POLYMERIC MATERIAL WITH MULTIMODAL PORE SIZE DISTRIBUTION

专利摘要:
polymeric material with multimodal pore size distribution. a polymeric material having an intermodal pore size distribution is provided. the material is formed by applying a stress to a thermoplastic composition that contains a first and second inclusion additive dispersed in a continuous phase that includes a polymeric matrix. through the use of particular types of inclusion additives and careful control over the way in which such additives are dispersed within the polymer matrix, the present inventors have found that a unique multimodal porous structure can be achieved.
公开号:BR112015029119B1
申请号:R112015029119-8
申请日:2014-06-06
公开日:2021-06-22
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Antonio J. Carrillo；Theodore T. Tower；David G. Biggs；Neil T. Scholl；Thomas A. Eby
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

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[1] The present application claims priority over temporary applications with serial numbers 61/833,983, filed June 12, 2013, and 61/907,566, filed November 22, 2013, which are hereby incorporated in their entirety for purposes of of reference. Invention History
[2] Significant efforts have been made to produce low density polymeric materials to improve the use of natural resources and reduce the carbon footprint of finished products. The typical approach to producing such low-density materials is through polymeric foaming using physical or chemical blowing agents, which create gas-filled pores throughout the volume. Chemical blowing agents are compounds that undergo a chemical gas-releasing reaction that creates the pore structure through the polymer mass. Physical blowing agents are usually compressed gases that are dispersed in the polymer and expand, creating pores. Regardless, typical foaming processes induce low molecular orientation, as pore formation occurs when the polymer is in a molten state. This prevents the polymer from hardening, which usually occurs at temperatures well above the polymer's melting temperature or glass transition temperature, resulting in products with low mechanical strength. In addition, typical foaming processes generate large cell sizes, such as larger than 100 µm. This reduces melt strength, thus leading to breakdowns in high-speed production processes with high strain rates (eg fiber spinning, film forming, molding, etc.).
[3] Thus, there is currently a need for an improved polymeric material that is porous. Invention Summary
[4] According to an embodiment of the present invention, a porous polymeric material containing a thermoplastic composition is disclosed. The thermoplastic composition includes a continuous phase, wherein a first inclusion additive and a second inclusion additive are dispersed as discrete domains, the continuous phase including a polymer matrix. A plurality of micropores are formed in and/or around the first domains, which have an average cross-sectional dimension of approximately 0.5 to 30 microns, and a plurality of nanopores are formed in and/or around the second domains, which have an average transverse dimension of approximately 50 to 500 nanometers.
[5] Other properties and aspects of the present invention will be discussed in more detail below. Brief description of the illustrations
[6] A complete and clarifying description of the present invention, including its best mode, aimed at people with technical knowledge in the area, is shown in more detail in the rest of the specification, which makes reference to the attached figures in which:
[7] Figs. 1-2 are SEM photomicrographs of the unstretched film of Example 1 (the film was cut parallel to the machine direction orientation);
[8] Figs. 3-4 are SEM micrographs of the unstretched film of Example 1 (film was cut parallel to machine direction orientation);
[9] Figs. 5-6 are SEM micrographs of the unstretched film of Example 2, characterized by being cut perpendicular to the machine direction in Fig. 5 and parallel to the machine direction in Fig. 6;
[10] Figs. 7-8 are SEM photomicrographs of the unstretched film of Example 2 (film was cut parallel to machine direction orientation);
[11] Fig. 9 is an SEM photomicrograph of the unstretched, injection-molded sample of Example 3 (polypropylene, polylactic acid, and polyepoxide) after freezing fracture in liquid nitrogen;
[12] Fig. 10 is an SEM photomicrograph of the stretched injection molded sample from Example 3 (polypropylene, polylactic acid, and polyepoxide) after freeze fracture in liquid nitrogen;
[13] Fig. 11 is a stress-strain curve of the drawn sample from Example 3;
[14] Fig. 12 is an SEM (1000X) photomicrograph of the fiber from Example 4 (polypropylene, polylactic acid, and polyepoxide) after freeze fracture in liquid nitrogen;
[15] Fig. 13 is an SEM (5,000X) photomicrograph of the fiber from Example 4 (polypropylene, polylactic acid, and polyepoxide) after freeze fracture in liquid nitrogen; and
[16] Fig. 14 is an SEM (10,000X) photomicrograph of the fiber surface of Example 4 (polypropylene, polylactic acid, and polyepoxide).
[17] The repeated use of reference characters in this specification and in the drawings is intended to represent the same or similar features or elements of the present invention. Detailed Description of Representative Embodiments
[18] Detailed references will be made to various configurations of the invention, with one or more examples described below. Each example is provided by way of explanation of the invention, without limitation to the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations can 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 application to produce yet another embodiment. Thus, it is intended that the present invention cover such modifications and variations as are within the scope of the appended claims and their equivalents.
[19] In general, the present invention is directed to a polymeric material that has a multimodal pore size distribution. The material is formed by applying a stress to a thermoplastic composition that contains a first and second inclusion additive dispersed in a continuous phase that includes a polymeric matrix. The first and second inclusion additives are generally selected so as to be partially incompatible (eg different modulus of elasticity) with the polymer matrix. In this way, the inclusion additive can be better spread in the polymer matrix in the form of discrete domains.
[20] The first inclusion additive is usually dispersed in the polymer matrix in the form of relatively large sized discrete first domains. These first domains can have an average transverse dimension of from about 0.05 to about 50 micrometers, in some embodiments from about 0.2 to about 10 micrometers, and in other embodiments from about 0. 5 to about 5 micrometers. The term "transverse dimension" generally refers to a characteristic dimension (eg, width or diameter) of a domain, which is substantially perpendicular to its major axis (eg, length) and also typically substantially orthogonal to the direction of applied stress. during the stretch. The first domain also has an average axial dimension of 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 and, in other embodiments, from about 5 to about 25 micrometers. The “axial dimension” is the dimension in the direction of the major axis (eg, length), which is usually in the direction of stretch. This can result in a first domain shape ratio (the ratio of axial dimension to orthogonal dimension to axial dimension) of from about 2 to about 150, in some embodiments from about 3 to about 100 and, in other embodiments, from about 4 to about 50. Likewise, the second inclusion additive generally is dispersed in the polymeric matrix as discrete second domains, which are smaller in size than the first domains. For example, the second domains can have an average transverse dimension of from about 50 to about 500 nanometers, in some embodiments from about 60 to about 400 nanometers, and in other embodiments from about 80 to about 300 nanometers. Due to their small size, second domains are typically not elongated in the same way as microscale domains. For example, the second domains can be substantially spherical in nature. Additional include additives can also be used, which have a size that is equal to, larger or smaller than the first or second domain.
[21] Through the use of particular types of inclusion additives and careful control over the way in which such additives are dispersed within the polymeric matrix, the present inventors have found that a single porous structure can be achieved. Namely, when the composition is subjected to an externally applied stress (eg mechanical stretching), areas of stress intensification can be created in and around the domains, the location depending on the specific nature of the additives. When the inclusion additives have a higher modulus than the polymer matrix, for example, the maximum areas of stress enhancement are located at the domain pole and aligned in the direction of applied stress. Notably, the areas of stress enhancement created by the first inclusion additive may overlap with those created by the second inclusion additive. In this way, a dramatic increase in local stress (ie, stress amplification) can occur in and around the inclusion limits, with the smallest inclusion additives located in the stress enhancing areas of the first inclusion additive exhibiting the greatest amplification of tension. The present inventors have discovered that this stress amplification phenomenon can initiate a controlled, cascading process of deagglutination and pore formation in or around inclusion additives, starting with the second smallest domains exhibiting the greatest stress amplification and propagating to the larger first domains as the external applied voltage increases. Also, because the pores are located adjacent to the discrete domains, a bridge can be formed between the pore boundaries, which act as internal structural hinges to help prevent the pores from collapsing.
[22] The cascade form in which pore formation is initiated allows the formation of a porous network with a multimodal distribution. For example, a plurality of micropores can be formed in or around first domains which have an average transverse dimension (e.g. width or diameter) of from about 0.5 to about 30 micrometers, in some embodiments of about 1 to about 20 micrometers, and in some embodiments, about 2 micrometers to about 15 micrometers. In addition, a plurality of nanopores can be formed in and/or around the second domains which have an average cross-sectional dimension (e.g. width or diameter) of from about 50 to about 500 nanometers, in some embodiments of from about 60 to about 450 nanometers, and in some embodiments, from about 100 to about 400 nanometers. It should also be understood that pores of different sizes can also be formed in and/or around the inclusion additives. For example, in certain cases, a plurality of second pores may also be formed in and/or around the second domains, which have an average transverse dimension of about 1 to about 50 nanometers, in some embodiments of about 2 to about 45 nanometers and, in other embodiments, from about 5 to about 40 nanometers. The micropores and/or nanopores can have any regular or irregular shape, such as spherical, elongated, etc., and can also have a shape ratio (the ratio of axial dimension to transverse dimension) of from about 1 to about 30, in some embodiments from about 1.1 to about 15 and, in other embodiments, from about 1.2 to about 5.
[23] The present inventors also discovered that pores (eg, micropores, nanopores, or both) can be distributed fairly evenly throughout the material. For example, pores can be distributed in columns oriented in a direction normally perpendicular to the direction in which stress is applied. These columns can generally be parallel to each other across the entire width of the material. Without intending to impose theoretical limitations, it is believed that the presence of this homogeneously distributed porous network can result in high thermal resistance as well as good mechanical properties (eg, energy dissipation under load and impact resistance ). There is a stark contrast to conventional pore-making techniques that involve the use of a blowing agent, which tends to result in uncontrolled pore distribution and poor mechanical properties. Notably, the formation of the porous network by the above-described process does not necessarily result in a substantial change in the transverse size (e.g., width) of the material. In other words, the material is not substantially narrow, which can allow the material to retain its initial transverse dimension and a greater degree of strength properties.
[24] The average percent volume occupied by micropores and nanopores within a given unit volume of material 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 material. In certain cases, nanopores can be present in a relatively high amount. For example, nanopores can constitute about 15% by vol. to about 99% by vol.; in some embodiments, 20% by vol. to about 95% by vol.; and in other embodiments, about 40% by vol. to about 90% by vol. of the total pore volume in the polymeric material. Likewise, micropores can constitute about 1% by vol. to about 85% by vol.; in some embodiments, 5% by vol. to about 80% by vol.; and in other embodiments, about 10% by vol. to about 60% by vol. of the total pore volume in the polymeric material. Of course, additional classes of pores can also be present in the polymeric material. Regardless, with such a high pore volume, the resulting polymeric material can have a relatively low density, such as about 1.2 grams per cubic centimeter ("g/cm3") or less, in some embodiments about 1 .0 g/cm3 or less, in some embodiments from 0.2 g/cm3 to about 0.8 g/cm3, and in some embodiments from about 0.1 g/cm3 to about 0. 5 g/cm3.
[25] In addition to reduced density, the unique multimodal pore structure can also provide a variety of functional benefits to the resulting polymeric material. For example, such a structure can help restrict fluid flow through the material and generally be impervious to liquids (eg, liquid water), thus allowing the material to insulate a water-penetrating surface. In that regard, the polymeric material may have a relatively high hydrostatic charge value of about 50 centimeters ("cm") or more, in some embodiments about 100 cm or more, in some embodiments, about 150 cm or more, and in some embodiments, from about 200 cm to about 1000 cm, as determined in accordance with ATTCC 1272008. Other beneficial properties can also be achieved. For example, the resulting polymeric material can generally be permeable to water vapor. The material's water vapor permeability can be characterized by its relatively high water vapor transmission rate ("TTVA"), which is the rate at which water vapor penetrates through a material, measured in units of grams per square meter for 24 hours (g/m2/24 h). For example, the polymeric material may exhibit an TTVA 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/ m2-24 hours or more, and in other 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 IST Procedure -70.4 (01). The polymeric material can also act as a thermal barrier that exhibits a relatively low thermal conductivity, such as about 0.40 watts per meter-Kelvin ("W/mK") or less, in some embodiments about 0.20 W/mK or less, in some embodiments from about 0.15 W/mK or less, in some embodiments from about 0.01 to about 0.12 W/mK, and in some embodiments , from about 0.02 to about 0.10 W/mK. Notably, the material is able to achieve these low thermal conductivity values with relatively low thicknesses, which can allow the material to have a greater degree of flexibility and moldability, as well as reduce the space it takes up in an article. For this reason, polymeric material may also have a relatively low “thermal inlet”, which is equal to the thermal conductivity of the material divided by its thickness and is given in units of watts per square meter-Kelvin (“W/m2K”). For example, the material may have a heat input of about 1000 W/m2K or less, in some embodiments from about 10 to about 800 W/m2K, in some embodiments from about 20 to about 500 W/m2K, and in some embodiments, from about 40 to about 200 W/m2K. The actual thickness of the polymeric material may depend on its particular shape, but generally ranges from about 5 micrometers to about 100 millimeters, in some embodiments from about 10 micrometers to about 50 milliliters, in some embodiments from about from 200 micrometers to about 25 millimeters.
[26] We will now describe several embodiments of this invention in more detail. 1. Thermoplastic compound A. Polymeric matrix
[27] As indicated above, the thermoplastic composition contains a continuous phase in which the first and second inclusion additives are dispersed. The continuous phase contains one or more polymeric matrices, which generally consist of 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 variety of renewable polyesters can normally be employed, such as those with aliphatic polyesters such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (eg, polyethylene carbonate), poly-3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, copolymers of poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3-hydroxybutyrate-co- 3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxydecanoic, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and aliphatic succinate-based polymers (for example , polybutylene succinate, polybutylene succinate adipate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (for example, polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene adipate isophthalate, polybutylene adipate isophthalate, etc.); aromatic polyesters (for example polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[28] In certain cases, the thermoplastic composition contains 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 approximately 0°C or more, in some embodiments from approximately 5°C to 100°C, in some embodiments from approximately 30°C to approximately 80°C, and in some embodiments, from approximately 50°C to approximately 75°C. Polyester can also have a melting 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 to about 220°C. The melting temperature can be determined by differential scanning calorimetry (DSC) in accordance with ASTM D3417. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM E1640-09.
[29] An especially suitable rigid polyester is polylactic acid, which can be derived from monomeric units of any lactic acid isomer, such as levorotatory lactic acid ("L-lactic acid"), dextrorotatory lactic acid ("D-lactic acid") , mesolatic acid or combinations thereof. Monomer units can also be formed from anhydrides of any lactic acid isomer, including L-lactide, D-lactide, mesolactide, 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 may also be employed (for example, a diisocyanate compound, an epoxy compound or acid anhydride). The polylactic acid can be a homopolymer or a copolymer, such as one containing monomeric units derived from L-lactic acid and monomeric 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 approximately 85% by mol or more, in some embodiments, approximately 90% by mole or more and, in other embodiments, approximately 95% by mole or more. Various polylactic acids, each with a different ratio between the L-lactic acid-derived monomer unit and the D-lactic acid-derived monomer unit, can be mixed at any random percentage. Of course, polylactic acid can be blended with other types of polymers (eg polyolefins, polyesters, etc.).
[30] In a specific embodiment, polylactic acid has the following general structure:

