polymeric material, thermal insulation, article and method for forming a polymeric material

专利摘要:
POLYMERIC MATERIAL FOR USE IN THERMAL INSULATION A polymeric material is provided for use in thermal insulation. The polymeric material is formed from a thermoplastic composition containing a continuous phase that includes a matrix polymer and within which a nano-inclusion and micro-inclusion additive are dispersed in the form of discrete domains. A porous network is defined in the material that includes a plurality of nanopores with an average cross-sectional dimension of about 800 nanometers or less. The polymeric material exhibits thermal conductivity of about 0.20 watts per meter-kelvin or less.
公开号:BR112015030318B1
申请号:R112015030318-8
申请日:2014-06-06
公开日:2020-12-08
发明作者:Vasily A. Topolkaraev；Ryan J. Mceneany；Neil T. Scholl；Charles W. Colman Iii；Mark M. Mleziva
申请人:Kimberly-Clark Worldwide, Inc；
IPC主号:

专利说明:

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[1] This application claims priority over Provisional Patent Applications Serial No. 61 / 833,992, filed on June 12, 2013, and 61 / 907,562, filed on November 22, 2013, which are incorporated into this document. in its entirety by way of reference. Fundamentals of the Invention
[2] Polymeric foams are commonly used in thermal insulation. In typical cases of foam insulation, the dominant mode of heat transfer is conduction of cellular gas. When the cell size of such foams is less than about one micrometer, for example, the overall thermal conductivity decreases, while reducing the number of cell gas molecules inside each cell to collide and transfer heat inside each individual cell - a phenomenon often referred to as Knudsen Diffusion. Knudsen's Diffusion is particularly significant as the cell size and connectivity between cells becomes the same order of magnitude as the average free gas pathway filling the cells. For this reason, nanoscale cell sizes in foams are desired to maximize Knudsen Diffusion. Unfortunately, attempts to reduce the cell size of polymeric foams often compromise the processability and elastic properties of the resulting material due to uncontrolled pore sizing and distribution. There are other problems as well. Various polymers (e.g., polyesters), for example, have relatively high glass transition temperatures and typically demonstrate very high rigidity, while having relatively low ductility / elongation at the breaking point. Such low values of elastic elongation significantly limit the use of such polymers in cases of thermal insulation, where a good balance between strength and ductility is required.
[3] As such, there is currently a need for a reinforced material that can be used in thermal insulation. Summary of the Invention
[4] In accordance with an embodiment of the present invention, a polymeric material is disclosed for use in cases of thermal insulation. The polymeric material is formed from a thermoplastic composition containing a continuous phase that includes a matrix polymer and within which a nano-inclusion and micro-inclusion additive are dispersed in the form of discrete domains. A porous network is defined in the material that includes a plurality of nanopores with an average cross-sectional dimension of about 800 nanometers or less. The polymeric material exhibits thermal conductivity of about 0.20 watts per meter-kelvin or less.
[5] Other properties and aspects of the present invention will be discussed in more detail below. Brief Description of the Figures
[6] A complete and illuminating description of the present invention, including its best mode, aimed at people skilled in the art, is established more particularly in the rest of the specification, which makes reference to the attached figures in which: Fig. 1 presents a partial representative view of a building foundation wall manufactured with a building panel that can be formed according to the invention, Fig. 2 is a cross-sectional view of the building panel of Fig. 1 along a line 2 -2; Fig. 3 is a top view of a shoe lining that can be formed according to the present invention; Fig. 4 is a cross-sectional view of the shoe lining of Fig. 3; Fig. 5 is a perspective view of an embodiment of a lining for a coat that can be formed in accordance with the present invention. Figures 6-7 are SEM microphotographs of the stripped film of Example 7 (the film was cut in parallel to the machine's direction orientation ); as Figure s 8-9 are SEM microphotographs of the stretched film of Example 7 (the film was cut in parallel to the machine's orientation orientation); Figures 10-11 are SEM microphotographs of the de-strained film of Example 8, where the film was cut perpendicularly to the machine direction in Fig. 10 and parallel to the machine direction in Fig. 11; Figures 12-13 are SEM microphotographs of the stretched film of Example 8 (the film was cut parallel to the direction of the machine direction); 14 is a SEM (1,000X) photomicrograph of the fiber of Example 9 (polypropylene, polylactic acid and polypoxy) after fracturing by freezing in liquid nitrogen; Fig. 15 is a SEM (5,000X) photomicrograph of the fiber of Example 9 (polypropylene, polylactic acid and polyepoxy) after fracturing by freezing in liquid nitrogen; and Fig. 16 is a SEM photomicrograph (10,000X) of the fiber surface of Example 9 (polypropylene, polylactic acid and polypoxy).
[7] The repeated use of reference characters in this specification and in the figures is intended to represent characteristics or similar or analogous elements of the invention. Detailed Description of Representative Modalities
[8] Detailed references will be made to various modalities of the invention, with one or more examples described below. Each example is provided by way of explanation of the invention, without limitation of the invention. Indeed, it will be apparent to those skilled in the art that various modifications and variations 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 modality, can be used in another modality to produce yet another modality. Thus, it is intended that the present invention covers such modifications and variations that are within the scope of the appended claims and their equivalents.
[9] In general, the present invention is oriented to a polymeric material (for example, film, fibrous material, etc.). for use in cases of thermal insulation. The polymeric material acts as a thermal barrier and therefore exhibits relatively low thermal conductivity, such as, for example, 0.20 watts per meter-kelvin ("W / mK") or less, in some embodiments around 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 such low conductivity values at relatively low thicknesses, which can allow the material to have a greater degree of flexibility and conformability, as well as reducing the space it occupies in an article. For this reason, the polymeric material may also have relatively low "thermal admittance", which is equal to the thermal conductivity of the material divided by its thickness and provided in units of watts per square meter-kelvin ("W / m2K"). For example, the material may have a thermal admittance of about 1000 W / m 2K or less, in some modalities from about 10 to about 800 W / m2K, in some modalities from about 20 to about 500 W / m2K, and in some modalities from about 40 to about 200 W / m2K. The actual thickness of the polymeric material may depend on its particular shape, however, it typically ranges from about 5 micrometers to about 100 millimeters, in some modalities from about 10 micrometers to about 50 millimeters, in some modalities from about 200 micrometers at about 25 millimeters, and in some embodiments, from about 50 micrometers to about 5 millimeters.
[10] To achieve such excellent thermal properties, the polymeric material of the present invention defines a porous network with a portion of pores in “nanoscale” size (“nanopores”), such as those with an average cross-sectional dimension of about 800 nanometers or less, in some modalities from about 1 to about 500 nanometers, in some modalities from about 5 to about 450 nanometers, in some modalities from about 5 to about 400 nanometers, and in some modalities, from about from 10 to about 100 nanometers. The term "transverse dimension" generally refers to a characteristic dimension (for example, width or diameter) of a pore, which is substantially orthogonal to its main axis (for example, length) and also normally orthogonal to the direction of the stress applied during stretching. Such nanopores can, for example, constitute about 15% by volume or more, in some embodiments about 20% by volume or more, in some embodiments about 30% by volume to about 100% by volume, and in some embodiments from about 40% by volume to about 90% by volume of total pore in the polymeric material. Likewise, the material is highly porous in that the average percentage volume occupied by the pores within a given unit volume of the material is typically from 15% to about 80% per cm3, in some modalities of about from 20% to about 70%, and in some modalities, from about 30% to about 60% per cubic centimeter of the material. In addition to improving thermal insulation properties, such a high vacuum volume can also significantly decrease the density of the material. For example, the composition may 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 about 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. Due to their low density, lighter materials can be formed which can still achieve good thermal resistance.
[11] Unlike conventional techniques for forming thermal insulation materials, the present inventors may have discovered that the porous material of the present invention can be formed without the use of gaseous blowing agents. This is due in part to the unique nature of the material's components, as well as the matter in which the material is formed. More specifically, the porous material can be formed from a thermoplastic composition containing a continuous phase that includes a matrix polymer, micro-inclusion additive and nano-inclusion additive. Additives can be selected so that they have an elastic modulus different from the matrix polymer. In this way, the micro-inclusion and nano-inclusion additives can be dispersed within the continuous phase as discrete microscale and nanoscale phase domains, respectively. The present inventors have found that the microscale and nanoscale phase domains are capable of interacting in a unique way when subjected to a deformation and stretching force (for example, stretching) to create a pore network, a substantial part of which has a nanoscale size. That is, it is believed that the stretching force can initiate the intensive localized shear zones and / or stress intensity zones (for example, normal stresses) close to the discrete microscale phase domains, as a result of stress concentrations that arise from the incompatibility of materials. These zones of shear intensity and / or stress cause an initial detachment in the polymer matrix adjacent to the microscale domains. In particular, however, the shear intensity and / or stress zones located can also be created close to the discrete nanoscale phase domains that overlap the microscale zones. Such overlapping shear and / or stress zones further cause the detachment to occur in the polymer matrix, thereby creating a substantial number of nanopores adjacent to the nanoscale and / or microscale domains.
[12] Various modalities of the present invention will now be described in more detail.1. Thermoplastic Composition A. Matrix Polymer
[13] As indicated above, the thermoplastic composition contains a continuous phase within which micro-inclusion and nano-inclusion additives are dispersed. The continuous phase contains one or more matrix polymers, which typically constitute 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 embodiment, 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 critical and any suitable polymer can be employed in general, such as polyesters, polyolefins, styrenic polymers, polyamides, etc. In certain embodiments, for example, polyesters can be used in the composition to form the polymer matrix. Any of a variety of polyesters can generally be used, such as aliphatic polyesters, such as polycaprolactone, polyesteramides, polylactic acid (PLA) and its copolymers, polyglycolic acid, polyalkylene carbonates (eg polyethylene carbonate), copolymers of poly-3-hydroxybutyrate (PHB), poly-3-hydroxyvalerate (PHV), poly-3-hydroxybutyrate-co-4-hydroxybutyrate, poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), poly-3 -hydroxybutyrate-co-3-hydroxyhexanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctanoate, poly-3-hydroxybutyrate-co-3-hydroxidecanoate, poly-3-hydroxybutyrate-co-3-hydroxyoctadecanoate, and aliphatic polymers based succinate (for example, polybutylene succinate, polybutylene adipate succinate, polyethylene succinate, etc.); aliphatic-aromatic copolyesters (for example, polybutylene adipate terephthalate, polyethylene adipate terephthalate, polyethylene isophthalate adipate, polybutylene isophthalate adipate, etc.); aromatic polyesters (for example, polyethylene terephthalate, polybutylene terephthalate, etc.); and so on.
[14] In certain cases, the thermoplastic composition may contain at least one polyester which is rigid in nature and thus have a relatively high glass transition temperature. For example, the glass transition temperature ("Tg") can be about 0 ° C or more, in some embodiments, from about 5 ° C to about 100 ° C, in some embodiments, about 30 ° C at about 80 ° C, and in some embodiments, from about 50 ° C to about 75 ° C. The polyester can also have a melting temperature of about 140 ° C to about 300 ° C, in some embodiments, from about 150 ° C to about 250 ° C, and in some embodiments, about 160 ° C at about 220 ° C. The melting temperature can be determined using differential scanning calorimetry (“DSC”) according to ASTM D-3417. The glass transition temperature can be determined by dynamic mechanical analysis in accordance with ASTM E1640-09.
[15] A particularly suitable rigid polyester is polylactic acid, which can generally be derived from monomeric units of any lactic acid isomer, such as levogyrous lactic acid (“L-lactic acid”), dextrogyrous lactic acid (“D- lactic ”), meso-lactic acid or combinations thereof. Monomeric units can also be formed by anhydrides of any isomer of lactic acid, including L-lactide, D-lactide, meso-lactide or combinations thereof. Cyclic dimers of these lactic acids and / or lactides can also be used. Any known polymerization method, such as polycondensation or ring opening polymerization, can be used to polymerize lactic acid. A small amount of a chain extension agent (for example, a diisocyanate compound, an epoxy compound or acid anhydride) can also be employed. The polylactic acid can be a homopolymer or a copolymer, such as one that contains 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 monomeric units derived from L-lactic acid and the monomeric unit derived from D-lactic acid is preferably about 85 mol% or more, in some embodiments, about 90 mol% or more and, in other embodiments, about 95 mol% or more. Various polylactic acids, each with a different ratio between the monomeric unit derived from L-lactic acid and the monomeric unit derived from D-lactic acid, can be mixed in any random percentage. Of course, polylactic acid can be mixed with other types of polymers (for example, polyolefins, polyesters, etc.).
[16] In a specific embodiment, polylactic acid has the following general structure:

