Polystyrene foams with fluoropolymer additives, compositions and methods of making same

Abstract

A foamed polymer composition includes: a matrix polymer component including polystyrene (PS), a copolymer thereof, or a combination thereof; and from 0.003 wt% to 0.15 wt%, based on the weight of the polymer composition, of a fluoropolymer component comprising a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulation polymer, or a combination thereof. The composition has a specific compressive strength of from 8 kPa / m < 3 > / m < 3 > (kPa.m < 3 > / kg) to 65 kPa.m < 3 > / kg, or in some aspects from 8 kPa.m < 3 > / kg to 35 kPa.m < 3 > / kg, or from 12 kPa.m < 3 > / kg to 65 kPa.m < 3 > / kg, or from 12 kPa.m < 3 > / kg to 35 kPa.m < 3 > / kg, as determined according to ISO 844 using a universal testing machine. A method for preparing the foamed polymer composition is also described.

Description

Technical Field

[0001] The present disclosure relates to foamable polymer compositions, and more particularly to foamable polymer compositions comprising polystyrene and a fluoropolymer component including a fibrillated fluoropolymer. Background Art

[0002] Nanofibrillated polytetrafluoroethylene (PTFE) can improve the mechanical properties of polymer blends, such as increasing modulus, strength, ductility, and viscoelasticity. To maximize the degree of PTFE nanofibrillation in thermoplastic resins during extrusion without agglomeration, specific die designs and process windows are employed. More specifically, to maximize nanofibrillation, lower throughput and higher melt temperatures are employed, unfortunately resulting in unfavorable manufacturing economics. These disadvantages are less pronounced for semicrystalline resins such as polyethylene terephthalate (PET), polypropylene (PP), polylactic acid (PLA), and polyamide (PA), due to their inherently low viscosity. However, for amorphous resins such as polystyrene, a base resin with an optimal viscosity is required to achieve high throughput and ensure efficient nanofibrillation during industrial extrusion processes. Specifically, since using polystyrene resins with higher flowability (lower viscosity, lower molecular weight) can compromise their mechanical properties, there is a need for high-flow polystyrene resins with improved mechanical properties.

[0003] In addition, due to new environmental policies, all industries need to reduce carbon dioxide (CO2) emissions. More specifically, for the transportation, logistics and mobility industries, lightweight structures are needed to reduce vehicle fuel consumption, improve energy efficiency or increase payload capacity. For example, the panels, walls and / or roof of a refrigerated truck or caravan may include structural and thermally insulating extruded polystyrene (XPS) foam boards. There are various XPS boards on the market with different compressive strength, foam density, flame retardant properties and sizes (thickness, width and length); the selection of a suitable XPS board depends on the application requirements. Specifically, a thickness of 10-50 millimeters (mm), a compressive strength of 500-700 kilopascals (kPa) and a foam density of 35-38 kilograms per cubic meter (kg / m 3 ) thin XPS foam is used in some applications. Conventional XPS foam is available from, for example, Ravago (Ravatherm™ XPS foam) and JACKON (JACKODUR® XPS foam).

[0004] There is also a desire to reduce the energy footprint of residential buildings through the use of floor and / or wall insulation. Thin XPS foam boards are ideal for use in wet indoor environments such as bathrooms and shower areas during new construction or renovations. However, producing thin (4-20 mm thick) and wide (900-1200 mm wide) XPS boards with compressive strengths of 300 kPa or higher is difficult due to processing inconsistencies (surface quality, cell size uniformity) caused by limitations of conventional talc foam nucleating agents. More specifically, talc masterbatches cannot adequately control foam morphology, resulting in non-uniform cell size, increased thickness due to expansion, increased width due to necking at the die exit, and poor foam skin appearance. Conventional foam nucleating agents, such as talc masterbatches (40-60 wt% talc in a polystyrene (PS) matrix), are typically used at dosages up to 1.5%, but they fail to meet the width, thickness, and performance criteria mentioned above. Higher talc foam nucleating dosages of up to 10 wt% have been reported, but these foams fail to meet the desired size and performance criteria mentioned above. See, for example: (1) Demirtas et al., “Extrusion Foaming of High Impact Polystyrene: Effects of Processing Parameters and Materials Composition,” Int J Mater Sci Res. 2018, 1(1): 9-15; and (2) U.S. Patent No. 10,160,843, issued December 25, 2018, “Nucleation efficiency of talc in the foaming behavior and cellular structure of polymer-based foams.” Conventional building boards are available from JACKON (JACKOBOARD® Plano building boards). However, conventional XPS foams suffer from one or more different disadvantages. Therefore, new compositions and processes are needed that can produce thin, wide, and strong XPS foams.

