073A2|2017-08-15|

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RU2016148475A|2018-06-09|

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SG11201609508RA|2016-12-29|

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MX371283B|2020-01-24|

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WO2015187924A1|2015-12-10|

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ZA201608335B|2018-05-30|

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CN107124874A|2017-09-01|

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KR102330971B1|2021-11-25|

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KR20170013901A|2017-02-07|

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US20170080628A1|2017-03-23|

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法律状态:
2020-04-07| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-05-04| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2021-08-03| B350| Update of information on the portal [chapter 15.35 patent gazette]|

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2021-11-09| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2022-01-04| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 04/06/2015, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US201462008697P| true| 2014-06-06|2014-06-06|

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US62/008,697|2014-06-06|

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PCT/US2015/034158|WO2015187924A1|2014-06-06|2015-06-04|Thermoformed article formed from a porous polymeric sheet|

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