[17] In a specific example of a suitable polylactic acid polymer that can be used in the present invention is commercially available from Biomer, Inc. of Krailling, Germany) under the name BIOMER ™ L9000. Other suitable polylactic acid polymers are commercially available from Natureworks LLC of Minnetonka, Minnesota (NATUREWORKS®) or Mitsui Chemical (LACEATM). Still other suitable polylactic acids can be described in U.S. Patent Nos. 4,797,468; 5,470,944; 5,770,682; 5,821,327; 5,880,254; and 6,326,458.
[18] Polylactic acid typically has an average molecular weight (“Mn”) number that ranges from about 40,000 to about 180,000 grams per mol, in some embodiments, from about 50,000 to about 160,000 grams per mol and, in some embodiments, from about 80,000 to about 120,000 grams per mol. Likewise, the polymer usually also has an average molecular weight ("Mn") that ranges from about 80,000 to about 250,000 grams per mol, in some embodiments, from about 100,000 to about 200,000 grams per mol and, in some embodiments, from about 110,000 to about 160,000 grams per mol. The ratio between the average weight molecular weight and the number of the average molecular weight (“Mw / Mn”), that is, the "polydispersity index", is also relatively low. For example, the polydispersity index usually ranges from about 1.0 to about 3.0, in some embodiments, from about 1.1 to about 2.0, and, in embodiments, from about 1.2 about 1.8. The average molecular weight and average weight numbers can be determined by methods known to those skilled in the art.
[19] Polylactic acid can also have an apparent viscosity of about 50 to about 600 Pascal-seconds (Pa-s), in some embodiments, from about 100 to about 500 Pa ^ s, and in some embodiments, of about 200 to about 400 Pa-s, as determined at a temperature of 190 ° C and a shear rate of 1000 sec-1. The melt flow rate of polylactic acid (on a dry basis) can also vary from about 0.1 to about 40 grams for 10 minutes, in some embodiments, from about 0.5 to about 20 grams for 10 minutes , and, in some embodiments, from about 5 to about 15 grams for 10 minutes, determined at a load of 2160 grams and at 190 ° C.
[20] Some types of pure polyester (eg polylactic acid) can absorb water from the environment, such that it has a moisture content of about 500 to 600 parts per million (“ppm”), or even higher, based on dry weight of the initial polylactic acid. The moisture content can be determined in several ways, as is known in the art, such as according to ASTM D 7191-05, as described below. Since the presence of water during melt processing can hydrolytically degrade the polyester and reduce its molecular weight, it is sometimes desired to dry the polyester before mixing it. In most modalities, for example, it is desired that the polyester has a moisture content of about 300 parts per million ("ppm") or less, in some modalities, of about 200 ppm or less, in some modalities, of about 1 to about 100 ppm, before mixing with micro-inclusion and nano-inclusion additives. The drying of the polyester can take place, for example, at a temperature of about 50 ° C to about 100 ° C and, in some embodiments, from about 70 ° C to about 80 ° C.B.
[21] As used herein, the term "microinclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material capable of being dispersed within the polymer matrix in the form of discrete domains of microscale size. For example, before drawing, the domains may have an average cross-sectional dimension of about 0.05 μm to about 30 μm, in some modalities, from about 0.1 μm to about 25 μm, in some modalities, from about 0.5 μm to about 20 μm, and in some embodiments, from about 1 μm to about 10 μm. The term "transverse dimension" generally refers to a characteristic dimension (for example, width or diameter) of a domain, which is substantially orthogonal to its main axis (for example, length) and also substantially orthogonal to the direction of the stress applied during stretching. Although normally formed from the micro-inclusion additive, it should be understood that the micro-scale domains can also be formed from a combination of the micro-inclusion and nano-inclusion additives and / or other components of the composition.
[22] The microinclusion additive is generally polymeric in nature and has a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. Typically, the microinclusion polymer can generally be immiscible with the matrix polymer. In this way, the additive can be better spread as the discrete phase domains within a continuous phase of the matrix polymer. The discrete domains are able to absorb energy due to an external force, which increases the stiffness and the general resistance of the resulting material. Domains can have a variety of different shapes, such as elliptical, spherical, cylindrical, plate-like, tubular, etc. In one embodiment, for example, the domains are substantially elliptical in shape. The physical dimension of an individual domain is typically small enough to minimize the propagation of cracks through the polymeric material when applying external stress, but large enough to initiate microscopic plastic deformation and allow for shear and / or intensity zones of stress in and around particle inclusions.
[23] Although the polymers may be immiscible, the microinclusion additive can nevertheless be selected because it has a solubility parameter that is relatively similar to that of the matrix polymer. This can improve the interfacial compatibility and physical interaction of the discrete and continuous phase boundaries and thus reduce the likelihood of the compound breaking. In that respect, the ratio between the solubility parameter for the matrix polymer and that of the additive is usually about 0.5 to about 1.5 and, in some embodiments, from about 0.8 to about 1, two. For example, the polymeric microinclusion additive may have a solubility parameter of about 15 to about 30 MJoules1 / 2 / m3 / 2 and, in some embodiments, from about 18 to about 22 MJoules1 / 2 / m3 / 2 , while polylactic acid may have a solubility parameter of about 20.5 MJoules1 / 2 / m3 / 2. The term “solubility parameter”, as used in this document, refers to the “Hildebrand Solubility Parameter”, which is the square root of the density of cohesive energy and is calculated according to the following equation:
where: Δ Hv = heat of vaporizationR = Ideal gas constantT = TemperatureVm = Molecular volume
[24] Hildebrand's solubility parameters for various polymers are also available from Wyeych's Solubility Handbook of Plastics (2004), which is incorporated into this document by reference.
[25] The microinclusion additive can also have a certain melt flow rate (or viscosity) to ensure that the discrete domains and the resulting pores can be maintained properly. For example, if the melt flow rate of the additive is too high, it tends to flow and disperse uncontrollably in the continuous phase. This results in lamellar or plate-like domains or co-continuous phase structures that are difficult to maintain and are also likely to crack prematurely. On the other hand, if the melt flow rate of the additive is too low, it will tend to agglutinate and form very large elliptical domains, which are difficult to disperse during mixing. This may cause an irregular distribution of the additive throughout the continuous phase. In this regard, the present inventors have found that the ratio between the melt flow rate of the microinclusion additive and the melt flow rate of the matrix polymer is usually about 0.2 to about 8, in some embodiments, from about 0.5 to about 6 and, in some embodiments, from about 1 to about 5. The microinclusion additive can, for example, have a melt flow rate of about 0.1 to about 250 grams for 10 minutes, in some modalities, from about 0.5 to about 200 grams for 10 minutes and, in some modalities, from about 5 to about 150 grams for 10 minutes, determined in a load of 2160 grams and the 190 ° C.
[26] In addition to the properties noted above, the mechanical characteristics of the micro-inclusion additive can also be selected to achieve the desired porous network. For example, when a mixture of the matrix polymer and the micro-inclusion additive is applied with an external force, stress concentrations (for example, including normal or shear stress) and shear and / or plastic production zones can be applied. be initiated around and in the discrete phase domains as a result of the stress concentrations that arise from a difference in the elastic modulus of the additive and the matrix polymer. Higher concentrations of stress promote a more intense localized plastic flow in the domains, allowing them to become significantly stretched when stresses are applied. These elongated domains allow the composition to exhibit a more flexible and softer behavior than the matrix polymer, such as when it is a rigid polyester resin. To improve stress concentrations, the microinclusion additive can be selected to have a relatively low Young's modulus of elasticity compared to the matrix polymer. For example, the ratio of the modulus of elasticity of the matrix polymer to that of the additive is usually about 1 to about 250, in some embodiments, from about 2 to about 100 and, in some embodiments, about 2 to about 50. The modulus of elasticity of the micro-inclusion additive can, for example, vary from about 2 to about 1000 megapascals (MPa), in some embodiments, from about 5 to about 500 MPa and, in some modalities, from about 10 to about 200 MPa. On the other hand, the modulus of elasticity of polylactic acid, for example, is usually from about 800 MPa to about 3000 MPa.
[27] Although a wide variety of micro-inclusion additives that have the properties identified above can be employed, particularly suitable examples of such additives may also include synthetic polymers, such as polyolefins (for example, 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 (for example, recycled polyester, polyethylene terephthalate, etc.); polyvinyl acetates (for example, poly (ethylene vinyl acetate), polyvinyl acetate and chloride, etc.); polyvinyl alcohols (for example, polyvinyl alcohol, poly (ethylene vinyl alcohol), etc.); polyvinyl butyrals; 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 (for example, low density polyethylene (“LDPE”), high density polyethylene (“HDPE”), linear low density polyethylene (“LLDPE”), etc.), propylene homopolymers (for example, syndiotactic, atactic, isotactic, etc.), propylene copolymers, and so on.
[28] In a given embodiment, the polymer is a propylene polymer, such as homopolypropylene, or a propylene copolymer. The propylene polymer can, for example, be formed by a substantially isotactic polypropylene homopolymer or by a copolymer containing an amount equal to or less than about 10% of the other monomer, i.e., at least about 90% by weight of propylene. Such homopolymers can have a melting point of about 160 ° C to about 170 ° C.
[29] In yet another embodiment, the polyolefin can be a copolymer of ethylene or propylene with another α-olefin, such as α-olefin C3-C20 or α-olefin C3-C12. Specific examples of suitable α-olefins include 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1-heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The particularly desired comonomers of α-olefin are 1-butene, 1-hexene and 1-octene. The ethylene or propylene content of such copolymers can vary from about 60 mol% to about 99 mol%, in some embodiments, from about 80 mol% to about 98.5 mol%, and in some embodiments, from about 87 mol% to about 97.5 mol%. The α-olefin content can vary from about 1 mol% to about 40 mol%, in some embodiments, from about 1.5 mol% to about 15 mol%, and in some embodiments, from about 2.5 mol% to about 13 mol%.
[30] Examples of olefin copolymers for use in the present invention include ethylene-based copolymers available under the name EXACT ™, from ExxonMobil Chemical Company of Houston, Texas. Other suitable ethylene copolymers are available under the designation ENGAGE ™, AFFINITY ™, DOWLEX ™ (LLDPE) and ATTANE ™ (ULDPE) from Dow Chemical Company of Midland, Michigan. Other suitable ethylene polymers are described in U.S. Patent Nos. 4,937,299 to Ewen et al .; 5,218,071 to Tsutsui et al .; 5,272,236 to Lai, et al .; and 5,278,272 to Lai, et al. Suitable propylene copolymers are also commercially available under the VISTAMAXX ™ designations of ExxonMobil Chemical Co. of Houston, Texas; FINA ™ (eg 8573) from Atofina Chemicals of Feluy, Belgium; TAFMER ™ available from Mitsui Petrochemical Industries; and VERSIFY ™, available from Dow Chemical Co. of Midland, Michigan. Suitable polypropylene homopolymers can 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. Patent Nos. 6,500,563 to Datta et al .; 5,539,056 to Yang et al .; and 5,596,052 to Resconi et al.
[31] A wide variety of known techniques can be employed, in general, to form olefin copolymers. For example, olefin polymers can be formed using a free radical or a coordinating catalyst (for example, Ziegler-Natta). Preferably, the olefin polymer is formed by a single site coordination catalyst, such as a metallocene catalyst. Such a catalyst system produces ethylene copolymers, in which the comonomer is randomly distributed within a molecular chain and uniformly distributed among the different molecular weight fractions. Metallocene-catalyzed polyolefins are described, for example, in U.S. Patent 5,571,619 to McAlpin et al .; 5,322,728 for Davis et al .; 5,472,775 to Obijeski et al .; 5,272,236 to 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, methyl (dichloro) dichloride bis (methylcyclopentadienyl) zirconium, cobaltocene, cyclopentadienyltitanium trichloride, ferrocene, hafnocene dichloride, isopropyl dichloride (cyclopentadienyl, -1-flourenyl) zirconium, molybdocene dichloride, nickelocene, dichlorocene, nickelocene, dichlorocene zirconocene chloride, zirconocene dichloride, and so on. Polymers produced using metallocene catalysts typically have a narrow molecular weight range. For example, metallocene-catalyzed polymers may have polydispersity numbers (Mw / Mn) below 4, controlled short chain branch distribution and controlled isotacticity.
[32] Regardless of the materials used, the relative percentage of the microinclusion additive in the thermoplastic composition is selected to achieve the desired properties without significantly affecting the basic properties of the composition. For example, the microinclusion additive is normally employed in an amount of about 1% by weight to about 30% by weight, in some embodiments, from about 2% by weight to about 25% by weight and, in some embodiments , from about 5% by weight to about 20% by weight of the thermoplastic composition, based on the weight of the continuous phase (polymer (s) of the matrix). The concentration of the microinclusion additive in the entire thermoplastic composition can be from about 0.1% by weight to about 30% by weight, in some embodiments, from about 0.5% by weight to about 25% by weight and , in some embodiments, from about 1% by weight to about 20% by weight.
[33] As used herein, the term "nanoinclusion additive" generally refers to any amorphous, crystalline or semi-crystalline material that is capable of being dispersed within the polymer matrix in the form of discrete domains of a nanoscale size. For example, before stretching, the domains may have an average cross-sectional dimension of about 1 to about 500 nanometers, in some modalities, from about 2 to about 400 nanometers, and in some modalities, from about 5 to about 300 nanometers. It should also be understood that nanoscale domains can also be formed from a combination of micro-inclusion and nano-inclusion additives and / or other components of the composition. For example, the nanoinclusion additive is normally employed in an amount of about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight and in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (polymer (s) of the matrix). The concentration of the nano-inclusion additive in the entire thermoplastic composition can be from about 0.01% by weight to about 15% by weight, in some embodiments, from about 0.05% by weight to about 10% by weight and, in some embodiments, from about 0.3% by weight to about 6% by weight of the thermoplastic composition.
[34] The nanoinclusion additive can be polymeric in nature and have a relatively high molecular weight to help improve the melt strength and stability of the thermoplastic composition. To increase its ability to become dispersed in nanoscale domains, the nano-inclusion additive can also be selected from materials that are generally compatible with the matrix polymer and the micro-inclusion additive. This can be particularly useful when the matrix polymer or micro-inclusion additive has a polar fraction, such as a polyester. An example of such a nano-inclusion additive is a 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 nano-inclusion additive olefin compound can generally be formed of any branched or linear α-olefin monomer, oligomer, or polymer (including copolymers) derived from an olefin monomer, as described above.
[35] The functional group of the nanoinclusion additive can be any group, segment and / or molecular block that provides a polar component for the molecule and is not compatible with the matrix polymer. Examples of segment and / or molecular blocks not compatible with polyolefin may include acrylates, styrenics, polyesters, polyamides, etc. The functional group may be ionic in nature and comprise charged metal ions. Particularly 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 particularly suitable for use in the present invention. Such modified polyolefins are usually formed by grafting maleic anhydride into a material of the polymeric backbone. These maleatated polyolefins are available from EI du Pont de Nemours and Company under the name Fusabond®, such as the P series (chemically modified polypropylene), E series (chemically modified polyethylene), C series (chemically modified ethylene vinyl acetate), series A (chemically modified ethylene acrylate copolymers or terpolymers), or series N (chemically modified ethylene-propylene diene monomer ("EPDM") or ethylene-octene). Alternatively, maleatated polyolefins are also available from Chemtura Corp. under the name of Polybond® and Eastman Chemical Company under the name of Eastman G series.
[36] In certain embodiments, the nano-inclusion additive can also be reactive. An example of such a reactive nano-inclusion additive is a polyepoxide that contains, on average, at least two axirane rings per molecule. Without the intention of limiting themselves by theory, it is believed that these polyepoxide molecules can induce a reaction of the matrix polymer (for example, polyester) under certain conditions, thereby improving their melt resistance without significantly 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 reaction pathways. For example, the modifier can allow a nucleophilic reaction for ring opening through a carboxyl terminal group of a polyester (esterification) or through a hydroxyl group (etherification). Side reactions of oxazoline can occur to form esteramide fractions. Through these reactions, the molecular weight of the matrix polymer can be increased to counteract degradation frequently during the melting process. Although it is desirable to induce a reaction with the matrix polymer as described above, the present inventors have found that too much reaction can cause crosslinking between the main structures of the polymer. If this crosslinking has been allowed to proceed to a significant extent, the resulting polymer mixture may become brittle and difficult to process in a material with the desired properties of strength and elongation.
[37] In this regard, the present inventors have found that polyepoxides with relatively low epoxy functionality are particularly effective, which can be quantified by "epoxy equivalent weight". The epoxy equivalent weight reflects the amount of resin that contains a molecule of an epoxy group, and can be calculated by dividing the average molecular weight in number of the modifier by the number of epoxy groups in the molecule. The polyepoxide of the present invention normally has an average molecular weight in number of about 7,500 to about 250,000 grams per mol, in some embodiments, from about 15,000 to about 150,000 grams per mol and, in some embodiments, from about 20,000 to about 100,000 grams per mole, with a polydispersity index ranging from 2.5 to 7. Polyepoxide may contain less than 50, in some embodiments, from 5 to 45 and, in some embodiments, from 15 to 40 epoxy groups. In turn, the epoxy equivalent weight may be less than about 15,000 grams per mole, in some embodiments, from about 200 to about 10,000 grams per mole and, in some embodiments, from about 500 to about 7,000 grams per mol.
[38] The polyepoxide can be a linear or branched homopolymer or copolymer (for example, 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 monomeric (meth) acrylic component. As used herein, the term “(meth) acrylic” includes acrylic and methacrylic monomers, as well as their salts or esters, such as acrylate and methacrylate monomers. For example, suitable epoxy-functional (meth) acrylic monomers can include, but are not limited to, those containing 1,2-epoxy groups, such as glycidyl acrylate and glycidyl methacrylate. Other suitable epoxy-functional monomers include allyl glycidyl ether, glycidyl ethacrylate and glycidyl itoconate.
[39] Polyepoxide normally has a relatively high molecular weight, as indicated above, so that it can not only result in chain extension, but also achieve the desired morphology of the mixture. The melt flow rate resulting from the polymer is thus typically within a range of about 10 to about 200 grams for 10 minutes, in some embodiments, from about 40 to about 150 grams for 10 minutes, and in some modalities, from about 60 to about 120 grams for 10 minutes, determined in a load of 2160 grams and at a temperature of 190 ° C.
[40] If desired, additional monomers can also be used in the polyepoxide to help achieve the desired molecular weight. Such monomers may vary and include, for example, ester monomers, (meth) acrylic monomers, olefin monomers, amide monomers, etc. In a specific embodiment, for example, the polyepoxide includes at least one linear or branched α-olefin monomer, such as those having 2 to 20 carbon atoms and preferably 2 to 8 carbon atoms. Specific examples include ethylene, propylene, 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene; 1-pentene; 1-pentene with one or more methyl, ethyl or propyl substituents; 1-hexene with one or more methyl, ethyl or propyl substituents; 1- heptene with one or more methyl, ethyl or propyl substituents; 1-octene with one or more methyl, ethyl or propyl substituents; 1-nonene with one or more methyl, ethyl or propyl substituents; 1-decene substituted by ethyl, methyl or dimethyl; 1-dodecene; and styrene. The particularly desired α-olefin comonomers are ethylene and propylene.
[41] Another suitable monomer may include a (meth) acrylic monomer that is not epoxy-functional. Examples of such (meth) acrylic monomers may include methyl acrylate, ethyl acrylate, n-propyl acrylate, i-propyl acrylate, n-butyl acrylate, s-butyl acrylate, i-butyl acrylate, t-acrylate -butyl, n-amyl acrylate, i-amyl acrylate, isobornyl acrylate, n-hexyl acrylate, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl acrylate, acrylate methylcyclohexyl, cyclopentyl acrylate, cyclohexyl acrylate, methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, n-propyl methacrylate, n-butyl methacrylate, i-propyl methacrylate, methacrylate, methacrylate, methacrylate of n-amyl, n-hexyl methacrylate, i-amyl methacrylate, s-butyl methacrylate, t-butyl methacrylate, 2-ethylbutyl methacrylate, methylcyclohexyl methacrylate, cinnamyl methacrylate, methacrylate methacrylate , cyclopentyl methacrylate, 2-ethoxyethyl methacrylate, isobornyl methacrylate, etc., good as a combi nations of the same.
[42] In a particularly desirable embodiment of the present invention, polyepoxide is a terpolymer formed by an epoxy-functional monomeric (meth) acrylic component, an α-olefin monomeric (meth) component, and a non-epoxy-functional monomeric (meth) acrylic component . For example, the polyepoxide can be poly (ethylene-co-methylacrylate-co-glycidyl) methacrylate, which has the following structure:
where x, y and z are 1 or greater.
[43] The epoxy-functional monomer can be transformed into a polymer using a variety of known techniques. For example, a monomer containing polar functional groups can be grafted into the main structure of a polymer to form a graft copolymer. Such grafting techniques are well known in the art and described, for example, in U.S. Patent No. 5,179,164. In other embodiments, a monomer containing epoxy-functional groups can be copolymerized with a monomer to form a random block or copolymer using known free radical polymerization techniques, such as high pressure reactions, reaction systems with Ziegler-Natta catalyst, systems reaction with single site catalyst (eg metallocene), etc.