[0005] Aspects of the present disclosure address these and other shortcomings. Summary of the Invention

[0006] Aspects of the present disclosure relate to a foamable polymer composition comprising: a matrix polymer component comprising polystyrene (PS), a copolymer thereof, or a combination thereof; and 0.003 wt% to 0.15 wt% of a fluoropolymer component, based on the weight of the polymer composition, the fluoropolymer component comprising a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof. The foamable composition has a specific compressive strength of 8 kilopascals per cubic meter (kPa.m 3 / kg) to 65 kPa.m 3 / kg, or in some respects 8 kPa.m 3 / kg to 35 kPa.m 3 / kg, or 12 kPa.m 3 / kg to 65 kPa.m 3 / kg, or 12 kPa.m 3 / kg to 35 kPa.m 3 / kg, as determined according to ISO 844 using a universal testing machine.

[0007] Another aspect of the present disclosure relates to a method for preparing a foamed polymer composition, the method comprising: forming a mixture comprising a matrix polymer component and 0.003 wt % to 0.15 wt % of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; injecting the molten mixture into a mold; and reducing pressure on the mixture to form the foamed polymer composition. In some aspects, the mold is a core-back mold.

[0008] Still further aspects of the present disclosure are directed to methods for preparing a foamed polymer composition, the methods comprising: forming a mixture comprising a matrix polymer component and 0.003 wt % to 0.15 wt % of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; and extruding the mixture in the presence of at least one blowing agent to introduce the at least one blowing agent into the mixture and form the foamed polymer composition. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] In the accompanying drawings, which are not necessarily drawn to scale, like numbers may describe similar components in different views. Like numbers with different letter suffixes may represent different instances of similar components. The accompanying drawings generally illustrate various aspects discussed in this document by way of example and not by way of limitation.

[0010] Figure 1 External views of exemplary molds according to aspects of the present disclosure are provided.

[0011] Figure 2 Provided Figure 1 Cross-sectional view of the mold.

[0012] Figure 3 Exemplary velocity profiles are provided for a directional channel according to the prior art (left) and a directional channel having a flow profile with a hyperbolic geometry according to the present disclosure (right).

[0013] Figure 4 Provided Figure 3 External view of the two directional channels shown.

[0014] Figure 5 Exemplary molds that may be used in conjunction with the mold holders of the present disclosure are shown.

[0015] Figure 6A and 6B 1 and 2 are side and top views, respectively, of an exemplary mold holder according to the present disclosure.

[0016] Figure 7A The extruder die is shown with the shutoff plate removed.

[0017] Figure 7B The extruder die is shown with the interrupter plate inserted.

[0018] Figure 8 is a graph presenting data from Tables 6A, 6B, 7A, and 7B showing the effect of nanofibrillated masterbatch type and loading on the specific compressive strength of XPS foam.

[0019] Figure 9 is a graph presenting data from Tables 6A, 6B, 7A, and 7B showing the effect of nanofibrillated masterbatch type on the compressive strength and density of XPS foams.

[0020] Figure 10 are graphs presenting data from Tables 9A and 9B showing the effect of nanofibrillated PTFE nucleating agent on the compressive strength and density of XPS foams. DETAILED DESCRIPTION

[0021] Before disclosing and describing the disclosed compounds, compositions, articles, systems, devices and / or methods, it should be understood that, unless otherwise specified, they are not limited to specific synthetic methods, or, unless otherwise specified, are not limited to specific reagents, as such, of course, may vary. It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.