[31] A specific example of a suitable polylactic acid polymer that can be used in the current invention is marketed by Biomer, Inc. of Krailling, Germany) under the name BIOMER™ L9000. Other suitable polylactic acid polymers are available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEA®). Still other suitable polylactic acids can be described in US Patents 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254 and 6,326,458.
[32] Polylactic acid typically has a number average molecular weight (“Mn”) that ranges from approximately 40,000 to 180,000 grams per mol; in some embodiments, from approximately 50,000 to 160,000 grams per mol, and in other embodiments, from approximately 80,000 to 120,000 grams per mol. Likewise, the polymer typically has a number average molecular weight ("Mw") ranging from approximately 80,000 to 250,000 grams per mol; in some embodiments approximately 100,000 to 200,000 grams per mole and in other embodiments approximately 110,000 to 160,000 grams per mole. The relationship between the weight average molecular mass and the number average molecular mass (“Mw/Mn”), that is, the “polydispersity index”, is also relatively low. For example, the polydispersity index typically ranges from 1.0 to 3.0 approximately; in some embodiments from 1.1 to 2.0 approximately, and in other embodiments from 1.2 to 1.8 approximately. The number and weight average molecular masses can be determined by methods known to those skilled in the art.
[33] Polylactic acid may also have an apparent viscosity of approximately 50 to 600 Pascal-seconds (Pa^s); in some embodiments approximately 100 to 500 Pa s and in other embodiments approximately 200 to 400 Pa s as measured at a temperature of 190°C and a shear rate of 1000 sec-1 . The melt index of polylactic acid (on a dry basis) can also range from about 0.1 to 40 grams per 10 minutes; in some embodiments, from about 0.5 to 20 grams per 10 minutes, and in other embodiments, from about 5 to about 15 grams per 10 minutes, measured at a load of 2,160 grams and 190 °C.
[34] Some types of pure polyester (eg, polylactic acid) can absorb water from an environment in such a way that it has a moisture content of approximately 500 to 600 parts per million (“ppm”), or even higher, based on dry weight of the starting polylactic acid. Moisture content can be determined in various ways, as is known in the art, in accordance with ASTM D 7191-05, as described below. As the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes better to dry the polyester before blending it. In most embodiments, for example, it is best for the renewable polyester to have a moisture content of approximately 300 parts per million ("ppm") or less, in some embodiments approximately 200 ppm or less, in some forms of carrying out, from approximately 1 to approximately 100 ppm, before mixing with the first and second inclusion additives. Drying of polyester can occur, for example, at a temperature of approximately 50°C to approximately 100°C and, in some embodiments, approximately 70°C to approximately 80°C. B. First inclusion additive
[35] The particular nature of the first inclusion additive is not critical, and may include liquids, semi-solids, or solids (eg, amorphous, crystalline, or semi-crystalline). In certain embodiments, the inclusion additive is polymeric in nature and has a relatively high molecular weight which can help improve melt strength and stability of the thermoplastic composition. Generally, the first inclusion additive polymer may be generally incompatible with the matrix polymer. In this way, the additive can best be spread as discrete phase domains within a continuous phase of the matrix polymer. The domains can have a number of different shapes, e.g. elliptical, spherical, cylindrical, dish-shaped, tubular, etc. In one embodiment, for example, the domains are quite elliptical in shape. The physical dimension of an individual domain is usually small enough to minimize the propagation of cracks in the polymeric material by applying an external stress, but large enough to initiate microscopic plastic deformation and allow for shear zones and/or stress intensity in and around the particle inclusions.
[36] Although polymers may be incompatible, the first inclusion additive can still be selected having a solubility parameter that is relatively similar to the matrix polymer. This can improve the interfacial compatibility and physical interaction of discrete and continuous phase boundaries and thus reduce the likelihood of composite disruption. For this, the ratio of the matrix polyester solubility parameter to the additive parameter is typically from approximately 0.5 to approximately 1.5 and, in some embodiments, from approximately 0.8 to approximately 1.2. For example, the first inclusion additive may have a solubility parameter from approximately 15 to approximately 30 MJoules1/2/m3/2 and, in some embodiments, from approximately 18 to approximately 22 MJoules1/2/m3/2, while polylactic acid can have a solubility parameter of approximately 20.5 MJoules1/2/m3/2. The term "solubility parameter", as used herein, refers to the "Hildebrand Solubility Parameter", which is the square root of the cohesive energy density, calculated using the following equation:
where: Δ Hv = heat of vaporization R = Ideal gas constant T = Temperature Vm = Molecular volume
[37] Hildebrand solubility parameters of many polymers are also found in Wyeych's Solubility Handbook of Plastics (2004), included herein as a reference.
[38] The first polymeric inclusion additive may also have a melt index (or viscosity) to ensure that the resulting discrete domains can be properly maintained. For example, if the pour index of the additive is too high, it tends to flow and disperse uncontrollably during the continuous phase. This results in lamellar or plaque-like domains or cocontinuous phase structures that are difficult to maintain and likely to rupture prematurely. On the other hand, if the pour index of the inclusion additive is too low, it will tend to clump together and form very large elliptical domains, which are difficult to disperse during mixing. This can cause an uneven distribution of the additive throughout the continuous phase. In this regard, the present inventors have found that the ratio of the melt index of the first inclusion additive to the melt index of the matrix polymer is typically from approximately 0.2 to approximately 8, in some embodiments, from approximately 0.5 to approximately 6 and, in other embodiments, from approximately 1 to approximately 5. The first inclusion additive may have, for example, a pour index of 0.1 to 250 grams for approximately 10 minutes, in some embodiments from 0.5 to 200 grams for approximately 10 minutes and, in other embodiments, from 5 to 150 grams for approximately 10 minutes, determined at a load of 2,160 grams and at 190°C.
[39] In addition to the properties noted above, the mechanical characteristics of the first inclusion additive additive can also be selected to achieve the desired porous network. For example, when a mixture of matrix polymer and first inclusion additive is applied with an external force, stress concentrations (eg including normal and shear stresses) and shear and/or flow zones Plastic flow can be initiated in and around discrete phase domains as a result of stress concentrations that arise from a difference in the modulus of elasticity of the additive and the matrix polymer. Higher stress concentrations promote a more intense localized plastic flux in the domains, allowing them to undergo considerable elongation when subjected to stress. These elongated domains allow the composition to exhibit a more flexible and softer behavior than the matrix polymer, such as when in the form of a rigid polyester resin. To improve stress concentrations, the first inclusion additive can be selected so that it has a relatively low Young's modulus of elasticity compared to the matrix polymer. For example, the ratio of matrix polymer elastic modulus to additive is generally from about 1 to about 250, in some embodiments from about 2 to about 100, and in other embodiments, from about 2 to about 50. The modulus of elasticity of the first inclusion additive may, for example, range from 2 to 1000 megapascals (MPa) approximately, in some embodiments from approximately 5 to 500 MPa, and in other forms of performance, from 10 to 200 MPa approximately. On the other hand, normally the modulus of elasticity of polylactic acid, for example, is from about 800 MPa to about 3000 MPa.
[40] Although a wide variety of first inclusion additives can be employed, particularly suitable examples of such additives may include synthetic polymers such as polyolefins (eg, polyethylene, polypropylene, polybutylene, etc.); styrenic copolymers (for example, 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 (for example, poly(ethylene vinyl acetate), polyvinyl chloride acetate, etc.); polyvinyl alcohols (eg polyvinyl alcohol, poly(ethylene vinyl alcohol), etc.); polyvinyl butyral; acrylic resins (for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, etc.); polyamides (for example nylon); polyvinyl chlorides; polyvinylidene chlorides; polystyrenes; polyurethanes, etc. Suitable polyolefins may, for example, include ethylene polymers (eg, low density polyethylene ("PE-LD"), high density polyethylene ("HDPE"), linear low density polyethylene ("LDPE"), etc. .), propylene homopolymers (eg syndiotactic, atactic, isotactic, etc.), propylene copolymer and so on.
[41] In one embodiment, the polymer is a propylene polymer, such as homopolypropylene, or a copolymer of propylene. The propylene polymer can, for example, be formed of an isotactic polypropylene homopolymer or a copolymer containing an amount equal to or less than approximately 10% by mass of another monomer, i.e. at least approximately 90% by mass of propylene. Such polymers can have a melting point of about 160°C to about 170°C.
[42] In yet another embodiment, the polyolefin may be a copolymer of ethylene or propylene with another α-olefin, such as C3-C20 α-olefin or C3-C12 α-olefin. Specific examples of suitable α-olefins are 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. Especially 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% by mole to about 99% by mole, in some embodiments from 80% by mole to about 98.5% by mole and in other forms of realization from 87% by mol to about 97.5% by mol. The α-olefin content can range from about 1% by mole to about 40% by mole, in some embodiments from 1.5% by mole to about 15% by mole, and in some embodiments from 2 .5% by mol to about 13% by mol.
[43] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers, marketed under the name EXACTTM, from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are marketed under the names ENGAGE™, AFFINITY™, DOWLEX™ (LDPE) and ATTANE™ (PEUBD) from the Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in US Patents 4,937,299 para. 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. There are propylene copolymers marketed under the name VISTAMAXX™ from ExxonMobil Chemical Co. of Houston, Texas; FINA™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMERTM marketed by Mitsui Petrochemical Industries; and VERSIFYTM, available from the Dow Chemical Co. of Midland, Michigan. Suitable polypropylene homopolymers may also include Exxon Mobil 3155 polypropylene, Exxon Mobil Achieve™ resins and Total M3661 PP resin. Other examples of suitable propylene polymers are described in U.S. Patents 6,500,563 to Datta et al.; 5,539,056 for Yang et al.; and 5,596,052 for Resconi et al.
[44] A wide variety of known techniques can be employed to form olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordination catalyst (eg Ziegler-Natta). Typically, the olefin polymer is formed by a single-site coordination catalyst such as a metallocene catalyst. This catalyst system produces ethylene copolymers, in which the comonomer is randomly distributed within a molecular chain and evenly distributed among the 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 for Davis et al.; 5,472,775 to Obijeski et al.; 5,272,236 for Lai et al.; and 6,090,325 for 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 , bis(methylcyclopentadienyl) zirconium dichloride, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl(cyclopentadienyl,-1-flourenyl) zirconium dichloride, molybdenum dichloride, dichlorene, nickelocene dichloride, titanium dichloride zirconocene chloride hydride, zirconocene dichloride and so on. Polymers created using the metallocene catalyst typically have a narrow molecular mass range. For example, metallocene-catalyzed polymers can have polydispersity numbers (Mw/Mn) below 4, controlled short chain branching distribution, and controlled isotacticity.
[45] Regardless of the materials used, the relative percentage of the first additive included in the thermoplastic composition is selected to achieve the desired properties without significantly affecting the basic properties of the composition. For example, the first inclusion additive is normally employed in the amount of from about 1% to about 30% by weight, in some embodiments from about 2% by weight to about 25% by weight, and in others embodiments, from about 5% by weight to about 20% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymers). The concentration of the first inclusion additive in the entire thermoplastic compound can also be formed from about 0.1% to about 30% by weight, in some embodiments, from about 0.5% to about 25% by weight. weight and, in other embodiments, from about 1% to about 20% by weight. C. Second inclusion addendum
[46] The second inclusion additive is generally used in the amount of from about 0.05% to about 20% by weight, in some embodiments from about 0.1% by weight to about 10% by weight and, in other 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 polymers). The concentration of the second inclusion additive in the entire thermoplastic compound can also be from about 0.01% to about 15% by weight, in some embodiments, from about 0.05% to about 10% by weight. weight and, in other embodiments, from about 0.1% to about 8% by weight.
[47] The particular state or form of the second inclusion additive is not critical as long as the desired domains can be formed. For example, in some embodiments, the second inclusion additive can be in the form of a liquid or semi-solid at room temperature (e.g., 25°C). Such liquid can be easily dispersed in the matrix to form a metastable dispersion, and then quenched to preserve domain size by reducing the temperature of the mixture. In still other embodiments, the second inclusion additive is in the form of a solid, which can be amorphous, crystalline or semi-crystalline. For example, the second inclusion additive can be polymeric and have a relatively high molecular weight which can help improve melt strength and stability of the thermoplastic compound.
[48] To improve its dispersibility in nanoscale domains, the second inclusion additive may contain a polar component that is compatible with a part of the matrix polymer and/or the first inclusion additive. This can be especially useful when the matrix polymer or first inclusion additive has a polar part, such as a polyester. An example of a second inclusion additive is functionalized polyolefin. The polar compound can, for example, be provided by one or more functional groups, and the non-polar component can be provided by an olefin. The olefin compound of the second inclusion additive normally can be formed from any branched or linear α-olefin monomer, oligomer or polymer (including copolymers) derived from an olefin monomer as described above.
[49] The functional group of the second inclusion additive can be any group, molecular segment and/or block that provides a polar component to the molecule and is not compatible with the matrix polymer. Examples of non-polyolefin compatible molecular segment and/or blocks may include acrylates, styrenes, polyesters, polyamides, etc. The functional group can 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, etc. 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 marketed by EI du Pont de Nemours and Company under the name Fusabond® as the P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified satin vinyl foam), A series (chemically modified ethylene acrylate copolymers or terpolymers), or the N series (chemically modified ethylene-propylene, ethylene-propylene diene ("EPDM") or ethylene-octene monomer). Alternatively, maleated polyolefins are also marketed by Chemtura Corp. under the name Polybond® and by Eastman Chemical Company under the name Eastman G series.
[50] In certain embodiments, the second inclusion additive may also be reactive. An example of this second inclusion additive is the polyepoxide modifier that contains, on average, at least two axirane rings per molecule. Without intending to be bound by theory, it is believed that these polyepoxide molecules can induce a matrix polymer (eg, polyester) reaction under certain conditions, thus improving their melt strength without greatly reducing the temperature of 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 can allow a nucleophilic ring-opening reaction via a terminal carboxyl group of a polyester (esterification) or via a hydroxyl group (etherification). Reactions on the oxazoline side can occur to form amide ester moieties. Through these reactions, the molecular mass of the matrix polymer can be increased in order to counteract the degradation often observed during the melting process. While it is desirable to induce a reaction with the matrix polymer, as described above, the inventors have found that too much of a reaction can cause crosslinking between polymeric structures. If this crosslinking is allowed to proceed to a considerable extent, the resulting polymer blend can become brittle and difficult to process into a material with the desired strength and elongation properties.
[51] In this regard, the present inventors have found that polyepoxides with a relatively low epoxy resource are especially effective, which can be quantified by their "epoxy equivalent weight". Epoxy equivalent weight reflects the amount of resin that contains a molecule of an epoxy group, and can be calculated by dividing the number average molecular mass 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 ranging 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 other embodiments, from about 20,000 to 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 from 5 to 45, and in other embodiments from 15 to 40 epoxy groups. In turn, the epoxy equivalent weight can be less than about 15,000 grams per mole; in some embodiments, from about 200 to about 10,000 grams per mole, and in other embodiments, from about 500 to about 7,000 grams per mole.
[52] Polyepoxide can be a linear or branched homopolymer or copolymer (eg, random, graft, block, etc.) 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 salts or esters thereof, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth)acrylic monomers can include, without limitation, 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 itoconate.
[53] Polyepoxide typically has a relatively high molecular mass, as indicated above, so it may not only result in chain extension but also help achieve the desired blend morphology. Thus, the resulting melt flow index of the polymer can thus range from about 10 to about 200 grams per 10 minutes; in some embodiments, from about 40 to about 150 grams per 10 minutes, and in other embodiments, from about 60 to about 120 grams per 10 minutes, determined at a 2,160 gram load and temperature 190°C.
[54] Other monomers can also be used in the polyepoxide to help achieve the desired molecular mass, if desired. Such monomers can vary and include, for example, ester monomers, (meth)acrylic monomers, olefin monomers, amide monomers, etc. In a certain embodiment, for example, the polyepoxide includes at least one linear or branched α-olefin monomer, such as those with 2 to 20 carbon atoms and preferably with 2 to 8 carbon atoms. Specific examples are 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. Specifically desired α-olefin comonomers are ethylene and propylene.
[55] Another suitable monomer may include a (meth)acrylic monomer that is not epoxy-functional. Examples of such (meth)acrylic monomers may be 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 of 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, methacrylate isobornyl, etc., as well as combinations of these.
[56] In a particularly desirable embodiment of the present invention, the polyepoxide is a terpolymer formed from an epoxy-functional (meth)acrylic monomeric component, an alpha-olefin monomeric component, and a non-epoxy-functional (meth)acrylic monomeric component. functional. For example, the polyepoxide can be poly(ethylene-co-methyl-co-glycidyl methacrylate acrylate), with the following structure:
where x, y and z are 1 or greater.
[57] The epoxy-functional monomer can be made into a polymer using several known techniques. For example, a monomer containing polar functional groups can be grafted onto a polymer backbone to form a grafted copolymer. Such grafting techniques are well known in the art and described, for example, in US Patent No. 5,179,164. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer to form a random block or copolymer using known free radical polymerization techniques such as high pressure reactions, Ziegler-catalyzing reaction systems. Natta, single-site catalysis reaction systems (eg metallocene), etc.
[58] The relative part of the monomeric components can be selected in order to achieve a balance between epoxy reactivity and melt index. More specifically, high epoxy monomer contents can result in good reactivity with the matrix polymer, but too high a content can reduce the melt index such that the polyepoxide will negatively affect the melt strength of the polymer blend. Thus, in most embodiments, the epoxy-functional (meth)acrylic monomers form about 1% to about 25% by weight, in some embodiments, from about 2% to about 20% by weight, and , in other embodiments, from about 4% to about 15% by weight of the copolymer. Alpha olefin monomers can also constitute from about 55% to about 95% by weight; in some embodiments; from about 60% to about 90% by weight and; in other embodiments; from about 65% to about 85% by weight of the copolymer. When employed, other monomeric components (e.g., non-epoxy-functional (meth)acrylic monomers) can constitute from about 5% to about 35% by weight, in some embodiments from about 8% to about 30%. % by weight and, in other embodiments, from about 10% to about 25% by weight of the copolymer. A specific example of a suitable polyepoxide that can be used in this invention is marketed by Arkema under the name LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a melt index of 70 to 100 g/10 min and has a glycidyl methacrylate monomer content of 7% to 11% by weight, a methyl acrylate monomer content of 13% to 17% by weight, and an ethylene monomer content of 72% to 80% by weight. Another suitable polyepoxide commercially available from DuPont under the name EVALOY® PTW, which is a terpolymer of ethylene, butyl acrylate and glycidyl methacrylate and has a melt index of 12 g/10 min.