[44] The relative part of the monomeric component (s) can be selected to achieve a balance between epoxy reactivity and melt flow rate. More specifically, a high epoxy monomer content can result in good reactivity with the matrix polymer, but a very high content can reduce the melt flow rate in such a way that the polyepoxide adversely affects the melt resistance of the mixture. polymer. Thus, in most modalities, the epoxy-functional acrylic (meth) monomer (s) constitutes (in) about 1% by weight to about 25% by weight, in some modalities, from about 2% by weight to about 20% by weight and, in some embodiments, from about 4% by weight to about 15% by weight of the copolymer. The α-olefin monomer (s) can also comprise from about 55% by weight to about 95% by weight, in some embodiments, from about 60% by weight to about 90% by weight. by weight and, in some embodiments, from about 65% by weight to about 85% by weight of the copolymer. When used, other monomeric components (for example, non-epoxy-functional (meth) acrylic monomers) may constitute from about 5% by weight to about 35% by weight, in some embodiments, from about 8% by weight to about from 30% by weight and, in some embodiments, from about 10% by weight to about 25% by weight of the copolymer. A specific example of a suitable polyepoxide that can be used in the present invention is commercially available from Arkema under the name LOTADER® AX8950 or AX8900. LOTADER® AX8950, for example, has a melt flow rate of 70 to 100 g / 10 min and has a 7% by weight to 11% by weight glycidyl methacrylate monomer content, an acrylate monomer content methyl content of 13% by weight to 17% by weight, and an ethylene monomer content of 72% by weight to 80% by weight. Another suitable polyepoxide is commercially available from DuPont under the name ELVALOY® PTW, which is an ethylene terpolymer, butyl acrylate, and glycidyl methacrylate and has a melt flow rate of 12 g / 10 min.
[45] In addition to controlling the type and relative content of the monomers used to form the polyepoxide, the overall weight percentage can also be controlled to achieve the desired benefits. For example, if the level of modification is very low, the desired increase in melt strength and mechanical properties may not be achieved. 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, crosslinking) and physical network formation by epoxy-functional groups. Thus, polyepoxide is normally employed in an amount of about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, in some embodiments from about 0.5% by weight to about 5% by weight and, in some embodiments, from about 1% by weight to about 3% by weight, based on the weight of the matrix polymer employed in the composition. Polyepoxide may also constitute about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.05% by weight to about 8% by weight, in some embodiments, from about 0 , 1% by weight to about 5% by weight and, in some embodiments, from about 0.5% by weight to about 3% by weight, based on the total weight of the composition.
[46] Other reactive nano-inclusion additives can also be employed in the present invention, such as functionalized oxazoline polymers, functionalized cyanide polymers, etc. When used, such reactive nano-inclusion additives can be used within the concentrations noted above for the polyepoxide. In a specific embodiment, a polyolefin grafted with oxazoline can be used, that is, a polyolefin grafted with a monomer containing an oxazoline ring. Oxazoline can include a 2-oxazoline, such as 2-vinyl-2-oxazoline (for example, 2-isopropenyl-2-oxazoline), 2-fatty-alkyl-2-oxazoline (for example, obtainable by oleic acid ethanolamine , linoleic acid, palmitoleic acid, gadoleic acid, erucic acid and / or arachidonic acid) and combinations thereof. In another embodiment, oxazoline can be selected from ricinoloxazoline maleinate, undecyl-2-oxazoline, soy-2-oxazoline, castor-2-oxazoline and combinations thereof, for example. In yet another modality, oxazoline is selected from 2-isopropenyl-2-oxazoline, 2-isopropenyl-4,4-dimethyl-2-oxazoline and combinations thereof.
[47] Nanocharges can also be used, such as carbon black, carbon nanotubes, carbon nanofibers, nano-clay, metallic nanoparticles, nanosilica, nanoalumina, etc. Nano-clays are particularly suitable. The term "nano-clay" generally refers to nanoparticles of a clay material (a naturally occurring mineral, an organically modified mineral, or a synthetic nanomaterial), which normally have a platelet structure. Examples of nanoclay include, for example, montmorillonite (2: 1 layered smectite clay structure), bentonite (aluminum phyllosilicate formed primarily by montmorillonite), kaolinite (1: 1 aluminosilicate with a flattened structure and an empirical Al2Si2O5 formula (OH) 4), haloisite (1: 1 aluminosilicate with a tubular structure and empirical formula of 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 nanoclay include, but are not limited to, mixed metal hydroxide nanoclay, double hydroxide nanoclay layered (eg, sepiocyte), laponite, hectorite, saponite, indonite, etc.
[48] If desired, the nanoclay may contain a surface treatment to help improve compatibility with the matrix polymer (eg, polyester). The surface treatment can be organic or inorganic. In one embodiment, an organic surface treatment is employed that is obtained by the reaction of an organic cation with the 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 chloride [hydrogenated tallow] ammonium (MB2HT ), methyl tris chloride [hydrogenated tallow alkyl] (M3HT), etc. Examples of commercially available organic nanoclay may include, for example, Dellite® 43B (Laviosa Chimica from Livorno, Italy), which is a montmorillonite clay modified with dimethyl tallow benzyl hydrogenated ammonium salt. Other examples include Cloisite® 25A and Cloisite® 30B (Southern Clay Products) and Nanofil 919 (Süd Chemie). If desired, the nanocharge can be mixed with a carrier resin to form a masterbatch that increases the compatibility of the additive 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.
[49] In certain embodiments of the present invention, several nano-inclusion additives can be used in combination. For example, a first nanoinclusion additive (e.g., polyepoxide) can be dispersed as domains with an average cross-sectional dimension of about 50 to about 500 nanometers, in some embodiments, from about 60 to about 400 nanometers, and in some modalities, from about 80 to about 300 nanometers. A second nanoinclusion additive (for example, nanocharge) can also be dispersed as domains that are smaller than the first nanoinclusive additive, such as those with an average cross-sectional dimension of about 1 to about 50 nanometers, in some embodiments, from about 2 to about 45 nanometers, and in some modalities, from about 5 to about 40 nanometers. When used, the first and / or second nanoinclusion additives normally comprise from about 0.05% by weight to about 20% by weight, in some embodiments, from about 0.1% by weight to about 10% by weight. weight, and in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase (polymer (s) of the matrix). The concentration of the first and / or second nano-inclusion additives in the entire thermoplastic composition can range from about 0.01% by weight to about 15% by weight, in some embodiments, from about 0.05% by weight to about 10% % by weight, and in some embodiments, from about 0.1% by weight to about 8% by weight of the thermoplastic composition.
[50] A wide variety of ingredients can be used in the composition for several different reasons. For example, in a specific modality, an interphasic modifier can also be used in the thermoplastic composition to help reduce the degree of friction and connectivity between the microinclusion additive and the matrix polymer and thus increase the degree and uniformity of the take-off . In this way, the pores can be distributed more evenly throughout the composition. The modifier can be in liquid or semi-solid form at room temperature (for example, 25 ° C) so that it has a relatively low viscosity, allowing it to be incorporated more easily into the thermoplastic composition and migrate more easily to the polymer surfaces. In this respect, the kinematic viscosity of the interphasic modifier is normally about 0.7 to about 200 centistokes ("cs"), in some modalities, from about 1 to about 100 cs and, in some modalities, from about 1.5 to about 80 cs, determined at 40 ° C. In addition, the interphasic modifier is also normally hydrophobic so that it has an affinity for the microinclusion additive, resulting, for example, in a change in the interfacial tension between the matrix polymer and the additive. By reducing the physical forces at the interfaces between the matrix polymer and the microinclusion additive, it is believed that the hydrophobic, low-viscosity nature of the modifier can help facilitate take-off. As used in this document, the term "hydrophobic" usually refers to a material that has a water and air contact angle of about 40 ° or more and, in some cases, about 60 ° or more. In contrast, the term "hydrophilic" usually refers to a material that has a contact angle of water and air less than about 40 °. A suitable test for measuring the contact angle is ASTM D5725-99 (2008).
[51] Suitable low-viscosity hydrophobic interphase modifiers may include, 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.), alkane diols (eg 1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 1,3-butanediol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6 hexanediol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, 2,2,4,4-tetramethyl-1 , 3-cyclobutanediol, etc.), amine oxides (eg octyldimethylamine oxide), fatty acid esters, fatty acid amides (eg oleamide, erucamide, stearamide, ethyl bis (stearamide), etc.), mineral and vegetable oils, and so on. A particularly suitable liquid or semi-solid is polyether polyol, such as that commercially available under the name Pluriol® WI from BASF Corp. Another suitable modifier is a partially renewable ester, such as the one commercially available under the name Hallstar HALLGREEN® IM.
[52] When used, the interphasic modifier may comprise from about 0.1% by weight to about 20% by weight, in some embodiments, from about 0.5% by weight to about 15% by weight, and in some embodiments, from about 1% by weight to about 10% by weight of the thermoplastic composition, based on the weight of the continuous phase (matrix polymer (s)). The concentration of the interphasic modifiers in the entire thermoplastic composition can be from about 0.05% by weight to about 20% by weight, in some embodiments from about 0.1% by weight to about 15% by weight and, in some embodiments, from about 0.5% by weight to about 10% by weight.
[53] When used in the amounts noted above, the interphasic modifier will have a feature that allows it to easily migrate to the interfacial surface of the polymers and facilitate detachment without damaging the general melting properties of the thermoplastic composition. For example, the interphasic modifier does not normally have a plasticizing effect on the polymer by reducing its glass transition temperature. On the contrary, the present inventors have found that the glass transition temperature of the thermoplastic composition can be substantially the same as that of the polymer of the initial matrix. In that respect, the ratio of the glass temperature of the composition to that of the matrix polymer is normally about 0.7 to about 1.3. in some modalities, from about 0.8 to about 1.2, and in some modalities, from about 0.9 to about 1.1. The thermoplastic composition can, for example, have a glass transition temperature of about 35 ° C to about 80 ° C, in some embodiments, from about 40 ° C to about 80 ° C, and in some embodiments, from about 50 ° C to about 65 ° C. The melt flow rate of the thermoplastic composition can also be similar to that of the matrix polymer. For example, the melt flow rate of the composition (on a dry basis) can be 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 some embodiments, from about 5 to about 25 grams for 10 minutes, determined on a load of 2160 grams and at a temperature of 190 ° C.
[54] Compatibilizers can also be used to improve interfacial adhesion and reduce the interfacial tension between the domain and the matrix, thus allowing the formation of smaller domains during mixing. Examples of suitable compatibilizers may include, for example, epoxy functionalized copolymers or maleic anhydride chemical fractions. An example of a maleic anhydride compatibilizer is maleic anhydride grafted with polypropylene, which is commercially available from Arkema under the names Orevac ™ 18750 and Orevac ™ CA 100. When used, compatibilizers can make up about 0.05% by weight to about 10% by weight, in some embodiments, from about 0.1% by weight to about 8% by weight, and in some embodiments, from about 0.5% by weight to about 5% by weight of the thermoplastic composition, based on the weight of the continuous phase matrix.
[55] 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.), particulate compounds, and other materials added to increase the processability and mechanical properties of the thermoplastic composition. However, a beneficial aspect of the present invention is that good properties can be provided without the need for several conventional additives, such as blowing agents (for example, chlorofluorocarbons, hydrochlorofluorocarbons, hydrocarbons, carbon dioxide, supercritical carbon dioxide, nitrogen, etc.) and plasticizers (for example, solid or semi-solid polyethylene glycol). In fact, the thermoplastic composition can generally be free of blowing agents and / or plasticizers. For example, blowing agents and / or plasticizers can be present in an amount of no more than about 1% by weight, in some embodiments, not more than about 0.5% by weight, and in some embodiments, about from 0.001% by weight to about 0.2% by weight of the thermoplastic composition. In addition, due to the stress-bleaching properties, as described in more detail below, the resulting composition can achieve an opaque color (e.g., white) without the need for conventional pigments, such as titanium dioxide. In certain embodiments, for example, 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 some embodiments, about 0.001 % by weight to about 0.2% by weight of the thermoplastic composition.11. Polymeric Materials
[56] As indicated above, the polymeric material of the present invention is, in most cases, formed by extracting a thermoplastic composition containing the matrix polymer, micro-inclusion additives, nano-inclusion additives, as well as other optional components. To form the initial thermoplastic composition, the components are typically mixed using any one of a variety of known techniques. In one embodiment, for example, components can be supplied separately or in combination. For example, the components can first be dry blended to form an essentially homogeneous dry mix, and can be supplied simultaneously or in sequence to a melt processing device that dispersively mixes the materials. Discontinuous and / or continuous fusion processing techniques can be employed. For example, a mixer / kneader, Banbury mixer, Farrel continuous mixer, single screw extruder, double screw extruder, laminators, etc. can be used to mix and process materials by melting. Particularly suitable fusion processing devices may be a co-rotating twin screw extruder (eg, ZSK-30 extruder available from Werner & Pfleiderer Corporation of Ramsey, New Jersey or a USALAB 16 Thermo Prism ™ extruder, available from Thermo Electron Corp., Stone, England). These extruders can include supply and ventilation ports and provide a high intensity distributive and dispersive mix. For example, components can be introduced into the same feed ports as the twin screw extruder and mixed by melting to form a substantially homogeneous molten mixture. If desired, other additives can also be injected into the polymer melt and / or introduced separately into the extruder at a different point along its length.
[57] Regardless of the processing technique in question, the resulting melt-melt composition typically contains micro-scale domains of the micro-inclusion additive and nanoscale domains of the nano-inclusion additive, 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 domains, so that they are unable to achieve the desired properties. For example, mixing normally takes place at a temperature of about 180 ° C to about 260 ° C; in some embodiments, from about 185 ° C to about 250 ° C, and in other embodiments, from about 190 ° C to about 240 ° C. Likewise, the apparent shear rate during the melting process can vary 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 other modalities, 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 fusion of the polymer and R is the radius ("m") of the capillary (eg, extruder mold) through which the molten polymer flows. Obviously, other variables, such as the residence time during melt processing, which is inversely proportional to the production rate, can also be controlled to achieve the desired degree of homogeneity.
[58] To achieve the desired shear conditions (for example, rate, dwell time, shear rate, melt processing temperature, etc.), the speed of the extruder thread (s) can be selected with a certain interval. Generally, an increase in the temperature of the product is observed with the increase in the screw speed due to the additional input of mechanical energy in the system. For example, the thread speed can vary from about 50 to about 600 revolutions per minute (“rpm”), in some modalities, from about 70 to about 500 rpm, and in some modalities, from about 100 to about 300 rpm. This can result in a temperature high enough to disperse the microinclusion additive without adversely impacting 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 extruder mixing section. Distributive mixers suitable for single screw extruders may include, for example, Saxon, Dulmage, Cavity Transfer, etc. Likewise, suitable dispersive mixers may include Blister ring, Leroy / Maddock, CRD mixers, etc. As is well known in the art, mixing can be further improved by using pins in the barrel that create a bending and reorientation of the polymer melt, such as those used in Buss Kneader extruders, Cavity Transfer mixers, and Vortex Intermeshing Pin (VIP) mixers ).
[59] Once mixed, the porous mesh structure is introduced by extracting the composition in a longitudinal direction (eg machine direction), transverse direction (eg machine direction), etc., as well as combinations of themselves. To perform the desired extraction, the thermoplastic composition can be formatted in a precursor format, extracted, and then converted into the desired material (for example, film, fiber, etc.). In one embodiment, the precursor form may be a film with a thickness from about 1 to about 5000 micrometers, in some embodiments from about 2 to about 4000 micrometers, in some embodiments from about 5 to about 2500 micrometers, and in some embodiments, from about 10 to about 500 micrometers. As an alternative to forming a precursor form, the thermoplastic composition can also be extracted in situ as it is being shaped into the desired shape for the polymeric material. In one embodiment, for example, the thermoplastic composition can be extracted while it is being formed into a film or fiber.
[60] In any case, several extraction techniques can be employed, such as suction (for example, fiber extraction units), elastic frame extraction, biaxial extraction, multiaxial extraction, profile extraction, vacuum extraction, etc. In one embodiment, for example, the composition is pushed with a machine sense advisor ("MDO"), such as those commercially available from Marshall and Willams, Co. of Providence, Rhode Island. MDO units typically have a plurality of extraction cylinders (for example, 5 to 8) that progressively push and taper the film towards the machine. The composition can be extracted by means of discrete extraction operations, whether individual or multiple. It should be noted that some of the cylinders in an MDO device may not be operating at progressively higher speeds. To extract the composition in the manner described above, it is generally preferable that the MDO cylinders are not heated. However, if desired, one or more cylinders can be slightly heated to facilitate the extraction process, as long as the temperature of the composition remains below the ranges determined above.
[61] The degree of extraction depends, in part, on the nature of the material being extracted (for example, fiber or film). Generally, the composition is extracted (for example, in the machine direction) at an extraction rate from about 1.1 to about 3.5, in some embodiments from about 1.2 to about 3 , 0, and in some embodiments, from about 1.3 to about 2.5. The pull rate can be determined by dividing the length of the stretched material by its length before stretching. The tensile rate can also vary to help achieve the desired properties, such as within the range of about 5% to about 1500% per minute of deformation, in some embodiments, from about 20% to about 1000% per minute. minute of deformation, and in some modalities, from about 25% to about 850% per minute of deformation. Generally, the composition is maintained at a temperature below the glass temperature of the matrix polymer and / or micro-inclusion additive during extraction. Among other things, this helps to ensure that the polymer chains are not altered to such an extent that the porous network becomes unstable. For example, the composition can be extracted at a temperature of at least about 10 ° C, in some embodiments at least about 20 ° C, and in some embodiments, at least about 30 ° C below the glass transition temperature. matrix polymer. For example, the composition can be extracted at a temperature of from about 0 ° C to about 50 ° C, in some embodiments from 15 ° C to about 40 ° C, and in some embodiments, at from about 20 ° C to about 30 ° C. Although the composition is usually extracted without the application of external heat (for example, heated cylinders), this heat can be optionally employed in order to improve processability, reduce extraction force, increase extraction rates and improve fiber uniformity.
[62] Extracting in the manner described above can result in the formation of pores that have a nanoscale dimension ("nanopores"). For example, nanopores can have an average cross-sectional dimension of about 800 nanometers or less, in some modalities, from about 1 to about 500 nanometers, in some modalities, from about 5 to about 450 nanometers, in some modalities , from about 5 to about 400 nanometers, and in some modalities, from about 10 to about 100 nanometers. Micropores can also be formed around and in the microscale domains during stretching to have an average cross-sectional dimension of about 0.5 to about 30 micrometers, in some embodiments, from about 1 to about 20 micrometers, and in some modalities, from about 2 micrometers to about 15 micrometers. Micropores and / or nanopores can have any regular or irregular shape, such as spherical, elongated, etc. In certain cases, the axial dimension of the micropores and / or nanopores can be greater than the transverse dimension so that the aspect ratio (the ratio between the axial dimension and the transverse dimension) is from about 1 to about 30, in some modalities, from about 1.1 to about 15, and in some modalities, from about 1.2 to about 5. The "axial dimension" is the dimension in the direction of the main axis (for example, length), which it is usually in the direction of the stretch.
[63] The present inventors have also discovered that pores (for example, micropores, nanopores, or both) can be distributed in a substantially homogeneous manner throughout the material. For example, pores can be distributed in columns that are oriented in a direction generally perpendicular to the direction in which the tension is applied. These columns can generally be parallel to each other over the entire width of the material. Without intending to be limited by theory, it is believed that the presence of this homogeneously distributed porous network can result in high thermal resistance, as well as good mechanical properties (for example, energy dissipation under load and impact resistance). There is a stark contrast to conventional techniques for creating pores that involve the use of blowing agents, which tends to result in an uncontrolled pore distribution and poor mechanical properties. Notably, the formation of the porous network by the process described above does not necessarily result in a substantial change in the transverse size (for example, width) of the material. In other words, the material is not substantially narrowed, which allows the material to retain a greater degree of strength properties.