[0022] The present disclosure encompasses various combinations of elements of the present disclosure, such as combinations of elements from dependent claims dependent upon the same independent claim.

[0023] Furthermore, it should be understood that, unless expressly stated otherwise, any method described herein is in no way intended to be construed as requiring that its steps be performed in a specific order. Therefore, where a method claim does not actually enumerate the order in which its steps are to be followed, or does not otherwise specifically state in the claims or description that the steps are to be limited to a specific order, no order is intended to be inferred in any respect. This applies to any possible non-express basis for interpretation, including matters regarding the logic of the arrangement of steps or operational flow, ordinary meaning derived from grammatical organization or punctuation, or the number or type of aspects described in the specification.

[0024] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are listed.

[0025] definition It should also be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term "comprising" may include aspects "consisting of" and "consisting essentially of." Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. In this specification and the claims that follow, reference will be made to a number of terms that shall be defined herein.

[0026] As used in the specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a polystyrene polymer" includes a mixture of two or more polystyrene polymers.

[0027] As used herein, the term "combination" is inclusive of blends, mixtures, alloys, reaction products, and the like.

[0028] Ranges may be expressed herein as from a value (a first value) to another value (a second value). When such a range is expressed, the range includes, in some aspects, one or both of the first value and the second value. Similarly, when a value is expressed as an approximation by using the antecedent 'about', it is understood that the specific value forms another aspect. It will be further understood that the endpoints of each range are significant relative to the other endpoint and independently of the other endpoint. It will also be understood that many values ​​are disclosed herein, and in addition to the value itself, each value is disclosed herein as "about" that specific value. For example, if the value "10" is disclosed, then "about 10" is also disclosed. It will also be understood that every unit between two specific units is also disclosed. For example, if 10 and 15 are disclosed, then 11, 12, 13, and 14 are also disclosed.

[0029] As used herein, the terms "about" and "at or about" mean that the amount or value in question can be a specified value, an approximate specified value, or about the same as a specified value. It is generally understood that, as used herein, unless otherwise indicated or inferred, nominal values ​​indicate a variation of ±10%. The terms are intended to convey that similar values ​​promote equivalent results or effects as described in the claims. That is, it is understood that amounts, sizes, formulations, parameters, and other quantities and characteristics are not and need not be exact, but can be approximate and / or larger or smaller as needed, thereby reflecting tolerances, conversion factors, rounding, measurement errors, etc., as well as other factors known to those skilled in the art. Typically, amounts, sizes, formulations, parameters, or other quantities or characteristics are "about" or "approximate," whether or not explicitly stated as such. It is understood that when "about" is used before a quantitative value, unless otherwise specifically stated, the parameter also includes the specific quantitative value itself.

[0030] Disclosed are components used to make the compositions of the present disclosure, as well as the compositions themselves used in the methods disclosed herein. Disclosed herein are these materials and other materials and that when combinations, subsets, interactions, groups, etc. of these materials are disclosed herein, it is understood that when a combination, subset, interaction, group of items so disclosed is implemented, each individual item is specifically contemplated. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules including the compounds are discussed, it is understood that each combination and permutation of the compound is specifically contemplated unless specifically indicated to the contrary. Thus, for example, even if a particular combination is not recited the combination is specifically included in the disclosure as described herein. Similarly, where a particular aspect of the disclosure is disclosed with respect to one particular aspect, it is understood that such disclosure applies to all aspects of the disclosure and vice versa, unless specifically noted.

[0031] References in the specification and concluding claims to parts by weight, of a particular element or component in a composition or article, denote the weight relationship between the element or component and any other elements or components in the composition or article for which a part by weight measurement is expressed. Thus, in a compound containing 2 parts by weight of component X and 5 parts by weight component Y, X and Y are present at a weight ratio of 2:5, and are present in such ratio regardless of whether additional components are contained in the compound.

[0032] A weight percent of a component, unless specifically stated to the contrary, is based on the total weight of the formulation or composition in which the component is included.