[59] 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 in order to achieve the desired benefits. For example, if the modification level is too low, the desired increase in melt strength and mechanical properties may not be obtained. The present inventors have also found, 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 epoxy-functional groups. Thus, polyepoxide is normally employed in an amount of 0.05 wt% to approximately 10 wt%; in some embodiments from 0.1% to 8% by weight approximately, in other embodiments from 0.5% to 5% by weight approximately, and in other embodiments from 1% to 3% of the approximately weight based on the mass of the matrix polymer employed in the composite. The polyepoxide can also constitute from about 0.05% to about 10% by weight; in some embodiments, from about 0.05% to about 8% by weight, in other embodiments, from about 0.1% to about 5% by weight, and in other embodiments, from about 0.5% to about 3% by weight, based on the total weight of the compound.
[60] Other reactive second inclusion additives may also be employed in the present invention, such as oxazoline functionalized polymers, cyanide functionalized polymers, etc. When employed, these reactive second inclusion additives may be employed within the concentrations indicated above for the polyepoxide. In a specific embodiment, an oxazoline grafted polyolefin can be employed, that is, a polyolefin grafted with a monomer containing an oxazoline ring. Oxazoline may include 2- oxazolines such as 2-vinyl-2-oxazoline (eg 2-isopropenyl-2-oxazoline), 2-fatty acid-alkyl-2-oxazoline (eg obtained 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, ricino-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. D. Other inclusion additives
[61] As indicated above, the pores of the present invention can be shaped through a cascade deagglutination process created by inclusion additives of different sizes. In this regard, it may be desired to employ additional inclusion additives to further facilitate the deagglutination process. In a particular embodiment, for example, a third inclusion additive may be spread on the polymeric matrix in the form of discrete third domains. For example, the third domains may be smaller than the second domains and, for example, have an average cross-sectional dimension of approximately 1 to 50 nanometers, in some embodiments approximately 2 to 45 nanometers, and in some embodiments of 5 to 40 nanometers. A plurality of nanopores can also be formed in and/or around the third domains which have an average transverse dimension of from about 1 to about 50 nanometers, in some embodiments from about 2 to about 45 nanometers, and in other embodiments, from about 5 to about 40 nanometers. Nanopores can have any regular or irregular shape, such as spherical, elongated, etc. Nanopores can be distributed fairly evenly throughout the material. For example, nanopores can be distributed in columns that are oriented in a direction normally perpendicular to the direction in which stress is applied. These columns can generally be parallel to each other across the entire width of the material.
[62] The material used for the third inclusion additive is not particularly critical. In certain embodiments, for example, nanoparticles can be used, such as carbon black, carbon nanotubes, carbon nanofibers, clays, metallic nanoparticles, nanosilica, nanoalumina, etc. Nanoclays are particularly suitable for the third inclusion additive. 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 silicate formed primarily from montmorillonite), kaolinite (1:1 aluminosilicate having a lamellar structure and 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 in double layer (eg sepiocite), laponite, hectorite, saponite, indonite, etc. 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 achieved by relating the organic cation to clay. Suitable organic cations may include, for example, organoquaternary ammonium compounds that are capable of exchanging cations with clay, such as dimethyl-bis [hydrogenated tallow] ammonium chloride (2M2HT), benzyl methyl bis [hydrogenated tallow] of ammonium chloride (MB2HT), methyl tris [hydrogenated tallow alkyl] chloride (M3HT), etc. Examples of commercially available organic clays may include, for example, Dellite® 43B (Laviosa Chimica of Livorno, Italy), which is a montmorillonite clay modified with dimethyl benzyl hydrogenated tallow ammonium. Other examples include Cloisite® 25A and Cloisite® 30B (Southern Clay Products) and Nanofil 919 (Süd Chemie).
[63] When employed, the third inclusion additive generally comprises from about 0.05% to about 20% by weight, in some embodiments from about 0.1% by weight to about 10% by weight and, in other 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 polymers). The concentration of the third inclusion additive in the entire thermoplastic compound can also be from about 0.01% to about 15% by weight, in some embodiments, from about 0.05% to about 10% by weight. weight and, in other embodiments, from about 0.1% to about 8% by weight.
[64] If desired, the third inclusion additive (eg, nanoclay) can be blended with a carrier resin to form a masterbatch that increases the additive's compatibility with the other polymers in the composition. Particularly suitable carrier resins include, for example, polyesters (for example, polylactic acid, polyethylene terephthalate, etc.); polyolefins (for example, ethylene polymers, propylene polymers, etc.); and so on, as described in more detail above. In some cases, the carrier resin can become dispersed in the form of microscale size domains, such as an average cross-sectional dimension of from about 0.5 to about 30 micrometers, in some embodiments from about 1 to about 1 to about 20 micrometers, and in some embodiments, from about 2 micrometers to about 15 micrometers. However, at least a portion of the third inclusion additive may migrate from the inner regions to form discrete domains of a nanoscale size, such as an average transverse dimension of about 1 to about 50 nanometers, in some embodiments of about from 2 to about 45 nanometers and, in other embodiments, from about 5 to about 40 nanometers. Thus, the carrier resin can result in the formation of a plurality of micropores, such as within the aforementioned size ranges, while the migrated inclusion additive can result in the formation of a plurality of nanopores, such as within the size ranges. noted above. For this reason, the polymer used to form the base mixture for the third inclusion additive can, if desired, serve both as the first inclusion additive and as a carrier resin for the third inclusion additive. Of course, it should be understood that this is by no means necessary and that a separate carrier resin and first inclusion additive can be used. E. Other Components
[65] A wide variety of ingredients can be used in compost for a number of different reasons. For example, in a particular embodiment, an interphase modifier can also be employed in the thermoplastic compound to help reduce the degree of friction and connectivity between the hardening additive and the matrix polymer and thus increase the grade and uniformity. of take-off. In this way, the pores can be distributed more evenly throughout the compound. The modifier form can be liquid or semi-solid at room temperature (eg 25°C) so that it has a relatively low viscosity, allowing it to be more quickly incorporated into the thermoplastic compound and easily migrated to the polymer surfaces. In this regard, the kinematic viscosity of the interphase modifier is typically from approximately 0.7 to approximately 200 centistokes ("cs"), in some embodiments from approximately 1 to approximately 100 cs, and in other embodiments from approximately 1.5 to approximately 80 cs, determined at 40 °C. In addition, the interphase modifier is also typically hydrophobic, so that it has an affinity for the first inclusion additive, for example, resulting 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 inclusion additives, it is believed that the hydrophobic and low viscosity nature of the modifier can help facilitate debonding. As used herein, the term "hydrophobic" typically refers to material that has a contact angle of water and air of approximately 40° or more and, in some cases, approximately 60° or more. By contrast, the term “hydrophilic” usually refers to material that has a contact angle of water and air less than approximately 40°. A suitable test for measuring contact angle is ASTM D5725-99 (2008).
[66] Some suitable, low viscosity, hydrophobic interphase modifiers are, for example, silicones, silicone-polyether copolymers, aliphatic polyesters, aromatic polyesters, alkylene glycols (eg, ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.), alkanes diols, (for example, Propane-1,3-diol, 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 (eg, octyldimethylamine oxide), fatty acid esters, fatty acid amides (eg, oleamide, erucamide, stearamide, ethylene bis(stearamide), etc.), mineral and vegetable oils, etc. A particularly suitable liquid or semi-solids is the polyether polyol, as commercially available under the trade name Pluriol® WI from Basf Corp. Another particularly suitable modifier is the partially renewable ester, marketed under the trade name HALLGREEN® IM by Hallstar.
[67] When employed, the third inclusion additive generally comprises from about 0.1% to about 20% by weight, in some embodiments from about 0.5% by weight to about 15% by weight and, in other embodiments, from about 1% by weight to about 10% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymers). The concentration of interphase modifiers in the entire thermoplastic compound can likewise be formed from about 0.05% to about 20% by weight, in some embodiments from about 0.1% to about 15% by weight and, in other embodiments, from about 0.5% to about 10% by weight.
[68] The interphase modifier has a feature that allows it to quickly migrate to the interfacial surface of polymers and facilitate debonding without damaging the melt properties of the thermoplastic compound. For example, the interphase modifier typically does not have a plasticizing effect on the polymer by reducing its glass transition temperature. Rather, the present inventors have found that the glass transition temperature of the thermoplastic compound can be substantially the same as that of the starting matrix polymer. In this regard, the ratio of the glass transition temperature of the compound to that of the matrix polymer is typically from about 0.7 to about 1.3, in some embodiments from about 0.8 to about 1, 2 and, in other embodiments, from about 0.9 to about 1.1. The thermoplastic compound may, for example, have a glass transition temperature of from about 35°C to about 80°C, in some embodiments from about 40°C to about 80°C, and in other forms of realization, from about 50°C to about 65°C. The melt index of the thermoplastic compound can also be similar to that of the matrix polymer. For example, the melt flow index of the compound (on dry basis) can be from about 0.1 to about 70 grams per 10 minutes, in some embodiments from about 0.5 to about 50 ranges per 10 minutes and, in other embodiments, from about 5 to about 25 grams per 10 minutes, determined at a load of 2,160 grams and a temperature of 190°C.
[69] Compatibilizing agents can also be used to improve interfacial adhesion and reduce interfacial tension between the domain and the matrix, thus allowing the formation of small domains during mixing. Examples of suitable compatibilizing agents may include, for example, epoxide-functionalized copolymers or maleic anhydride chemical moieties. An example of a maleic anhydride compatibilizing agent is polypropylene grafted maleic anhydride, which is commercially available from Arkema under the tradenames Orevac™ 18750 and Orevac™ CA 100. When employed, the compatibilizers can consist of about 0.05% to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, and in other embodiments, from about 0.5% by weight. weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase matrix.
[70] Other suitable materials that can also be used in the thermoplastic composition, such as catalysts, antioxidants, stabilizers, surfactants, waxes, solid solvents, fillers, nucleating agents (eg calcium carbonate, etc.), and other materials added in order to improve the processability and mechanical properties of the thermoplastic compound. Regardless, a beneficial aspect of the current invention is that good mechanical properties can be provided without the need for various conventional additives such as blowing agents (eg, chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, supercritical carbon dioxide, nitrogen, etc. .) and plasticizers (eg solid or semi-solid polyethylene glycol). Indeed, the thermoplastic compound can be considerably free of blowing agents and/or plasticizers. For example, and/or plasticizers may be present in an amount of no more than about 1% by weight, in some embodiments no more than about 0.5% by weight, and in other embodiments of about from 0.001% to about 0.2% by weight of the thermoplastic compound. Furthermore, due to the stress whitening properties, as described in more detail below, the resulting compound can achieve an opaque color (eg white) without the need for conventional pigments such as titanium dioxide. In certain embodiments, for example, pigments may be present in an amount of no more than about 1% by weight, in some embodiments no more than about 0.5% by weight, and in other forms of realization, from about 0.001% to about 0.2% by weight of the thermoplastic compound. II. mixing
[71] Prior to initiating pores in the composition, the components are typically mixed using one of several known techniques. In one embodiment, for example, the components can be provided separately or as a combination. For example, the components can be dry blended to form an essentially homogeneous dry mixture and can be supplied simultaneously or sequentially in a melt processing apparatus which disperses the materials dispersively. Batch and/or continuous melt processing techniques may be employed. For example, a mixer/kneader, Banbury mixer, Farrel continuous mixer, single screw extruders, twin screw extruders, laminators, etc. can be used to mix and melt the materials. Especially suitable melt processing apparatus may be a co-rotating twin screw extruder (for example, the ZSK-30 extruder marketed by Werner & Pfleiderer Corporation of Ramsey, New Jersey or a Thermo Prism™ USALAB 16 extruder marketed by 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 introduced into the same feed ports as the twin screw extruder, or into other ports, and melt blended to form a very homogeneous molten mixture. If desired, other additives can also be injected into the molten polymer and/or separately introduced into the extruder at a different point along its length.
[72] Regardless of the particular processing technique chosen, the resulting blended and melted composition generally contains domains of inclusion additives as described above. 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 discrete domains, making them 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 from 190°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/πR3, where Q is the volumetric flow rate (“m3/s”) of the polymer melt and R is the radius (“m”) of the capillary (eg matrix extrusion) through which the molten polymer flows. Obviously, other variables, such as the residence time during the melting process, which is inversely proportional to the throughput, can also be controlled in order to achieve the desired degree of homogeneity.
[73] To achieve the desired shear conditions (eg rate, residence time, shear rate, melt processing temperature, etc.), the speed of the extruder rotations can be selected within a certain range. Generally, an increase in product temperature is observed with increasing rotational speed due to the additional input of mechanical energy into the system. For example, the rotation 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 other embodiments, from about 100 to about 300 rpm. This can result in a temperature high enough to disperse the first inclusion additive without negatively 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 during the use of 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 mixers, Leroy/Maddock, CRD, etc. As is known in the art, blending can be further improved by using pins in the barrel 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. pore initiation
[74] To initiate pore formation, the polymeric material is subjected to an externally applied stress as described above. If desired, the material can be drawn in-line while it is being formed. Alternatively, the material can be drawn in its solid state after being formed, before and/or after lamination, into any other optional materials, such as, by a mechanical stretching process (eg, bending, stretching, twisting, etc. .) which transmits energy to the continuous phase interface and inclusion additives. By "solid state" stretching, it is generally meant that the composition is maintained at a temperature ("stretching temperature") below the melting temperature of the matrix polymer. Among other things, this helps to ensure that the polymer chains are not altered in such a way that the pore network becomes unstable. For example, the material can be stretched at a temperature of between about -50°C to about 125°C, in some embodiments between about -25°C to about 100°C, and in some forms of realization, from about -20°C to about 50°C. The stretching temperature can also be lower than the glass transition temperature of the component with the highest glass transition temperature (e.g. matrix polymer, first inclusion additive, etc.). For example, the stretch temperature can be at least approximately 10 °C, in some embodiments at least approximately 20 °C, and in other embodiments at least approximately 30 °C below the temperature of glass transition of the matrix polymer and/or first inclusion additive.
[75] The stretching can take place in any direction, such as the longitudinal direction (eg machine direction), transverse direction (eg cross machine direction), or a combination of these. To accomplish the desired stretch, the thermoplastic composition can be made into a precursor form, taken out, and then converted into the desired material (eg, film, fiber, etc.). In one embodiment, the precursor form can be a film having a thickness of from about 1 to 5,000 micrometers approximately, in some embodiments from about 2 to 4,000 micrometers approximately, in some embodiments from about 5 to 2,500 micrometers. micrometers approximately, in other embodiments from about 10 to 500 micrometers approximately. As an alternative to forming a precursor form, the thermoplastic composition can also be taken in place as it is molded into the desired shape for the polymeric material. In one embodiment, for example, the thermoplastic composition can be taken as it is formed into a film or fiber.
[76] Various stretching techniques can be used. A suitable mechanical stretching technique, for example, is a nip-roll process in which material is passed between a defined nip between two rollers, at least one of which is rotatable. In one embodiment, at least one of the cylinders contains a pattern of raised elements embossed, which can create local deformation in the material. The other roller can also be patterned or smooth (eg anvil roller). If the deformed areas are forced to a level above the elasticity limit of cavitation, these areas can form initial pores. When subjected to more stretching stress, the pore areas will grow in size before the rest of the material cavitates. Another suitable nip roller process involves the use of a grooved cylinder through which the polymeric material can pass. In addition to the use of a pinch zone, the rotation speed of the cylinders can also be used to help provide the desired degree of mechanical tension. In one embodiment, for example, material is passed through a series of rollers which progressively pull the material. A suitable method for performing such stretching is through the use of a machine direction guide (“OSM”). OSM units generally have a plurality of cylinders (eg 5 to 8) that can progressively stretch the polymeric material in the machine direction. The material can be stretched in single or multiple discrete stretching operations. It should be noted that some of the cylinders in an OSM apparatus may not be operating at higher progressive speeds. To stretch the material in the manner described above, it is generally preferable that the OSM rolls are not heated. However, if desired, one or more rolls can be heated slightly to facilitate the drawing process, as long as the temperature of the composition remains below the ranges noted above.
[77] Of course, it should be understood that rotating cylinders are not required to mechanically stretch the polymeric material. Die drawing, for example, can be used to mechanically stretch the material. In a typical die-stretching process, the material is initially extruded into a precursor form (eg, profile) and quenched. The precursor is then mechanically stretched through a converging matrix while in the solid state. A particularly suitable die drawing process is pultrusion, during which the material is stretched or pulled through the die to form a machined profile or shape determined by the shape of the mold. In addition to die drawing, other mechanical drawing techniques can also be employed. In one embodiment, for example, sheet stretching can be used, such as fabric stretcher stretching, brake stretching, etc. In a particular embodiment, for example, the polymeric material can be mechanically stretched into sheet form using a mechanical, electrical, hydraulic or pneumatic brake assembly. The brake assembly may include a surface where the material is initially placed, an anchor bar, and a bending member that is raised to create a bend in the material. More particularly, the brake assembly may include a plurality of generally C-shaped members, each having opposing clamping surfaces for receiving a polymeric material. Furthermore, a socket can be used to orientableably support the folding element to bend the material disposed between the clamping surfaces. The socket generally includes a male part and a female part in sliding fit with each other or connecting a pin-pivoted connection to each other. Such brake assemblies are known in the art and described in more detail, for example, in US Patent No. 4,282,735 for Break; 4,557,132 for Break, and 6,389,864 for Chubb.
[78] Yet another technique for mechanically stretching the polymeric material involves the use of a fluid medium (eg, gas) to impart the desired degree of energy and tension to the material. Such a process is, for example, aspiration, which typically involves the use of blown air to extract the material. For example, a fiber tensioning vacuum can be used, such as a linear fiber vacuum of the type shown in US Patent Nos. 3,802,817 and 3,423,255. A fiber tensioning vacuum generally includes a vertical stretching passage, through which the fibers are pulled, drawing in air entering the sides of the passage and forcing flow downward through the passage. A heater or blower supplies the suction air, which causes the fibers to strain or attenuate.