[64] In addition to forming a porous network, stretching can also significantly increase the axial dimension of the microscale domains so that they have a generally linear, elongated shape. For example, elongated microscale domains may have an average axial dimension that is about 10% or more, in some embodiments, from about 20% to about 500%, and in some embodiments, from about 50% to about 250% larger than the axial dimension of the domains before stretching. The axial dimension after stretching can, for example, vary from about 0.5 to about 250 micrometers, in some embodiments, from about 1 to about 100 micrometers, in some embodiments, from about 2 to about 50 micrometers micrometers, and in some modalities, from about 5 to about 25 micrometers. The microscale domains can also be relatively thin and thus have a small cross-sectional dimension. For example, the transverse dimension may be from about 0.05 to about 50 micrometers, in some embodiments, from about 0.2 to about 10 micrometers, and in some embodiments, from about 0.5 to about 5 micrometers. This can result in an aspect ratio for the microscale domains (the ratio of the axial dimension to the cross-sectional dimension) from from 2 to about 150, in some embodiments from about 3 to about 100, and in some modalities, from about 4 to about 50.
[65] As a result of the elongated and porous domain structure, the present inventors have found that the resulting polymeric material can expand evenly in terms of volume when extracted in the longitudinal direction, which is reflected in a reduced "Poisson's ratio", as determined according to the following equation: Poisson's ratio = - Etransversal / Elongitudinal where Etransversal is the transversal deformation of the material and Elongitudinal is the longitudinal deformation of the material. More specifically, the Poisson's ratio of the material can be approximately 0 or even negative. For example, the Poisson's ratio may be about 0.1 or less, in some embodiments from about 0.08 or less, and in some embodiments, from about -0.1 to 0.04. When the Poisson's ratio is zero, there is no contraction in the transverse direction when the material is expanded in the longitudinal direction. When the Poisson's ratio is negative, the transversal or lateral dimensions of the material also expand when the material is stretched in the longitudinal direction. Materials with a negative Poisson's ratio can thus exhibit an increase in width when stretched in the longitudinal direction, which can result in greater absorption of energy in the cross direction.111.
[66] The polymeric material of the present invention can generally have a variety of different shapes, depending on the particular application, such as films, fibrous materials, molded articles, profiles, etc., as well as composites and laminates thereof, for use in cases of thermal insulation. In one embodiment, for example, the polymeric material is in the form of a film or film layer. Multilayer films can contain two (2) to fifteen (15) layers, and in some embodiments, three (3) to twelve (12) layers. Such multilayer films normally contain at least one base layer and at least one additional layer (e.g., surface layer), but can contain as many layers as desired. For example, the multilayer film can be formed from a base layer and one or more surface layers, wherein the base layer and / or surface layer or layers are formed from the polymeric material of the present invention. It should be understood, however, that other polymeric materials can also be employed in the base layer and / or surface layer or layers, such as polyolefin polymers.
[67] The film thickness can be relatively small in order to increase flexibility. For example, the film may have a thickness of 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 some embodiments , from about 10 to about 60 micrometers. Despite the low thickness, the film may, however, be able to maintain good mechanical properties during use. For example, the film can be relatively malleable. A parameter indicative of the film's ductility is the percentage of its elongation at its breaking point, as determined by the strain strain curve, as obtained in accordance with ASTM D638-10 at 23 ° C. For example, the percentage of elongation at the break of the film in the machine direction (“MD”) can be about 10% or more, in some modalities about 50% or more, in some modalities about 80% or more and , in other modalities, from about 100% to about 600%. Likewise, the percentage of elongation at the break of the film in the transverse direction (“CD”) can be around 15% or more, in some modalities around 40% or more, in some modalities around 70% or more and , in other modalities, from about 100% to about 400%. Another parameter indicative of ductility is the modulus of elasticity of the film, which is equal to the ratio of the tensile strength to elastic strain and is determined from the slope of the strain strain curve. For example, the film typically exhibits an MD and / or CD elastic modulus of about 2500 Megapascals ("MPa") or less, in some embodiments about 2200 MPa or less, in some embodiments of about 50 MPa to about 2000 MPa, and in some modalities, from about 100 MPa to about 1,000 MPa. The modulus of elasticity can be determined in accordance with ASTM D638-10 at 23 ° C.
[68] Although the film is ductile, it can still be relatively strong. A parameter indicative of the relative strength of the film is its maximum stress resistance, which is equal to the maximum stress obtained on a stress-strain curve, as obtained according to the ASTM D638-10 standard. For example, the film can exhibit a maximum strain MD and / or CD of about 5 to about 65 MPa, in some embodiments from about 10 to about 60 MPa and, in other embodiments, from about 20 MPa to about 55 MPa. The film may also exhibit an MD and / or CD voltage drop of about 5 MPa to about 60 MPa, in some embodiments from about 10 MPa to about 50 MPa and, in some embodiments, from about 20 MPa to about 45 MPa. The maximum stress and the breaking voltage can be determined in accordance with ASTM D638-10 at 23 ° C.
[69] In addition to a film, the polymeric material may also be in the form of a fibrous material or a layer or component of a fibrous material, which may include individual staple fibers or filaments (continuous fibers), as well as yarns, fabrics, etc., formed from such fibers. Yarns can include, for example, several staple fibers that are twisted together ("spun yarn"), filaments grouped without twist ("zero-twist yarn"), filaments defined together with a degree of twist, single filament with or without torsion ("monofilament"), etc. The yarn may or may not be textured. Suitable fabrics may also include, for example, fabrics, knitted fabrics, non-woven fabrics (heat-sealed continuous filament fabric, blow-extruded fabric, carded and combed fabric, wet fabric, airway fabric, co-form fabrics, hydraulically matted fabrics etc) and others.
[70] Fibers formed from the thermoplastic composition can generally have any desired configuration, including single-component and multi-component (for example, core-coat configuration, side-by-side configuration, segmented mixed configuration, island-at-sea configuration , and so on). In some embodiments, the fibers may contain one or more additional polymers as a component (eg, bicomponent) or constituent (eg, biconstituent) to further increase strength and other mechanical properties. For example, the thermoplastic composition 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, for example, polylactic acid, polyethylene terephthalate, polybutylene terephthalate, and so on; polyolefins, for example, polyethylene, polypropylene, polybutylene, and so on; 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.
[71] When used, fibers may, instead of fracturing, deform when pressure is applied. The fibers can thus continue to function as load-bearing members, even after the fiber has shown substantial elongation. In this respect, the fibers of the present invention are capable of exhibiting improved maximum elongation properties, for example, percentage of elongation of the fiber at its maximum loading. For example, the fibers of the present invention may exhibit a peak elongation of about 50% or more, in some embodiments, about 100% or more, in some embodiments, from about 200% to about 1500%, and in some embodiments some embodiments, from about 400% to about 800%, as determined according to ASTM D638-10 at 23 ° C. These stretches can be obtained for fibers that have a wide variety of average diameters, such as those that range from about 0.1 to 50 micrometers, in some modalities, from about 1 to 40 micrometers, in some modalities, from about 2 to about 25 micrometers, and in some modalities, from about 5 to about 15 micrometers.
[72] Although they have the ability to stretch under pressure, the fibers of the present invention can also remain relatively strong. For example, fibers may exhibit peak elastic stresses of about 25 to about 500 Megapascals ("MPa"), in some embodiments, from about 50 to about 300 MPa, and in some embodiments, from about 60 to about 200 MPa, as determined according to ASTM D638-10 at 23 ° C. Another parameter that is indicative of the relative strength of the fibers of the present invention is the "toughness", 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 have a toughness of 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. The denier of the fibers may vary, depending on the desired application. Normally fibers are formed to have a denier per filament (ie, the unit of linear density equal to the mass in grams per 9000 meters of fiber) less than about 6, in some embodiments, less than about 3 and, in some modalities, from about 0.5 to about 3.
[73] If desired, the polymeric material of the present invention can be subjected to one or more additional steps, before and / or after extraction. Examples of such processes include, for example, grooved cylinder extraction, engraving, coating etc. In certain embodiments, the polymeric material can also be annealed to ensure that it retains the designed shape. Annealing normally occurs at temperatures above the glass transition temperature of the matrix polymer, such as temperatures from about 40 ° C to about 120 ° C; in some embodiments from about 50 ° C to about 100 ° C; and in other embodiments, from about 70 ° C to about 90 ° C. The fibers can also be surface treated using any of several known techniques to improve their properties. For example, high-energy beams (for example, plasma, x-rays, electron beam, etc.) can be used to remove or reduce any surface layers, change surface polarity, porosity, topography, weaken a surface layer , etc. If desired, such a surface treatment can be used before and / or extraction of the thermoplastic composition.
[74] Regardless of its particular shape, the polymeric material can be used in a wide range of types of insulation for thermal administration of essentially any surface or volume, whether fully or partially inserted. Non-limiting examples include insulation materials for refrigeration units (eg refrigerators, freezers, vending machines, etc.); automotive components (for example, rear and front seats, head rests, arm rests, door panels, rear shelves / luggage racks, steering wheels and interior trim, car dashboard, etc.); clothing (for example, coats, shirts, pants, gloves, aprons, bibs, shoes, boots, headwear, lining for socks, etc.); furniture and bedding (for example, sleeping bags, comforters, etc.); fluid storage / transfer systems (for example, tubes or tanks for liquid or gaseous hydrocarbons, liquid nitrogen, oxygen, hydrogen or crude oil); extreme environments (for example, submarine or space); food or drink products (for example, cups, cup holders, plates, etc.); containers and bottles; and others.
[75] Building panels, for example, can be formed from the polymeric material of the present invention and used without limitation in the construction of foundation walls, front walls (for example, in buildings that do not have a basement), curtain walls of manufactured home base, floor systems, ceiling systems, upper exterior walls, curtain walls, exterior walls in areas using exterior masonry, etc. With reference, for example, to Figs. 1-2, an embodiment of a construction panel (e.g., foundation wall panel) that can be formed in accordance with the present invention is shown in more detail. As illustrated, a building contains exterior and interior foundation walls 10 that collectively define a foundation 12. Each foundation wall 10 is in turn defined by one or more foundation wall panels 14. In the illustration, each foundation panel foundation wall 14 includes a bottom plate 16 and a vertical wall section 18, and an upper plate 20. Each vertical wall section 18 includes a main wall section 22 and vertically oriented reinforcement pins 23 affixed to or integral with the section of main wall, evenly spaced along the length of the wall section and extending internally in relation to the interior surface of the main wall section. In the embodiment illustrated in Fig. 1, wedge-shaped anchoring brackets 24 are attached to the pins at the top and bottom of the wall section to assist in anchoring the bottom and top plates, and / or any other attachment, to the portion main section of the vertical wall section.
[76] As illustrated, conventional beams 26 (for example, I-shaped steel beams) are attached to the wall sections, as necessary, in order to support overlying stretches of floor. Such beams can be supported as needed by columns 28 and / or fillers 30. Additional support columns can also be employed at the ends of the beams, or adjacent to them, in order to meet specific requirements of the individual building design. Solid reinforcement pins 23 can be used to attach the beams to respective panels of the foundation wall. As shown in Fig. 2, a main wall section 22 is generally defined between an inner surface and the extreme surface of the wall panel 14. In accordance with an embodiment of the present invention, the wall section 22 may include the polymeric material of the present invention as thermal insulation 32, which provides a thermal barrier between the face surface facing inwards of the wall and the wall surface facing outwards of the wall. The lower plate 16 and the upper plate 20 can be fixed to the main section 22 with the support of wedge-shaped supports 24 or other support structures. The bottom plate 16 can support the foundation wall and superstructure of overlying construction from an underlying fabricated base, such as, for example, concrete baseboard 55.
[77] In more embodiments of the present invention, the polymeric material of the present invention can be used in clothing, such as shoes and clothing. The polymeric material can be used to form the garments themselves or simply as a lining. Referring to Figs. 3-4, for example, an embodiment of a thermal lining 100 for a shoe is shown, which can be formed from the polymeric material of the present invention. In this specific embodiment, the thermal liner 100 contains a thermal insulation layer 112, which can be formed from the polymeric material of the present invention, and which is encapsulated within the limits of the support layers 114 and 116. Normally, the insulation 112 is cut and then arranged on an upper surface 113 of the first support layer 114. The thermal lining 100 is completed with the second support layer 116 having a garment material 118 laminated to an upper surface 122 of a layer of material polymeric 120, on the insulation layer 112. The periphery of the first and second support layer 114 and 116 can be hermetically sealed by an ultrasonic or high frequency welder to surround the insulation layer 112. The lining 100 can also include a region front 125, which includes the upper and lower layers joined together without any insulation material 112 between them. This front region includes raised contour lines 127 with cut lines along which lining 100 can be trimmed to fit various shoe sizes. In other additional embodiments, the thermal liner 100 is formed entirely from the polymeric material of the present invention.
[78] Other types of clothing and thermal linings can also be formed in accordance with the present invention. With reference to Fig. 5, for example, an embodiment of a vest 200 (for example, a jacket) that includes a body portion 220, sleeves 222 and a collar 224 attached to the body portion. In this specific embodiment, the garment 200 is formed from a fabric 202 that is a laminate that includes an outer layer 212 and an inner layer 214, which defines a surface facing the body 225. The outer layer 212 also includes a closure front 226 which includes latches 228, or alternatively a sliding fastener (not shown). If desired, outer layer 212 and / or inner layer 214 can be formed from the polymeric material of the present invention. However, in certain embodiments, the outer wall 212 may be another material, such as nylon, polyester, cotton, or mixtures thereof. In yet other embodiments, the garment 200 is formed entirely from the polymeric material of the present invention.
[79] The polymeric material can be used in the formation of thermal insulation materials in automotive applications. For example, fibers of the polymeric material can be used beneficially in articles that can improve the comfort and / or aesthetics of a vehicle, as well as providing a thermal barrier (for example, covers and / or padding for visors, housings for loudspeakers and covers, seat covers, sealing slip agents and linings for seat covers, carpets and carpet reinforcements including carpet liners, car mats and car mat liners, seat belt covers and belt anchors safety cover, luggage compartment cover, decorative fabrics in general, etc.), as well as materials that can provide thermal insulation in general (for example, column filling, fillings for door linings, hood linings, sound insulation materials exhaust mufflers, body parts, windows, sunroofs, pneumatic reinforcements, etc.).
[80] Use of polymeric material is applicable to a wide range of transport applications and is in no way intended to be limited to the automotive industry. For example, the polymeric material can be used in the transport industry in any suitable application, including, without limitation, air and space applications (for example, aircraft, helicopters, space transport, military aerospace devices, etc.), marine applications ( boats, ships, recreational vehicles), trains and others.
[81] The present invention can be better understood with reference to the following examples. Test Methods Conductive Properties:
[82] Thermal conductivity (W / mK) and thermal resistance (m2K / W) were determined in accordance with ASTM E-1530-11 (“Resistance to Technical Transmission of Materials by the Guarded Heat Flow Meter Technique) ) using an Anter Unitherm Model 2022 tester. The target test temperature was 25 ° C and the applied load was 0.17 MPa. Before testing, the samples were conditioned for more than 40 hours at a temperature of 23 ° C (+2 ° C) and a relative humidity of 50% (+ 10%). Thermal admittance (W / m2K) was also calculated by dividing 1 by thermal resistance. Melt Flow Rate:
[83] The melt flow rate (“MFR”) is the weight of a polymer (in grams) forced through an extrusion rheometer orifice (0.0825 inch in diameter) when subjected to a load of 2,160 grams in 10 minutes, usually at 190 ° C, 210 ° C, or 230 ° C. Unless otherwise stated, the melt flow rate is measured according to the ASTM D1239 test method with a Tinius Olsen Extrusion Plastometer. Thermal Properties:
[84] The glass transition temperature (Tg) can be determined by means of dynamic-mechanical analysis (DMA), according to ASTM E1640-09. A TA Instruments Q800 instrument can be used. Experimental runs can be performed in tension / tension geometry, in a temperature sweep mode in the range of -120 ° C to 150 ° C with a heating rate of 3 ° C / min. The frequency of the power amplitude 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 between the loss module and the storage (tangent δ = E ”/ E ').
[85] The melting temperature can be determined using differential scanning calorimetry (DSC). The differential scanning calorimeter can be a DSC Q100 differential scanning calorimeter, which can be prepared with a liquid nitrogen cooling accessory and with a UNIVERSAL ANALYSIS 2000 (version 4.6.6) analysis software program, both available from TA Instruments Inc. of New Castle, Delaware. To avoid direct handling of the samples, tweezers and other tools can be used. The samples can be placed on an aluminum plate and weighed to the nearest 0.01 milligram on an analytical balance. A lid can be placed over the material sample on the plate. Normally, resin pellets can be placed directly on the weighing pan.
[86] The differential scanning calorimeter can be calibrated using an Indian metal standard and a baseline correction can be made, as described in the operating manual of the differential scanning calorimeter. The material sample can be placed in the test chamber of the differential scanning calorimeter for testing, and an empty plate can be used as a reference. All tests can be performed by purging with nitrogen of 55 cubic centimeters per minute (industrial grade) in the test chamber. For resin pellet samples, the heating and cooling program is a 2-cycle test that started with the chamber balance at - 30 ° C, followed by a first heating period, at a heating rate of 10 ° C per minute to a temperature of 200 ° C, followed by equilibrating the sample at 200 ° C for 3 minutes, followed by a first cooling period at a cooling rate of 10 ° C per minute, at a temperature of -30 ° C, followed by equilibrating the sample at -30 ° C for 3 minutes, and then a second heating period, at a heating rate of 10 ° C per minute at a temperature of 200 ° C. For fiber samples, the heating and cooling program can be a 1-cycle test that starts with the chamber balance at -25 ° C, followed by a warm-up period at a heating rate of 10 ° C per minute at temperature of 200 ° C, followed by equilibrating the sample at 200 ° C for 3 minutes, and then a cooling period at a cooling rate of 10 ° C per minute to a temperature of -30 ° C. All tests are carried out with a nitrogen purge of 55 cubic centimeters per minute (industrial grade) in the test chamber.
[87] Results can be evaluated using the UNIVERSAL ANALYSIS 2000 analysis software program, 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 graphs . The glass transition temperature can be identified as the region of the graph line where a sharp change in slope has occurred, and the melting temperature can be determined using an automatic inflection calculation. Elastic Film Properties:
[88] The elastic properties of films (maximum stress, modulus, rupture deformation and energy per rupture volume) were tested on an MTS Synergie 200 elasticity frame. The test was carried out in accordance with ASTM D638-10 (a about 23 ° C). Film samples were cut into a canine bone shape with a central width of 3.0 mm before testing. Canine bone film samples can be held in place using handle elements on the MTS Synergie 200 device with a measurement length of 18.0 mm. The film samples were stretched at a traction speed of 5.0 in / min until rupture occurred. Five samples can be tested for each film in both the machine (MD) and transverse (CD) directions. A computer program (for example, TestWorks 4) can be used to collect data during the test and generate a stress versus strain curve, from which various properties can be determined, including modulus, maximum stress, elongation and energy in the break. Fiber Elastic Properties:
[89] Elastic properties of the fiber can be determined in accordance with ASTM 638-10 at 23 ° C. For example, individual specimens of fiber can be initially shortened (for example, cut with scissors) to 38 mm in length, and placed separately on a piece of black velvet. 10 to 15 samples can be collected in this way. The fiber samples can then be mounted in a substantially straight condition on a rectangular paper structure, with external dimensions of 51 mm x 51 mm and internal dimensions of 25 mm x 25 mm. The ends of each fiber sample can be operationally attached to the structure, carefully attaching the ends of the fibers to the sides of the structure with adhesive tape. Each fiber sample can then be measured for its relatively short, external, cross-fiber dimension, using a conventional laboratory microscope, which can be properly calibrated and adjusted with 40X magnification. The cross fiber dimension can be recorded as the diameter of the individual fiber sample. The structure assists in the assembly of the ends of the fiber samples in the upper and lower fixations of a constant rate of the extension type elastic tester, in order to avoid excessive damage to the fiber samples.
[90] A constant rate of the type of extension of the elastic tester and an appropriate load cell can be employed in the test. The load cell can be chosen (for example, 10N) so that the test value is between 1090% of the total load scale. The elastic tester (ie, MTS SYNERGY 200) and the load cell can be obtained from MTS Systems Corporation, of Eden Prairie, Michigan. The fiber samples in the frame assembly can then be mounted between the clamps of the elastic tester, such that the ends of the fibers are operationally maintained by the clamps of the elastic tester. Then, the sides of the paper structure that extend parallel to the length of the fiber can be cut or otherwise separated so that the elastic tester applies the test force only to the fibers. The fibers can then be subjected to a tensile test, with a tensile rate and claw speed of 12 inches per minute. The resulting data can be analyzed using a TESTWORKS 4 software program from MTS Corporation, with the following test setup:


[91] The toughness values can be expressed in terms of gram-force per denier. Peak elongation (% of force at break) and peak stress can also be calculated. Expansion Ratio, Density and Percent Pore Volume:
[92] To determine the expansion ratio, density and percentage pore volume, the width (Wi) and thickness (Ti) of the sample were initially measured before stretching. The length (Li) before stretching could also be determined by measuring the distance between two marks on a sample surface. Consequently, the sample could be stretched to start emptying. The width (Wf), thickness (Tf) and length (Lf) of the sample could then be measured as close to 0.01 mm using a Digimatic Compass (Mitutoyo Corporation). The volume (Vi) before stretching could be calculated by Wi x Ti x Li = Vi. The volume (Vf) after stretching could be calculated by Wf x Tf x Lf = Vf. The expansion ratio (Φ) could be calculated by Φ = Vf / Vi; density (Pf) was calculated by: Pf = Pi / Φ, where Pi is the density of the precursor material; and the percentage pore volume (% Vv) could be calculated by:% Vv = (1 - 1 / Φ) x 100. Moisture content:
[93] The moisture content can be determined using an Arizona Instruments Computrac Vapor Pro moisture analyzer (Model No. 3100) substantially in accordance with ASTM D 7191-05, which is incorporated in its entirety in this document by reference for all purposes. . The test temperature (§X2.1.2) can be 130 ° C, the sample size (§X2.1.1) can be 2 to 4 grams, and the bottle purging 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 calculate the moisture content parameter) are met.
[94] The ability to form a polymeric material for use in thermal insulation has been demonstrated. At first, a mixture of 85.3% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.5% by weight of a micro-inclusion additive, 1.4% by weight of a nano-inclusion additive was demonstrated , and 3.8% by weight of an interfacial modifier. The microinclusion additive was Vistamaxx ™ 2120 (ExxonMobil), which is a polyolefin / elastomer copolymer with a melt flow rate of 29 g / 10 min (190 ° C, 2160 g) and a density of 0.866 g / cm3 . The nanoinclusion additive was poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (Lotader® AX8900, Arkema) with a melt flow rate of 5-6 g / 10 min (190 ° C / 2160 g) , a glycidyl methacrylate content of 7 to 11% by weight, methyl acrylate content of 13 to 17% by weight, and ethylene content of 72 to 80% by weight, the internal interfacil modifier was the WI 285 PLURIOL lubricant ® from BASF which are polyalkylene glycol functional fluids. The polymers were introduced into a co-rotating twin screw extruder (ZSK-30, diameter 30 mm, length 1328 mm) for compounds that were manufactured by Werner and Pfleiderer Corporation, of Ramsey, New Jersey. The extruder had 14 zones, numbered sequentially from 1-14, from the feed funnel to the mold. The first zone of barrel No. 1 received the resins by means of a gravimetric feeder at a total flow of 15 pounds per hour. PLURIOL® WI285 was added by means of an injection pump in barrel zone no. 2. The mold used to extrude the resin had 3 mold openings (6 mm in diameter) that were separated by 4 mm. After formation, the extruded resin was cooled on a conveyor belt cooled by ventilation and formed into pellets by a Conair pelletizer. The screw speed of the extruder was 200 revolutions per minute ("rpm"). The pellets were then fed en masse to a signal screw extruder heated to a temperature of 212 ° C where the molten mixture exited through a 4.5 inch slit and extracted at a film thickness between 0.54 to 0, 58 mm. EXAMPLE 2
[95] The sheet produced in Example 1 was cut to a length of 6 "and extracted until reaching 100% elongation using hydraulic tension frame MTS 820 in an elastic mode at 50 mm / min. EXAMPLE 3
[96] The sheet produced in example 1 was cut to a length of 6 "and then stretched to 150% elongation using an 820 MTS hydraulic pull frame in 50 mm / min pull mode. EXAMPLE 4
[97] The sheet produced in Example 1 was cut to a length of 6 "and then stretched to 200% elongation using MTS 820 hydraulic tension frame in tension mode at 50 mm / min.
[98] The thermal properties of Examples 14 were then determined. The results are shown in the table below.
EXAMPLE 5
[99] The pellets were formed as described in Example 1 and then mass fed to a Rheomix 252 signal screw extruder with an L / D ratio of 25: 1 and heated to a temperature of about 212 ° C where the molten mixture came out of a 6-inch cast film Haake matrix, and was extracted to a film thickness in the range between 39.4 μm and 50.8 μm using a Haake collection cylinder. The film was extracted in the machine direction at a 160% longitudinal deformation at a tensile rate of 50 mm / min (deformation rate of 67% per min) using the MTS Synergie 200 tension frame with long handle elements. of 75 mm. EXAMPLE 6
[100] Films were formed as described in Example 5, but the film was also extracted transversely to 100% deformation at a tensile rate of 50 mm / min (deformation rate of 100%) with handle elements at measurement lengths of 50 mm.
[101] Various properties of the films of examples 5 to 6 were tested as described above. The results are shown in tables 1 and 2. Table 1: Film properties
Table 2: Elastic properties
EXAMPLE 7
[102] The pellets were formed as described in Example 1 and then fed in bulk to a signal screw extruder heated to a temperature of 212 ° C, where the molten mixture came out through a 4-slot die , 5 inches and extracted to a film thickness between 36 μm to 54 μm. The films were extracted in the machine direction up to about 100% in order to initiate cavitation and vacuum formation. The film morphology was analyzed by scanning electron microscopy (SEM) before and after stretching. The results are shown in Figs. 6 to 9. As shown in Figs. 6-7, the microinclusion additive was initially dispersed by domains with axial size (in the machine direction) from about 2 to about 30 micrometers and a transverse dimension (in a transverse direction) from about 1 to about 3 micrometers, whereas the nanoinclusion additive was initially dispersed as spherical and spheroidal domains with axial size from about 100 to about 300 nanometers. Figs. 8 to 9 show the film after stretching. As indicated, pores were formed around micro-inclusion and nano-inclusion additives. The micropores formed around the microinclusion additive were generally elongated in a 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 nanoinclusion additive are generally between 50 and 500 nanometers in size. EXAMPLE 8
[103] The compound pellets of Example 7 were dry mixed with another nanoinclusion additive, which was a halo-clay masterbatch (MacroComp MNH-731-36, MacroM) containing 22% by weight of a modified styrenic copolymer nano-clay. 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 masterbatch, which provided a total clay content of 2.2%. The dry mixture was then fed in bulk to a signal screw extruder heated to a temperature of 212 ° C, where the molten mixture came out through a 4.5 inch wide slit matrix and extracted to a film thickness in a range of 51 to 58 μm. The films were extracted in the machine direction up to about 100% in order to initiate cavitation and vacuum formation.
[104] The morphology of the films was analyzed using electron scanning microscopy (SEM) before and after stretching. The results are shown in Figs. 10-13. As shown in Figs. 10-11, some of the nano-clay particles (visible as lighter regions) have become dispersed in the form of very small domains - that is, of axial dimension in a range of about 50 to about 300 nanometers. The masterbatch itself also formed domains of a microscale size (axial dimension from about 1 to about 5 micrometers). Also, the micro-inclusion additive (Vistamaxx ™) formed elongated domains, while the nano-inclusion additives (Lotader®, visible as ultrafine dark spots and nano-clay masterbatch, visible as light platelets) formed spheroidal domains. The spheroidal film is shown in Figs. 12-13. As structured, the cavitated structure is more open and demonstrates a wide variety of pore sizes. In addition to highly elongated micropores formed by microinclusions (Vistamaxx ™), nano-clay masterbatch inclusions formed more open spheroidal micropores with an axial size of about 10 microns or less and a cross-sectional size of about 2 microns. Spherical nanopores are also formed by nano-inclusion additives (Lotader® and nano-clay particles).
[105] Various elastic properties (machine sense) of the films of Example 1 and 2 were also tested. The results are provided below in Table 3.Table 3