[0033] As used herein, the terms "number average molecular weight" or "Mn n " can be used interchangeably, and refer to the statistical average molecular weight of all polymer chains in a sample and is defined by the formula: , where M i is the molecular weight of a chain, and N iis the number of chains of said molecular weight. For polymers, such as polycarbonate polymers, M can be determined by methods well known to those skilled in the art using molecular weight standards (e.g., polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards). n .

[0034] As used herein, the term "weight average molecular weight" or "M w " can be used interchangeably and are defined by the following formula: , Among them, M i is the molecular weight of the chain, and N i is the number of chains of the molecular weight. n In comparison, M w The molecular weight of a given chain is taken into account in determining the contribution to the average molecular weight. Thus, the greater the molecular weight of a given chain, the greater the contribution of the chain to the average molecular weight. w For polymers, such as polycarbonate polymers, M can be determined by methods known to those skilled in the art using molecular weight standards (such as polycarbonate standards or polystyrene standards, preferably certified or traceable molecular weight standards). w .

[0035] As used herein, polycarbonate refers to an oligomer or polymer comprising the residues of one or more dihydroxy compounds (eg, dihydroxy aromatic compounds) connected by carbonate linkages; it also encompasses homopolycarbonates, copolycarbonates, and (co)polyester carbonates.

[0036] As used herein, unless otherwise specified, the terms "weight percent," "wt%," and "wt.%" are used interchangeably to indicate the weight percentage of a given component based on the total weight of the composition. That is, unless otherwise specified, all wt% values ​​are based on the total weight of the composition. It should be understood that the sum of the wt% values ​​of all components in a disclosed composition or formulation equals 100.

[0037] Unless otherwise stated herein to the contrary, all test standards are the most recent in effect at the time this application is filed.

[0038] Each raw material used in the examples and / or comparative compositions described herein is commercially available and / or its production method is known to those skilled in the art.

[0039] It is understood that the compositions disclosed herein have certain functions. Certain structural requirements are disclosed herein for performing the disclosed functions, and it is understood that there are various structures that can perform the same functions related to the disclosed structures, and these structures will generally achieve the same results.

[0040] Polymer composition Aspects of the present disclosure are directed to a polymer composition comprising: a matrix polymer component comprising a polystyrene polymer; and 0.005 wt.% to 9 wt.% of a fluoropolymer component based on the weight of the polymer composition, the fluoropolymer component comprising a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof. The polystyrene polymer has a molecular weight of less than 193,000 grams per mole (g / mol) as determined according to gel permeation chromatography (GPC) using polystyrene standards. The polystyrene polymer has a Vicat softening temperature of greater than 90 °C as tested according to ISO 306 / B50. The polymer composition has a tensile modulus of between 3300 megapascals (MPa) and 3800 MPa as tested according to ISO 527.

[0041] "Fibrillated" and "fibrillating" are technical terms referring to the treatment of a fluoropolymer to produce, for example, a "node and fibril" network or cage-like structure. In an aspect, the fluoropolymer comprises fibers having an average diameter of 5 nanometers (nm) to 2 micrometers (micrometers, pm) or about 5 nm to about 2 micrometers (pm). The average fibril diameter of the fluoropolymer can also be 30 nanometers to 750 nanometers, more specifically 5 nanometers to 500 nanometers. In further examples, the average fibril diameter of the fluoropolymer can also be about 30 nanometers to about 750 nanometers, more specifically about 5 nanometers to about 500 nanometers. Field emission scanning electron microscopy can be employed to observe the degree of fibrillation of the fluoropolymer throughout the matrix polymer in the fibrillated composition.