[79] Despite the particular technique employed, the polymeric material is generally stretched (eg, in the machine direction) to a "stretch ratio" of about 1.1 to about 3.5, in some embodiments of about 1.2 to about 3.0 and, in other embodiments, from about 1.3 to about 2.5. The draw ratio is determined by dividing the length of the stretched material by its length before stretching. The draw rate can also be varied to help achieve the desired properties, for example, ranging from about 5% to about 1,500% per minute of strain, in some embodiments from about 20% to about 1,000% per minute of deformation and, in other embodiments, from about 25% to about 850% per minute of deformation. In addition to forming a porous network as described above, stretching can also significantly increase the axial dimension of the domains so that they have a generally elongated and linear shape. For example, the first domains can have an average axial dimension of about 10% or more, in some embodiments from about 20% to about 500%, and in some embodiments from about 50% to about 250% greater than the axial dimension of the domains before stretching. Before stretching, for example, the first domains can have an average axial dimension (e.g., length) of from about 0.05 to about 30 micrometers, in some embodiments from about 0.1 to about 25 micrometers, in some embodiments from about 0.5 to about 20 micrometers and, in other embodiments, from about 1 to about 10 micrometers.
[80] As a result of the unique porous domain structure, the present inventors found that the resulting polymeric material can uniformly expand in volume when stretched in the longitudinal direction, which is reflected by a low "Poisson coefficient" as determined in accordance with the following equation: Poisson's Coefficient = - Etransversal / Elongitudinal where Etransversal 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's ratio may be approximately 0.1 or less, in some embodiments approximately 0.08 or less, and in other embodiments approximately -0.1 to approximately 0.04. When Poisson's coefficient is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When Poisson's coefficient is negative, the transverse or lateral dimensions of the material also expand when the material is stretched in the longitudinal direction. Thus, materials with a negative Poisson's coefficient may exhibit an increase in width when stretched in the longitudinal direction, which can result in increased energy absorption in the transverse direction.
[81] If desired, the polymeric material of the present invention can be subjected to one or more additional processing steps before and/or after drawing. Examples of such processes include, for example, roll embossing, embossing, coating, etc. In certain embodiments, the polymeric material may also be annealed to help ensure that it maintains the desired shape. Annealing typically occurs at temperatures above the glass transition temperature of the polymer matrix, such as temperatures from about 40 to 120 °C, in some embodiments from about 50 to 100 °C, and in some embodiments from about 70 to 90°C. The polymeric material can also be surface treated using any of several known techniques in order to improve its properties. For example, high energy beams (eg plasma, x-rays, electron beam, etc.) can be used to remove or reduce skin layers, change the polarity, porosity, topography of a surface layer, etc. If desired, such surface treatment can be used before and/or after stretching the thermoplastic composition. IV. Articles
[82] The polymeric material of the present invention can generally have several different shapes depending on the particular application, such as films, fibrous materials, molded articles, profiles, etc., as well as composite materials and laminates thereof. In one embodiment, the polymeric material is in the form of a film or film layer. Multilayer films can contain from two (2) to fifteen (15) layers and, in some embodiments, from three (3) to twelve (12) layers. These multilayer films contain at least one base layer and at least one additional layer (eg, surface layer), but can contain as many layers as desired. For example, the multilayer film can be formed of base layers and one or more surface layers, wherein the base layer and/or surface layer is formed of the polymeric material of the present invention. It should be understood, however, that other polymeric materials can also be used in base and/or surface layers, such as polyolefin polymers.
[83] Film thickness can be relatively small to increase flexibility. For example, the film may have a thickness of from about 1 to about 200 micrometers, in some embodiments from about 2 to about 150 micrometers, in some embodiments from about 5 to about 100 micrometers, and , in other embodiments, from about 10 to about 60 micrometers. Despite the small thickness, the film may nevertheless be able to maintain good mechanical properties during use. For example, the film can be relatively malleable. A parameter indicative of film malleability is the percentage of film elongation at its breaking point, as determined by the stress-strain curve in accordance with ASTM D638-10 at 23°C. For example, the percentage elongation at film break in the machine direction ("MD") can be about 10% or more, in some embodiments about 50% or more, in some embodiments about 80 % or more and, in other embodiments, from about 100% to about 600%. Likewise, the percentage elongation at break of the film in the transverse direction ("CD") may be about 15% or more, in some embodiments about 40% or more, in some embodiments about 70 % or more and, in other embodiments, from about 100% to about 400%. Another parameter indicative of malleability is the film's modulus of tension, which is equal to the ratio of tensile stress to shear stress, and is determined from the slope of a stress-strain curve. For example, the film typically exhibits an MD and/or CD elastic modulus of about 2,500 Megapascals ("MPa") or less, in some embodiments about 2200 MPa or less, in some embodiments about about 2200 MPa or less. 50 MPa to about 2,000 MPa, and in some embodiments, from about 100 MPa to about 1,000 MPa. The voltage modulus can be determined in accordance with ASTM D638-10 at 23°C.
[84] Although the film is malleable, it can also be relatively strong. A parameter indicative of the relative strength of the film 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 film may exhibit an MD and/or CD peak stress of from about 5 to about 65 MPa, in some embodiments from about 10 to about 60 MPa, and in other embodiments from about from 20 MPa to about 55 MPa. The film may also exhibit an MD and/or CD stress drop of from about 5 to about 60 MPa, in some embodiments from about 10 to about 50 MPa, and in some embodiments from about 20 MPa to about 45 MPa. Peak voltage and breakdown voltage can be determined in accordance with ASTM D638-10 at 23°C.
[85] In addition to a film, the polymeric material can also be in the form of a fibrous material or a layer or component of a fibrous material, which can include individual staple fibers or filaments (continuous fibers), as well as yarns, fabrics, etc. ., formed from such fibers. Yarns can include, for example, various staple fibers that are twisted together ("spun yarn"), filaments put together without twisting ("twisted yarn"), filaments put together with a degree of twist, each filament with or without twist (“monofilament”), etc. The yarn may or may not be textured. Suitable fabrics can include, for example, woven fabrics, knitted fabrics, non-woven fabrics (e.g., spunbond wefts, meltblown wefts, bonded carded wefts, wet-laid wefts, air-laid wefts, coform wefts, hydroentangled wefts, etc. ), and so on.
[86] Fibers formed from the thermoplastic composite can generally have any desired configuration, including single-component and multi-component (eg, a coating-core, side-by-side, pizza, island, and so on) configuration. In some embodiments, the fibers can contain one or more additional polymers as a component (e.g., bicomponent) or constituent (e.g., bicomponent) to further enhance strength and other mechanical properties. For example, the thermoplastic composite can form a coating component of a bicomponent coating/core fiber, while an additional polymer can form the core component, or vice versa. The additional polymer can be a thermoplastic polymer, such as polyesters, e.g., polylactic acid, polyethylene terephthalate, polybutylene terephthalate, and so on; polyolefins, for example polyethylene, polypropylene, polybutylene, etc.; polytetrafluoroethylene; polyvinyl acetate; polyvinyl acetate chloride; polyvinyl butyral; acrylic resins, for example, polyacrylate, polymethylacrylate, polymethylmethacrylate, and so on; polyamides, for example nylon; polyvinyl chloride; polyvinylidene chloride; polystyrene; polyvinyl alcohol; and polyurethanes.
[87] When used, fibers may deform on application of pressure rather than rupture. The fibers can therefore continue to function as load-bearing members even after the fiber has exhibited considerable elongation. In this regard, the fibers of the present invention may have better "peak elongation" properties, that is, the percentage of elongation of the fiber at its maximum load. For example, the fibers of the present invention can exhibit a peak elongation of approximately 50% or more; in some embodiments approximately 100% or more; in other embodiments from approximately 200% to approximately 1500%; and further in some embodiments, from approximately 400% to approximately 800%, as determined in accordance with ASTM D638-10 at 23°C. These elongations can be achieved for fibers that have a wide range of average diameters, ranging from approximately 0.1 µm to approximately 50 micrometers, in some embodiments from approximately 1 µm to approximately 40 micrometers, in some embodiments from approximately 2 µm to approximately 25 micrometers, and in other embodiments, from approximately 5 µm to approximately 15 micrometers.
[88] While exhibiting the ability to elongate under tension, the fibers of the present invention can also remain relatively strong. For example, fibers can exhibit a peak tensile stress of approximately 25 MPa to approximately 500 Megapascals (“MPa”); in some embodiments, from approximately 50 MPa to approximately 300 MPa; and in other embodiments, from approximately 60 MPa to approximately 200 MPa, as determined in accordance with ASTM D638-10 at 23°C. Another parameter that is indicative of the relative strength of the fibers of the present invention is "tenacity", which indicates the tensile strength of a fiber expressed as the strength per unit of linear density. For example, the fibers of the present invention can exhibit tenacity from about 0.75 to about 6.0 grams-strength ("gf") per denier, in some embodiments from about 1.0 to about 4.5 gf per denier, and in some embodiments from about 1.5 to about 4.0 gf per denier. Fiber denier may vary depending on the desired application. Typically the fibers are formed to have a denier per filament (i.e. the unit of linear density equal to the mass in grams per 9,000 meters of fiber) of less than about 6, in some embodiments less than about 3 and, in some embodiments, from about 0.5 to about 3.
[89] Due to its unique and beneficial properties, the resulting polymeric material of the present invention is well suited for use in a wide variety of different types of articles, such as an absorbent article, packaging film, barrier film, medical products ( for example, surgical gowns, mask, head covering, surgical cap, shoe covering, sterilization wrap, thermal blanket, heating pad, etc.), and so on. For example, the polymeric material can be incorporated into an "absorbent product" capable of absorbing water or other fluids. Examples of some absorbent articles, among others: absorbent personal care articles such as diapers, training diapers, absorbent panties, incontinence products, feminine hygiene products (eg sanitary napkins, menstrual pads, etc.), bathing suits , baby handkerchiefs, and so on; medical absorbent articles such as clothing, fenestration materials, bed covers, dressings, absorbent surgical cloths and medical wipes; paper towels for heavy cleaning in kitchens, articles of clothing, and so on. Suitable materials and processes for molding such products are well known to those skilled in the art. Absorbent articles, for example, typically include a highly liquid-impervious layer (eg, outer covering), a liquid-permeable layer (eg, body-contacting liner, expandable layer, etc.) and an absorbent core. In one embodiment, for example, the polymeric material can be in the form of a fibrous material (e.g., non-woven web) and used to form an outer covering of an absorbent article. If desired, the non-woven web can be laminated to a liquid impervious film, which will be vapor permeable or impermeable. The polymeric material can also be in the form of a film that is used in an absorbent article, such as a liquid-impermeable film of the outer shell, which is either vapor-permeable or vapor-impermeable.
[90] The polymeric material can also be used in a wide variety of other types of articles. Non-limiting examples include, for example, insulation materials for refrigeration units (eg refrigerators, freezers, vending machines, etc.); automotive components (eg, front and rear seats, headrests, armrests, door panels, rear shelves/package trays, steering wheels and interior trim, panels, etc.); building panels and sections (eg roofs, wall cavities, floors, etc.); clothing (eg coats, shirts, pants, gloves, aprons, coveralls, shoes, boots, socks, headgear, insoles, etc.); furniture and clothing (eg, sleeping bags, comforters, etc.); liquid storage/transfer systems (eg, hydrocarbon liquid/gas, liquid nitrogen, oxygen, hydrogen, or crude oil pipes or tankers); extreme environments (eg underwater or space); food and beverage products (eg glasses, cup holders, plates, etc.); containers and bottles; and so on. The polymeric material can also be used in a "garment," which is generally intended to include any article that is molded to fit a part of a body. Examples of such items include, without limitation, clothing (eg, shirts, pants, jeans, pants, skirts, jackets, fitness, athletic, aerobics, swimwear, cycling jerseys or shorts, swimsuit/swimwear, jogging clothing , wetsuit, bodysuit, etc.), footwear (eg shoes, socks, boots, etc.), protective clothing (eg firefighter jacket), accessories (eg belts, bra straps, side panels, gloves, socks, leggings, braces, etc.), underwear (eg, underwear, t-shirts, etc.), compression garments, draped clothing (eg, thong kilts, gowns, ponchos, coats, shawls, etc.), and so on.
[91] The polymeric material can also be used in a wide variety of other articles in any particular application. For example, when considering automotive applications, the polymeric material can be used in fibrous articles or as solid moldings. By way of example, polymeric material fibers can be beneficially used in articles that can improve the comfort and/or aesthetics of a vehicle (e.g. coverings and/or trim for sun visors, speaker cabinets and coverings, coverings of seats, seal slip agents and supports for seat covers, carpets and carpet reinforcement including carpet supports, car mats and car mat supports, seat belt coverings and fastenings, floor coverings and upholstery, panels of back shelf, ceiling coverings and supports, upholstery support, decorative fabrics in general, etc.), materials that can provide general insulation to temperature and/or noise (for example, column padding, door upholstery, door linings roof, general soundproofing and insulation materials, anti-noise enclosures, body parts, windows, roofs and sunroofs, tire reinforcements, etc.) and filtration/engine materials (by example, fuel filters, oil filters, battery separators, cabin air filters, transmission tunnel materials, fuel tanks, etc.).
[92] Solid moldings including the polymeric material can be used to enhance automobile safety components. For example, the polymeric material can be integrated into passive safety components, such as crumple zones in the rear, front and/or sides of a vehicle; inside the car's safety cell, as an airbag or steering wheel component (eg, a deformable steering column); as a load barrier; or as a component of a pedestrian safety system (eg as a component of the bumper, hood, window frame, etc.).
[93] The low density of the polymeric material can provide weight saving benefits in automotive applications. For example, the polymeric material can be a component of an automobile's structure, including, without limitation, the hood, bumper and/or bumper brackets, the trunk and/or compartment lid, and the underside of the vehicle body.
[94] Such a wide application of the polymeric material is applicable to a wide variety of fields, and is not intended to be in any way limited to the automotive industry. For example, the polymeric material can be used in the transportation industry in any suitable application, including, without limitation, aerospace applications (eg, aircraft, helicopters, space transport, military aerospace devices, etc.), marine applications (boats, ships , passenger vehicles), trains, and so on. The polymeric material can be used in transport applications in any desired shape, for example, in fibrous articles or solid moldings, in aesthetic applications, for temperature and/or acoustic insulation, in filtration and/or engine components, in security components, etc.
[95] The present invention can be better understood with reference to the following examples. Test Methods Fluidity Index:
[96] The melt flow index (“MFR”) is the weight of a polymer (in grams) forced through an extrusion rheometer hole (0.0825 inch diameter) when subjected to a load of 2,160 grams in 10 minutes, typically 190°C, 210°C or 230°C, unless otherwise noted, the melt flow rate is measured in accordance with ASTM test method D1239 with a Tinius Olsen extrusion plastomer. Thermal properties:
[97] The glass transition temperature (Tg) can be determined using dynamic-mechanical analysis (DMA) in accordance with ASTM E1640-09. A TA Instruments Q800 instrument can be used. Experimental tests can be performed in voltage/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 voltage 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 storage modulus (tangent δ = E”/E').
[98] Melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimetry equipment can be a DSC Q100 differential scanning calorimeter, which can be prepared with a liquid nitrogen cooling accessory and a UNIVERSAL ANALYSIS 2000 analysis software (version 4.6.6), both marketed by 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 dish and weighed to 0.01 milligram accuracy on an analytical balance. A lid can be placed over the material sample in the dish. Grains can normally be placed directly on the weighing pan.
[99] Differential scanning calorimetry equipment can be calibrated using an indium metal standard and a baseline correction can be made as described in the equipment operation manual. The sample of material can be placed in the test chamber of the differential scanning calorimetry equipment to be tested, and an empty plate can be used as a reference. All tests can be performed by purging 55 cubic centimeters per minute of nitrogen (industrial grade) in the test chamber. For resin grain samples, the heating and cooling program is a 2-cycle test, which started with chamber equilibration at -30°C, followed by a first heating period to a rate of 10°C per minute to a temperature of 200 °C, followed by a sample equilibration 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 the sample equilibration at -30 °C for 3 minutes, then 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 started with chamber equilibration at -25°C, followed by a first heating period to a rate of 10°C per minute to a temperature of 200 °C, followed by a sample equilibration at 200 °C for 3 minutes, followed by a first cool-down period of 10 °C per minute to a temperature of -30 °C. All tests can be performed by purging 55 cubic centimeters per minute of nitrogen (industrial grade) in the test chamber.
[100] The results can be evaluated using the UNIVERSAL ANALYSIS 2000 analysis software, which identifies and quantifies the glass transition temperature (Tg) of the inflection, the endothermic and exothermic peaks, and the areas under the peaks in the DSC traces. The glass transition temperature can be identified as the region of the drawn line where a sharp change in the curve has occurred, and the melting temperature can be determined using an automatic inflection calculation. Film Tension Properties
[101] The films were tested for tensile properties (maximum stress, modulus, strain at break, and energy per volume at break) on an MTS Synergie 200 tension frame. The test can be performed in accordance with ASTM D638 -10 (at about 23°C). Film samples can be cut into a dog bone shape with a center width of 3.0mm prior to testing. The dog bone shaped film samples can be held in place by means of fasteners on the MTS Synergie 200 device with a length of the piece to be measured of 18.0 mm. Film samples can be stretched at a tensile speed of 5.0 in./min until breakage occurs. Five samples of each film can be tested in machine direction (MD) and cross direction (CD). A computer program (eg TestWorks 4) can be used to collect the 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 for disruption. Fiber Tension Properties:
[102] Stress properties can be determined in accordance with ASTM 638-10 at 23°C. For example, individual fiber specimens may initially be reduced in length (eg cut with scissors) by 38 millimeters and be laid out separately on a black velvet cloth. From 10 to 15 specimens can be collected this way. Fiber specimens can then be placed in a straight line on a rectangular paper frame, with external dimensions of 51mm x 51mm and internal dimensions of 25mm x 25mm. The ends of each fiber specimen can be secured to the frame by carefully securing the fiber ends over the sides of the frame with adhesive tape. Each fiber specimen can then be measured, in the relatively shortest external dimension, using a conventional laboratory microscope, properly calibrated and adjusted to 40X magnification. Fiber dimension can be recorded as the diameter of the fiber specimen. The frame assists in assembling the ends of fiber samples to the top and bottom fastenings of a tensile tester with a constant extension rate to prevent excessive damage to the fiber samples.
[103] A constant rate of strain tester extension type and an appropriate load cell may be employed in the test. The load cell can be chosen (eg 10N) so that the test value is between 10% and 90% of full load scale. The tensile tester (ie, MTS SYNERGY 200) and load cell are available from MTS Systems Corporation of Eden Prairie, Michigan. The fiber specimens on the frame can then be placed between the grips of the tensile tester such that the ends of the fibers are caught in the grips of the tensile tester. Then, the edges of the paper structure that extend parallel to the length of the fibers can be cut so that the tensile tester applies the test force only to the fibers. The fibers can then be subjected to a tensile test at a pull rate and grip speed of 12 inches per minute. The resulting data can be analyzed using TESTWORKS 4 software, from MTS Corporation, with the following test parameters:

[104] Toughness values can be expressed in terms of gram-force per denier. Peak elongation (% stress at break) and peak stress are also calculated. Expansion ratio, density and percentage of pore volume
[105] To determine the expansion ratio, density, and percentage of pore volume, the width (Wi) and thickness (Ti) of the specimen were initially measured before stretching. The length (Li) before stretching can also be determined by measuring the distance between two marks on the specimen surface. Consequently, the sample must be stretched to initiate emptying. Width (Wf), thickness (Tf) and length (Lf) of the sample can be measured as close to 0.01 mm using a Digimatic Caliper Caliper (Mitutoyo Corporation). The volume (Vi) before stretching can be calculated by Wi x Ti x Li = Vi. The volume (Vf) after stretching can also be calculated by Wf x Tf x Lf = Vf. The expansion rate (Φ) can be calculated by Φ = Vf/Vi; the density (Pf) can be calculated by: Pf = Pi/Φ, where Pi is the density of the precursor material; and the percentage of pore volume (%Vv) can be calculated by: %Vv = (1 - 1/ Φ) x 100. Hydrostatic pressure test (Hydrohead):
[106] The hydrostatic pressure test is a measure of the resistance of a material to liquid water penetration under static pressure and is performed in accordance with AATCC Test Method 127-2008. The results of each sample can be averaged and recorded in centimeters (cm). A higher value indicates greater resistance to water penetration. Water Vapor Transmission Rate ("TTVA")
[107] The test used to determine the TTVA of a material may vary based on the nature of the material. One technique for measuring the TTVA value is ASTM E96/96M-12, Procedure B. Another method involves using the INDA Test Procedure IST-70.4 (01). The INDA test procedure is summarized below. A dry chamber is separated from a humid chamber of known temperature and humidity by a permanent protective film and the sample material to be tested. The purpose of the protective film is to define a definite air gap and to calm or quiet the air in the air gap as it is characterized. The dry chamber, the protective film and the wet chamber form a diffusion cell, in which the test film is sealed. The sample holder is known as the Permatran-W model 100K manufactured by Mocon/Modem Controls, Inc., Minneapolis, Minnesota. A first test of the TTVA of the protective film and the air gap between the evaporator assembly is carried out, generating 100% relative humidity. The water vapor diffuses through the air gap and the protective film and then mixes with the dry gas flow, proportional to the water vapor concentration. The electrical signal is routed to a computer for processing. The computer calculates the air gap and protective film baud rate and stores the value for later use.
[108] The transmission rate of the protective film and air gap is stored in the computer as CalC. The sample material is then sealed in the test cell. Again, water vapor diffuses through the air gap to the protective film and test material, and then mixes with the dry gas stream that sweeps the test material. Also, again, the mixture is conducted to the vapor sensor. The computer then calculates the baud rate from the combination of air gap, protective film, and test material. This information is then used to calculate the transmission rate at which moisture is transmitted by the test material according to the equation: TR-1test material = TR-test material, protective film, slack — TR-1 protective film, slack
[109] The water vapor transmission rate ("TTVA") is then calculated as follows:
where, F = the water vapor flow in cm3 per minute; Psat(T) = the density of water in saturated air at a temperature T; RH = the relative humidity at specific locations in the cell; A = the cross-sectional area of the cell; and Psat(T) = the saturated vapor pressure of water vapor at temperature T. Conductive properties
[110] Thermal conductivity (W/mK) and thermal resistance (m2K/W) can be determined in accordance with ASTM E-1530-11 (“resistance to thermal transmission of materials by shielded heat flow meter technique ”) using an Anter Unitherm Model 2022 tester. The desired test temperature can be 25 °C and the applied load can be 0.17 MPa. Before testing, the sample can be conditioned for +40 hours at a temperature of 23 °C (+2 °C) and a relative humidity of 50% (+10%). Thermal intake (W/m2K) can also be calculated by dividing thermal resistance by 1. Moisture content
[111] Moisture content can be determined using the Arizona Instruments Computrac Vapor Pro Moisture Analyzer (Model No. 3100) in accordance with ASTM D 7191-05, included herein in its entirety by reference to 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 emptying time (§X2.1.4) can be 30 seconds. In addition, the final criteria (§X2.1.3) can be defined as a “prediction” mode, which means that the test ends when the internally programmed criteria (which mathematically calculates the final moisture point) are met. EXAMPLE 1
[112] The possibility of forming films from a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of a first inclusion additive, 1.4% has been demonstrated. by weight of a second inclusion additive and 3.8% by weight of an internal interfacial modifier. The first inclusion additive was Vistamaxx™ 2120 (ExxonMobil), which is a polypropylene-polyethylene copolymer elastomer with a melt index of 29 g/10 min (190 °C, 2160 g) and a density of 0.866 g/cm3 . The second inclusion additive was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema) with a melt index of 5-6 g/10 min (190 °C/2160 g) , a glycidyl methacrylate content of 7 to 11% by weight, a methyl acrylate content of 13 to 17% by weight, and an ethylene content of 72 to 80% by weight. The internal interfacial modifier was BASF's PLURIOL® WI 285 Lubricant, which is a polyalkylene glycol functional fluid. Polymers were fed into a twin screw extruder and co-rotating (ZSK-30, 30 mm diameter, 1,328 mm long) for composites manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, sequentially numbered from 1 to 14, running from the hopper to the die. The #1 barrel zone first received the resins through the gravimetric feeder at a total transfer rate of 15 pounds per hour. PLURIOL® WI285 was added via injection pump in barrel zone #2. The die used to extrude the resin had 3 die openings (6 millimeters in diameter) 4 millimeters apart. After formation, the extruded resin was cooled on a ventilated conveyor belt and shaped into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute (“rpm”). The grains were introduced in large volume into a signal screw extruder at a temperature of 212°C, where the molten mixture exited through a die with an opening 4.5 inches wide and stretched and a film thickness ranging from 36 µm to 54 µm. The films were stretched in the machine direction by about 100% to initiate cavitation and void formation.
[113] The morphology of the films was analyzed by scanning electron microscopy (SEM) before and after stretching. The results are shown in Figs. 1-4. As shown in Figs. 1-2, the first inclusion additive was initially dispersed into domains with an axial dimension (machine direction) of about 2 to about 30 micrometers and a transverse dimension (cross machine direction) of about 1 to about of 3 micrometers, whereas the second inclusion additive was initially dispersed as spherical or spheroidal domains having an axial dimension of about 100 to about 300 nanometers. Figs. 3-4 displays the film after stretching. As indicated, pores formed around the first and second inclusion additive. The micropores formed around the first inclusion additive generally had an elongated or slit-like shape with a wide size distribution ranging from about 2 to about 20 micrometers in the axial direction. The nanopores associated with the second inclusion additive generally were about 50 to about 500 nanometers in size. EXAMPLE 2
[114] The composite pellets of Example 1 were dry blended with a third inclusion additive, which was a base mixture of halloysite clay (MNH MacroComp-731-36, Macrom) containing 22% by weight of a copolymer of nanoclay modified by styrene and 78% by weight of polypropylene (Exxon Mobil 3155). The mixing ratio was 90% by weight of the pellets and 10% by weight of the clay base mix, which provided a total clay content of 2.2%. The dry mix was then introduced in large volume into a signal screw extruder at a temperature of 212 °C, where the molten mix exited through a die with a 4.5 inch wide and stretched opening and a varying film thickness. from 51 µm to 58 µm. The films were stretched in the machine direction by about 100% to initiate cavitation and void formation.
[115] The morphology of the films was analyzed by scanning electron microscopy (SEM) before and after stretching. The results are shown in Figs. 5-8. As shown in Figs. 5-6, some of the nanoclay particles (visible as brighter regions) became dispersed in the form of very small domains - that is, the axial dimension ranging between about 50 and 300 nanometers. The base mixture also formed microscale size domains (axial dimension from about 1 to about 5 micrometers). In addition, the first inclusion additive (VistaMax ™) formed elongated domains, while the second (Lotader®, visible as ultra-thin dark spots) and third (nanoclay base mix, visible as shiny platelets) inclusion additive formed domains spheroidal. The stretched film is shown in Figs. 78. As shown, the hollow structure is more open and demonstrates a wide range of pore sizes. In addition to the highly elongated micropores formed by the first inclusions (Vistamaxx™), the nanoclay base blend inclusions formed more open spheroidal micropores, with an axial dimension of about 10 microns or less and a transverse dimension of about 2 microns. Spherical nanopores are also formed by the second inclusion additive (Lotader®) and the third inclusion additive (nanoclay particles).
[116] Various tensile properties (machine direction) of the films in examples 1 and 2 were also tested. The results are given below in Tables 1. Table 1