[106] As shown, the addition of the nanoclay load resulted in a slight increase in the tensile strength and a significant increase in elongation at break. EXAMPLE 9
[107] The ability to form fibers for use in thermal insulation has been demonstrated. Initially, a precursor mixture was formed by 91.8% by weight of isotactic propylene homopolymer (M3661, melt flow rate of 14 g / 10 at 210 ° C and melting temperature of 150 ° C, Total Petrochemicals), 7 , 4% by weight of polylactic acid (PLA 6252, melt flow rate from 70 to 85 g / 10 min at 210 ° C, Natureworks®), and 0.7% by weight of a polyepoxide. The polyepoxide was poly (ethylene-co-methyl acrylate-co-glycidyl methacrylate) (LOTADER® AX8900, Arkema) having a melt flow rate of 6 g / 10 min (190 ° C / 2160 g), a content of glycidyl methacrylate of 8% by weight, methyl acrylate content of 24% by weight, and ethylene content of 68% by weight. The components were composed in a co-rotation twin screw extruder (Werner and Pfleiderer ZSK-30 with a diameter of 30 mm and an L / D = 44). The extruder had seven heating zones. The temperature in the extruder ranged from 180 ° C to 220 ° C. The polymer was introduced by gravimetry into the funnel extruder at 15 pounds per hour and the liquid was injected into the barrel using a peristaltic pump. The extruder was operated at 200 revolutions per minute (RPM). In the last section of the barrel (front), a mold with 3 holes of 6 mm in diameter was used to form the extrudate. The extrudate was air-cooled on a conveyor belt and pelletized using a Conair pelletizer.
[108] The fiber was then produced from the precursor mixture using a Davis-Standard fiber rotation line equipped with a 0.75 inch single-screw extruder and a 16-hole die with a 0.6 mm diameter. The fibers were collected in different tensile ratios. The shortening speed varied from 1 to 1,000 m / min. The temperature of the extruder ranged from 175 ° C to 220 ° C. The fibers were stretched in an elastic testing machine at 300 mm / min up to 400% elongation at 25 ° C. To analyze the material's morphology, the fibers were broken by freezing in liquid nitrogen and analyzed using a Jeol 6490LV scanning electron microscope in high vacuum. The results are shown in Figs. 14-16. As shown, spheroid pores are formed which are stretched in the direction of stretching. Both nanopores (~ 50 nanometers wide, ~ 500 nanometers long) and micropores (~ 0.5 micrometer wide, ~ 4 micrometers long) were formed. EXAMPLE 10
[109] The pellets were formed as described in Example 1 and then fed in bulk to a single screw extruder at 240 ° C, melted and passed through a casting pump at a rate of 0.40 grams per orifice per minutes through a 0.6 mm diameter die. The fibers were collected in free fall (only gravity acting as a tensile force) and then tested for mechanical properties at a tensile rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an elastic MTS Synergie structure at a rate of 50 mm / min. The fibers were stretched at predefined forces of 50%, 100%, 150%, 200% and 250%. After stretching, the expansion ratio, void volume and density were calculated for various strength rates as shown in the tables below.
EXAMPLE 11
[110] The fibers were formed as described in Example 10, with the exception that they were collected at a collection cylinder speed of 100 meters per minute, resulting in a tensile rate of 77. The fibers were then tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an elastic MTS Synergie structure at a rate of 50 mm / min. The fibers were stretched at predefined forces of 50%, 100%, 150%, 200% and 250%. After stretching, the expansion ratio, void volume and density were calculated for various strength rates as shown in the tables below.