[0042] The polystyrene polymer can comprise, in some aspects, general purpose polystyrene (GPPS), where the GPPS is derived from styrene monomers. In certain aspects, the polystyrene polymer comprises a polystyrene copolymer, where the polystyrene copolymer comprises styrene monomers, substituted styrene compounds, conjugated 1,3-dienes, metal copolymers, or a combination thereof. The metal copolymer can include, but is not limited to: zinc diacrylate; zinc dimethacrylate; zinc diacetate ethylene; zinc di-fumarate ethyl; copper diacrylate; copper dimethacrylate; copper diacetate ethylene; copper di-fumarate ethyl; aluminum (III) isopropoxide; aluminum triacrylate; aluminum trimethacrylate; aluminum triacetate ethylene; aluminum tri-fumarate ethyl; zirconium tetraacrylate; zirconium tetramethacrylate; zirconium tetraacetate ethylene; zirconium tetra-fumarate ethyl; zirconium (IV) butoxide; or a combination thereof.

[0043] In certain aspects, the polystyrene copolymer is a styrene copolymer prepared by polymerizing a reaction mixture comprising a styrene monomer and 0.5 wt% to 20 wt% of a polar comonomer, including an alkyl methacrylate. Exemplary styrene monomers include, but are not limited to, styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, tert-butylstyrene, o-chlorostyrene, vinylpyridine, and combinations thereof. Such polystyrene copolymers are described, for example, in U.S. Patent No. 9,914,814, the disclosure of which is incorporated herein in its entirety.

[0044] As described, the composition includes 0.005 wt% to 9 wt% fluoropolymer component, based on the weight of the polymer composition. In some aspects, the composition includes 0.005 wt% to 8.5 wt%, or to 8.0 wt%, or to 7.0 wt%, or to 7.5 wt%, or to 6.5 wt%, or to 6.0 wt%, or to 5.5 wt%, or to 5.0 wt%, or to 4.5 wt%, or to 4.0 wt%, or to 3.5 wt%, or to 3.0 wt%, or to 2.5 wt%, or to 2.0 wt%, or to 1.5 wt%, or to 1.0 wt%, or to 0.9 wt%, or to 0.8 wt%, or to 0.7 wt%, or to 0.6 wt%, or to 0.5 wt% fluoropolymer component.

[0045] In certain aspects, the fibrillated fluoropolymer comprises polytetrafluoroethylene, polyhexafluoropropylene, polyvinylidene fluoride, polychlorotrifluoroethylene, ethylene tetrafluoroethylene, fluorinated ethylene-propylene, polyvinyl fluoride, ethylene chlorotrifluoroethylene, or combinations thereof.

[0046] In particular aspects, the encapsulating polymer comprises styrene-acrylonitrile copolymer, acrylonitrile-butadiene-styrene copolymer, α-alkyl-styrene-acrylonitrile copolymer, α-methylstyrene-acrylonitrile copolymer, styrene-butadiene rubber, acrylic acid, polymethyl methacrylate, or combinations thereof.

[0047] In a specific aspect, the fibrillated fluoropolymer comprises polytetrafluoroethylene.

[0048] In a further aspect, the fibrillated fluoropolymer encapsulated by the encapsulating polymer comprises polytetrafluoroethylene (PTFE) encapsulated by a styrene-acrylonitrile copolymer.

[0049] In some aspects, the ratio of styrene to acrylonitrile (S / AN) in the styrene-acrylonitrile copolymer can be from 60 / 40 to 90 / 10, or in specific aspects from 70 / 30 to 80 / 20. The ratio of SAN to PTFE in the SAN copolymer encapsulated PTFE can vary from 70 / 30 to 30 / 70 or 60 / 40 to 40 / 60, or in certain aspects can be about 50 / 50.

[0050] In some aspects, the composition has a viscosity measured at 100 reciprocal seconds (1 / s) of between 30 Pascal seconds (Pa-s) and 100 Pa·s, as determined according to ISO 11443 at a temperature of 280°C.