[117] As shown, the addition of the nanoclay filler resulted in a slight increase in breaking strength and a significant increase in elongation to break. EXAMPLE 3
[118] A precursor mixture was formed from 91.8% by weight of polypropylene (M3661, Total Petrochemicals) 7.4% by weight of a first inclusion additive (PLA 6252), and 0.7% by weight of a second inclusion additive. The second inclusion additive was poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) (LOTADER® AX8900, Arkema) with a melt flow index of 6 g/10 min (190 °C/2160 g ), a glycidyl methacrylate content of 8% by weight, a methyl acrylate content of 24% by weight, and an ethylene content of 68% by weight. The components were compounded in a co-rotated twin screw extruder (ZSK-30 from Werner and Pfleiderer, with a diameter of 30 mm and a C/D = 44). The extruder had seven heating zones. The temperature in the extruder ranged from 180 °C to 220 °C. Polymer was fed gravimetrically into the extruder hopper at 15 pounds per hour and the liquid was injected into the barrel via a peristaltic pump. The extruder was operated at 200 revolutions per minute (“rpm”). In the last section of the drum (front), a die of three holes 6 mm in diameter was used to form the extrudate. The extrudate was air cooled on a ventilated conveyor belt and shaped into pellets by a Conair pelletizer. Injected samples (ASTM D638 Type 1) were made from the precursor mixture using a Boy 22D injection molding machine with 3 heating sections. The temperature in the heating sections ranged from 185 to 220 °C. The injection hold pressure time ranged from 14s to 24s, the cooling time from 12 to 23s, cycle time ranged from 22s to 43s, and the mold temperature was set at about 21 °C. Once formed, the samples were drawn in an 810 Material Test System tension tester at a tensile speed of 25 mm/min at 25 °C.
[119] To analyze material morphology, stretched and unstretched injection molded bars were fractured by freezing in liquid nitrogen. The fractured surfaces were coated with gold-palladium alloy layers, and analyzed using a Jeol 6490LV Scanning Electron Microscope in high vacuum. The results are shown in Figs. 9-10. As indicated in Fig. 9, the mixture exhibited a relatively small domain size. After stretching, as shown in Fig. 10, the small blend domain sizes tended to form relatively small pores. A stress-strain curve was also generated for the drawn sample and is shown in Fig. 11. As shown, the mixture had good mechanical properties, similar to pure polypropylene. In addition, a section of the narrow region of the stretched molded bar was cut and then submerged in hexane (density 0.65 g/cc). The narrow region of the stretched molded bars was observed to float in hexane, suggesting that the density is less than 0.65 g/cc. EXAMPLE 4
[120] The fiber was produced from the precursor blend of Example 3 using a Davis-Standard fiber spinning line equipped with a 0.75 inch single screw extruder and 16 hole spinner, 0.6 mm diameter . Fibers were collected in different stretch proportions. Adoption speed ranged from 1 to 1000 m/min. The extruder temperature ranged from 175 °C to 220 °C. The fibers were drawn in a tensile tester at 300 mm/min to 400% stretch at 25 °C. To analyze the morphology of the materials, the fibers were fractured by freezing in liquid nitrogen and analyzed using a Jeol 6490LV Scanning Electron Microscope in high vacuum. The results are shown in Fig. 12-14. As shown, the spheroidal pores are formed so that they are highly elongated in the stretch direction. Both nanopores (~50 nanometers wide, ~500 nanometers long) and micropores (~0.5 micrometers wide, ~4 micrometers long) were formed.
[121] While the invention is described in detail with respect to specific embodiments thereof, it will be appreciated that those skilled in the art, upon gaining an understanding of the above, can easily devise changes and variations of equivalents for these forms of achievement. Therefore, the scope of the present invention must be evaluated as that of the appended claims and their equivalents