EXAMPLE 12
[111] The fibers were formed as described in Example 10, except that the mixture contained 83.7% by weight of polylactic acid (PLA 6201D, Natureworks®), 9.3% by weight Vistamaxx ™ 2120, 1 , 4% by weight of Lotader® AX8900, 3.7% by weight PLURIOL® WI 285 and 1.9% by weight of hydrophilic surfactant (Masil SF-19). PLURIOL® WI285 and Masil SF-19 were premixed in a 2: 1 ratio (WI-285: SF-19) and added via injection pump to barrel # 2. The fibers were collected at 240 ° C, 0.40 ghm and under free fall. EXAMPLE 13
[112] The fibers were formed as described in Example 12, with the exception that they were collected at a collection cylinder speed of 100 meters per minute, resulting in a tensile rate of 77. The fibers were then tested for mechanical properties at a pull rate of 50 millimeters per minute. The fibers were then cold drawn at 23 ° C in an elastic MTS Synergie structure at a rate of 50 mm / min. The fibers were stretched at a pre-defined strength of 100%. After stretching, the expansion ratio, void volume and density were calculated as shown in the tables below.

EXAMPLE 14
[113] The fibers of Example 12 were stretched on an MTS Synergie Tensile frame, at a speed of 50 millimeters per minute at 250% deformation. This opened the structure of empty spaces and made the fiber white. A one-inch sample was then cut from the tensioned white area of the fiber. The new fiber was then tested as described above. The density was estimated to be 0.75 grams per cubic centimeter and the tensile rate for the elastic test was 305 mm / min. EXAMPLE 15
[114] The fibers of Example 11 were heated in a 50 ° C oven for 30 minutes to anneal the fiber. EXAMPLE 16
[115] The fibers of Example 11 were heated in an oven at 90 ° C for 5 minutes to anneal the fiber and induce crystallization.
[116] The fibers in Examples 10-16 were then tested for mechanical properties at a tensile rate of 50 millimeters per minute. The results are shown in the table below.