[0051] The composition may further include a colorant, the colorant including a dye. The dye may include, but is not limited to, coumarin 460 (blue); coumarin 6 (green); Nile red; lanthanide complexes; hydrocarbon or substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; oxazole dyes; oxadiazole dyes; poly(C2-8) olefin dyes substituted with aryl or heteroaryl groups; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; naphthalenetetracarboxylic acid dyes; porphyrin dyes; bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; Indigo dyes; Thioindigo dyes; Diazo dyes; Nitro dyes; Quinoneimine dyes; Aminoketone dyes; Tetrazolium dyes; Thiazole dyes; Perylene dyes; Perylone dyes; Bisbenzoxazolylthiophene (BBOT); Triarylmethane dyes; Xanthene dyes; Thianthene dyes; Naphthalimide dyes; Lactone dyes; Fluorophores; 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; 2,5 -bis(4-biphenyl)oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3",5""-tetra-tert-butyl-p-pentaphenyl; 2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminophenyl)-4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide; 7 -dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2-ol; 7-dimethylamino-4-methylquinolone-2-ol; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazinium perchlorate; 2-(1-naphthyl)-5-phenyloxazole; 2,2'-p-phenylene-bis(5-phenyloxazole); rhodamine 700; rhodamine 800; pyrene; chrysene; rubrene; coronene; or a combination thereof.

[0052] Aspects of the present disclosure include methods for forming the polymer compositions described herein. The methods include passing a molten feed composition comprising a matrix polymer component and a fluoropolymer component through a die to form the polymer composition. The die includes: (a) an inlet section comprising at least one inlet; (b) a directional section in fluid communication with the directional section, the directional section comprising a plurality of directional channels having channel inlets and channel outlets; (c) a merging region defining a receiving volume in fluid communication with the outlets of the plurality of directional channels of the directional section, the merging region being configured to merge at least some of the fluid flows originating from the outlets of the directional channels of the directional section; and (d) an outlet region in fluid communication with the merging region, the outlet region comprising at least one outlet. At least some of the plurality of directional channels independently have an elongation between 2 and 45, the elongation being defined as the ratio of the cross-sectional area of ​​the channel inlet to the cross-sectional area of ​​the channel outlet, and wherein the directional channels comprise a hyperbolic region and a linear tapered region. Each of these sections / regions may have an effect on the elongation / orientation (eg fibrillation) of the material fed to the die.

[0053] The inlet section may include one or more inlets to the die. The inlet may generate a contraction flow, which may be generated by a contraction flow channel (if any) at the inlet. In the directional section, the shape of the inlet and outlet may be circular, but this is not necessary because the inlet and outlet can be independently circular, rectangular, polygonal or other shapes. In the merging area, the directional flows from the directional section are merged before being transported to the outlet section. In the outlet area, the merged fibers in the material leave the die under shear flow. The outlet area may have a tapered rectangular cross-section to form a belt or other cross-section of the output. The outlet section may include one or more directional channels, and the outlet area may act as a directional section to apply additional tensile force / orienting force to the processed material. The die described herein can be compared with conventional die designs in various ways. For example, existing die designs assembled at the end of the extruder do not have the feature of generating a strong tensile flow field; they only have a shear flow field.

[0054] As used herein, "oriented" means that one element shares an alignment (or nearly shares an alignment) with another element. As an example, the major axis of one element (e.g., a fibril) can be parallel to the corresponding major axis of another fibril, for example, within about 20 degrees. As another example, a region can include a plurality of oriented fibrils whose major axes are all aligned within about 20 degrees of a particular straight line in space.

[0055] Figure 1A view of an exemplary die 100 according to the present disclosure is provided. Die 100 can include an inlet section 101 including a hemispherical profile 103. Within die 100 are a merging region 103 and an outlet region 107. As described elsewhere herein, the merging region can be configured to produce an extensional or directional flow in a direction of downward flow through the die (e.g., flowing downward from inlet section 101, into merging region 103, and then in a vertical direction into outlet region 107) as well as an extensional or directional flow at least partially transverse to the downward direction.

[0056] Figure 2 A cross-sectional view of mold 200 is provided. As shown, mold 200 includes directional channel 203. Directional channel may include inlet 201. Directional channel 203 may terminate at merging region 205. Merging region 205 may define a spherical receiving area. Mold 200 may include outlet region 211. Outlet region 211 may include inlet 213 and tapered region 207. Inlet 213 may directly interface with merging region 205. Outlet region 211 may include outlet 209. Outlet 209 may have various cross-sections, such as a rectangular shape.