权利要求:
Claims (20)
[0001]
1. Porous polymeric material containing a thermoplastic composition, characterized in that the thermoplastic composition includes a continuous phase in which a first inclusion additive and a second inclusion additive are dispersed in the form of discrete domains, the continuous phase including a polymer of the matrix, wherein a plurality of micropores are formed in and/or around the first domains, and have an average cross-sectional dimension of 0.5 to 30 micrometers, and wherein a plurality of nanopores are formed in and/or around of the second domains, and have an average cross-sectional dimension of 50 to 500 nanometers, wherein the first inclusion additive includes a polyolefin; and wherein the first inclusion additive is present in the thermoplastic composition in an amount of from 1% by weight to 20% by weight, and the second inclusion additive is present in the thermoplastic composition in an amount of 0.01% by weight to 15%. % by weight.
[0002]
2. Porous polymeric material according to claim 1, characterized in that the nanopores have an average cross-sectional dimension of 60 to 450 nanometers; and/or wherein the micropores have an average cross-sectional dimension of 1 to 20 micrometers.
[0003]
3. Porous polymeric material according to claim 1 or 2, characterized in that the first domains have an average transverse dimension of 0.05 to 50 micrometers; and/or in which the second domains, which have an average cross-sectional dimension of 50 to 500 nanometers.
[0004]
4. Porous polymeric material according to any one of the preceding claims, characterized in that the porous network further comprises a plurality of second nanopores, which are formed in and/or around the second domains.
[0005]
5. Porous polymeric material according to claim 4, characterized in that the second nanopores have an average transverse dimension of 1 to 50 nanometers.
[0006]
6. Porous polymeric material according to any one of the preceding claims, characterized in that the total pore volume of the polymeric material is 15% to 80% per cubic centimeter of the material; and/or wherein the polymeric material has a density of 1.2 g/cm3 or less.
[0007]
7. Porous polymeric material according to any one of the preceding claims, characterized in that the continuous phase is composed of 60% by weight to 99% by weight of the thermoplastic composition, the first inclusion additive consists of 5% by weight of 20% by weight of the composition based on the weight of the continuous phase, and the second inclusion additive consists of 0.1% by weight to 10% by weight of the composition based on the weight of the continuous phase.
[0008]
8. Porous polymeric material according to any one of the preceding claims, characterized in that the matrix polymer includes a polyester or polyolefin; and/or wherein the matrix polymer has a glass transition temperature of 0°C or more.
[0009]
9. Porous polymeric material according to any one of the preceding claims, characterized in that the second inclusion additive is a functionalized polyolefin, such as a polyepoxide.
[0010]
10. Porous polymeric material according to any one of the preceding claims, characterized in that the thermoplastic composition also contains a third inclusion additive which is dispersed in the continuous phase in the form of third discrete domains.
[0011]
11. Porous polymeric material according to claim 10, characterized in that the third inclusion additive includes a nanoclay.
[0012]
12. Porous polymeric material according to claim 10 or 11, characterized in that the third domain has an average transverse dimension of 1 to 50 nanometers; and/or wherein the third domain constitutes from 0.05% by weight to 20% by weight of the thermoplastic composition, based on the weight of the continuous phase; and/or wherein the network further comprises a plurality of nanopores formed in and/or around the third domains that have an average transverse dimension of 1 to 50 nanometers.
[0013]
13. Porous polymeric material according to claim 10 or 11, characterized in that the third inclusion additive is mixed with a vehicle resin.
[0014]
14. Porous polymeric material according to claim 13, characterized in that the carrier vehicle resin is dispersed in the continuous phase in the form of domains with an average transverse dimension of 0.5 to 30 micrometers.
[0015]
15. Porous polymeric material according to any one of the preceding claims, characterized in that the thermoplastic composition further comprises an interphase modifier.
[0016]
16. Porous polymeric material according to any one of the preceding claims, characterized in that the polymeric material is generally free of gaseous expansion agents.
[0017]
17. Porous polymeric material according to any one of the preceding claims, characterized in that the micropores are elongated, and the nanopores are generally spherical; and/or wherein the porous network is substantially homogeneously distributed throughout the material; and/or wherein the micropores and/or nanopores are generally distributed in parallel columns.
[0018]
18. Method for forming the porous polymeric material as defined in any one of the preceding claims, characterized in that it comprises stretching the thermoplastic composition while in the solid state, to form the porous network.
[0019]
19. Method according to claim 18, characterized in that the stretching is mechanical stretching.
[0020]
20. Method according to claim 18 or 19, characterized in that the composition is stretched at a temperature comprised between -50°C to 50°C; and/or wherein the composition is drawn at a temperature that is at least 10°C below the glass transition temperature of the matrix polymer and/or the first inclusion additive.