[117] Although the invention has been described in detail in relation to its specific modalities, it will be contemplated that those skilled in the art, after obtaining an understanding of the above, can easily conceive of changes, variations and equivalents of these modalities. Accordingly, the scope of the present invention should be assessed as that of the appended claims and any equivalents thereto.

权利要求:
Claims (15)
[0001]
1. Polymeric material for use in thermal insulation, CHARACTERIZED by the fact that the polymeric material is formed from a thermoplastic composition that contains a continuous phase that includes a matrix polymer, and in which, additionally, a polymeric nanoinclusion additive is dispersed and a polymeric microinclusion additive within the continuous phase in the form of discrete domains, in which a porous network is defined in the material which includes a plurality of nanopores with an average cross-sectional dimension of 800 nanometers or less, with the polymeric material exhibiting conductivity temperature of 0.20 watts per meter-kelvin or less, where the micro-scale domains have an average cross-sectional dimension of 0.5 to 250 micrometers and the nanoscale domains have a cross-sectional dimension of 1 nanometer to 500 nanometers, in whereas the micro-inclusion additive constitutes 0.1% by weight to 30% by weight of the composition, and that the nano-inclusion additive constitutes 0.01% by weight at 15% by weight of the composition.
[0002]
2. Polymeric material, according to claim 1, CHARACTERIZED by the fact that the polymeric material exhibits a thermal conductivity of 0.02 to 0.10 watts per meter-kelvin and / or the polymeric material exhibits a thermal admittance of 1,000 watts per square meter-kelvin or less.
[0003]
3. Polymeric material, according to claim 1 or 2, CHARACTERIZED by the fact that the nanopores have a cross-sectional dimension of 5 to 400 nanometers and / or in which the nanopores constitute 20% by volume or more of the total pore volume polymeric material.
[0004]
4. Polymeric material, according to any of the preceding claims, CHARACTERIZED by the fact that the total pore volume of the polymeric material is 15% to 80% per cubic centimeter and / or in which the thermoplastic composition has a density of 1 , 2 grams per cubic centimeter or less.
[0005]
5. Polymeric material, according to any one of the preceding claims, CHARACTERIZED by the fact that the continuous phase constitutes from 60% by weight to 99% by weight of the thermoplastic composition and / or in which the microinclusion additive constitutes 1% in weight at 30% by weight of the composition, based on the weight of the continuous phase, and / or where the nanoinclusion additive constitutes from 0.05% by weight to 20% by weight of the composition, based on the weight of the continuous phase.
[0006]
6. Polymeric material according to any one of the preceding claims, CHARACTERIZED by the fact that the matrix polymer includes a polyester or polyolefin and / or in which the matrix polymer has a glass transition temperature of 0 ° C or more, such as polylactic acid.
[0007]
7. Polymeric material according to any one of the preceding claims, CHARACTERIZED by the fact that the microinclusion additive is a polyolefin, such as a propylene homopolymer, a propylene / α-olefin copolymer, an ethylene / α- copolymer olefin or a combination of these.
[0008]
8. Polymeric material, according to any one of the claims, CHARACTERIZED by the fact that the ratio of the matrix polymer solubility parameter to the microinclusion additive solubility parameter is 0.5 to 1.5, the rate ratio melt flow rate of the matrix polymer for the melt flow rate of the microinclusion additive is 0.2 to 8, and / or the ratio of the Young modulus of the matrix polymer to the Young modulus of the microinclusion additive is from 1 to 250.
[0009]
9. Polymeric material, according to any of the preceding claims, CHARACTERIZED by the fact that the nanoinclusion additive is a functionalized polyolefin, such as a polyepoxy; or where the nano-inclusion additive is a nanocharge.
[0010]
10. Polymeric material according to any one of the preceding claims, CHARACTERIZED by the fact that the thermoplastic composition additionally comprises an interphase modifier, such as silicone, silicone-polyether copolymer, aliphatic polyester, aromatic polyester, alkylene glycol, alkane diol, amine oxide, fatty acid ester or a combination thereof, preferably in an amount of 0.1% by weight to 20% by weight of the composition, based on the weight of the continuous phase.
[0011]
11. Polymeric material, according to any of the preceding claims, CHARACTERIZED by the fact that the polymeric material is generally free of gaseous blowing agents.
[0012]
12. Polymeric material, according to any of the previous claims, CHARACTERIZED by the fact that the porous network additionally includes micropores, in which the micropores have an average cross-sectional dimension of 0.5 to 30 micrometers; and or where the micropores have an aspect ratio of 1 to 30.
[0013]
13. Thermal insulation, CHARACTERIZED by the fact that it comprises the polymeric material as defined in any of the preceding claims.
[0014]
14. ARTICLE CHARACTERIZED by the fact that it comprises thermal insulation as defined in claim 13, in which the article is selected from the group consisting of a construction panel or section, an automotive component; a piece of clothing, an article of furniture, or an article of bedding.
[0015]
15. Method for forming the polymeric material as defined in any of claims 1 to 12, the method CHARACTERIZED by the fact that it comprises the extraction, at an extraction rate of 1.1 to 3.5, of the thermoplastic composition at a temperature which is less than the glass transition temperature of the matrix polymer to create the porous network, preferably at a temperature of at least 10 ° C lower than the glass transition temperature of the matrix polymer.

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法律状态:
2018-02-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|

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2019-12-10| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|

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2020-09-08| B09A| Decision: intention to grant|

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2020-12-08| 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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US201361833992P| true| 2013-06-12|2013-06-12|

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US61/833,992|2013-06-12|

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US201361907562P| true| 2013-11-22|2013-11-22|

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US61/907,562|2013-11-22|

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PCT/IB2014/062028|WO2014199276A1|2013-06-12|2014-06-06|Polymeric material for use in thermal insulation|

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