[0057] Directional channels, merging areas, and exit areas can include smooth walls, but can also include walls that are ridged, burred, particle-ridden, or otherwise non-smooth. Such surface features at various stages of the die can create flow fields that provide additional extensional or directional flow.

[0058] Figure 3 Views of a conventional directional channel 300 and a directional channel 302 according to aspects of the present disclosure are provided. The standard directional channel 300 includes a linear tapered cross section. The directional channel 302 includes a flow curve having a hyperbolic geometry. Figure 3 A flow rate graph is provided; as shown, higher flow rates are darker in color. Orienting channels 302 provide higher flow rates, thereby orienting the matrix polymer and any reinforcements therein. Without being bound by any particular theory, it is believed that increased wall stress may also contribute to orientation.

[0059] Figure 4 A conventional directional channel 400 and a directional channel 402 according to aspects of the present disclosure are shown. Figure 3 External view of the channel shown. Figure 4 As shown, channel 402 includes a hyperbolic inlet.

[0060] The directional channels in the system can be configured to apply, for example, a cumulative strain of about 3 to about 4 units over the length of the channel during operation. The directional channels in the system can also be configured to apply a Hencky strain of about 2 to about 8 units over the length of the channel, for example, 2, 2.5, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, or even about 8 units. These strain levels are not required, but without being bound by any particular theory, they may result in appropriate orientation of the reinforcement material disposed within the composition processed by the mold.

[0061] Flow curves with hyperbolic geometries are considered particularly suitable because they can produce relatively strong flow curves within directional channels. The angle of curvature of the entrance of a hyperbolic configured channel can vary between 120-150°, where the angle is the angle between the horizontal axis and the tangent of the hyperbola at the entrance.

[0062] The hyperbolic inlet can have a hyperbolic curvature in the scope of about 1% to about 95% of the length of the directional channel, for example, 1% to 95%, 5% to 90%, 10% to 85%, 15% to 80%, 15% to 75%, 20% to 70%, 25% to 65%, 30% to 60%, 35% to 55%, 40% to 50%, or even about 45%.The directional channel can comprise a hyperbolic region and a linear or other tapered region.On the length in the hyperbolic or parabolic region of the directional channel, the diameter of the directional channel can reduce by about 1% to about 95%.

[0063] Without being bound by any particular theory, the oriented channels can be configured (i.e., shaped) to impose a particular velocity profile (or wall stress, or both) on the fluid conveyed through the channels in the direction of the merging region. Without being bound by any particular theory, the velocity profile and / or stress tend to orient the polymer chains of any polymer matrix material fed through the die, as well as any reinforcement material that may be present in the feed of matrix material.

[0064] Figure 5 An exemplary enlarged mold 500 is provided that includes a plurality of directional channels 510. The mold 500 allows for the inclusion of different configurations of directional channels, such as the directional channels in the mold described herein, and can further be used in conjunction with a mold holder as described below.

[0065] The extruder may include a die holder 600 in some aspects, such as Figure 6A and 6BA mold holder is shown. The mold holder 600 can include an opening 610 for receiving a mold (e.g., mold 500) that includes a plurality of directional channels sized to fit within the mold holder 600. The mold holder can include any combination and number of variously configured directional channels as shown in the molds described herein.

[0066] In some aspects, the mold holder 600 is disposed at a distal end of an extruder. The mold holder 600 can be incorporated into the extruder in a similar manner as a conventional shut-off plate assembly, as shown in Figure 7A and 7B , which shows an extruder die 700 with a removed shut-off plate Figure 7A and inserted shut-off plate 710 Figure 7B . The inclusion of a plurality of directional channels in the mold holder allows for the achievement of high production / throughput of fibers / fibrils.