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同族专利:

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公开号 | 公开日

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MX2015016241A|2016-03-21|

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WO2014199273A1|2014-12-18|

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EP3008119B1|2020-10-21|

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KR20160019473A|2016-02-19|

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KR102224562B1|2021-03-08|

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RU2015155638A|2017-06-29|

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US20160102185A1|2016-04-14|

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JP2016521785A|2016-07-25|

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EP3008119A4|2017-02-01|

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ZA201509319B|2017-09-27|

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US11084916B2|2021-08-10|

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EP3008119A1|2016-04-20|

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AU2014279700B2|2017-09-14|

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SG11201510047YA|2016-01-28|

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CN105263997B|2018-10-26|

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CN105263997A|2016-01-20|

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BR112015029119A2|2017-07-25|

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AU2014279700A1|2016-01-21|

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RU2631796C2|2017-09-26|

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ES2837999T3|2021-07-01|

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-11-03| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

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2021-05-04| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-06-22| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 06/06/2014, 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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US201361833983P| true| 2013-06-12|2013-06-12|

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US61/833,983|2013-06-12|

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US201361907566P| true| 2013-11-22|2013-11-22|

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US61/907,566|2013-11-22|

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PCT/IB2014/062023|WO2014199273A1|2013-06-12|2014-06-06|Polymeric material with a multimodal pore size distribution|

---