[0067] Foamed polymer composition Aspects of the present disclosure are further directed to a foamed polymer composition comprising: a matrix polymer component comprising polystyrene (PS), a copolymer thereof, or a combination thereof; and 0.003 wt% to 0.15 wt%, based on the weight of the polymer composition, of a fluoropolymer component comprising a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof. The foamed polymer composition has a specific compressive strength of 8 kiloPascals per cubic meter (kPa.m 3 / kg) to 65 kPa.m 3 / kg, or in some aspects, 8 kPa.m 3 / kg to 35 kPa.m 3 / kg, or 12 kPa.m 3 / kg to 65 kPa.m 3 / kg, or 12 kPa.m 3 / kg to 35 kPa.m 3 / kg, as determined using a universal testing machine according to ISO 844.

[0068] In certain aspects, the foamed polymer composition includes 0.003 wt% to 0.14 wt%, or to 0.13 wt%, 0.12 wt%, or to 0.11 wt%, or to 0.10 wt%, or to 0.09 wt%, or to 0.08 wt%, or to 0.07 wt%, or to 0.06 wt%, or to 0.05 wt%, or to 0.04 wt%, or to 0.03 wt%, or to 0.02 wt%, or to 0.01 wt% of the fluoropolymer component. In certain aspects, the foamable polymer composition comprises from 0.004 wt% to 0.15 wt%, or from 0.005 wt% to 0.15 wt%, or from 0.006 wt% to 0.15 wt%, or from 0.007 wt% to 0.15 wt%, or from 0.008 wt% to 0.15 wt%, or from 0.009 wt% to 0.15 wt%, or from 0.010 wt% to 0.15 wt% of the fluoropolymer component. In specific aspects, the foamable polymer composition comprises from 0.01 wt% to less than 0.1 wt% of the fluoropolymer component.

[0069] In some aspects, the foamed polymer composition has an average cell size of 1 micrometer (µm) to 1000 µm. In other aspects, the foamed polymer composition has an average cell size of 1 µm to 900 µm, or 1 µm to 800 µm, or 1 µm to 700 µm, or 1 µm to 600 µm, or 1 µm to 500 µm, or 1 µm to 400 µm, or 1 µm to 300 µm, or 1 µm to 200 µm, or 5 µm to 1000 µm, or 10 µm to 1000 µm, or 15 µm to 1000 µm, or 20 µm to 1000 µm.

[0070] In certain aspects, the foamed polymer composition comprises at least 90% closed cells, as determined according to EN 13164. In further aspects, the foamed polymer composition comprises at least 91% closed cells, or at least 92% closed cells, or at least 93% closed cells, or at least 94% closed cells, or at least 95% closed cells, or at least 96% closed cells, or at least 97% closed cells, or at least 98% closed cells, or at least 99% closed cells.

[0071] In some aspects, the foamed polymer composition or an article formed therefrom has a specific compressive strength of 8 kPa / m3 (kPa.m 3 / kg) to 65 kPa.m 3 / kg as determined using a universal testing machine according to ISO 844. In other aspects, the composition has a specific compressive strength of at least 8, or at least 8.5, or at least 9, or at least 9.5, or at least 10, or at least 10.5, or at least 11, or at least 11.5, or at least 12, or at least 12.5, or at least 13, or at least 13.5, or at least 14, or at least 14.5, or at least 15, or at least 16, or at least 17, or at least 18, or at least 19, or at least 20, or at least 21, or at least 22, or at least 23, or at least 24, or at least 25, or at least 26, or at least 27, or at least 28, or at least 29, or at least 30, or at most 65, or at most 64, or at most 63, or at most 62, or at most 61, or at most 6 0, or at most 59, or at most 58, or at most 57, or at most 56, or at most 55, or at most 54, or at most 53, or at most 52, or at most 51, or at most 50, or at most 49, or at most 48, or at most 47, or at most 46, or at most 45, or at most 44, or at most 43, or at most 42, or at most 41, or at most 40, or at most 39, or at most 38, or at most 37, or at most 36, or at most 35, or at most 34, or at most 33, or at most 32, or at most 31, or at most 30, or at most 29, or at most 28, or at most 27, or at most 26, or at most 25, or at most 24, or at most 23, or at most 22, or at most 21, or at most 20 kPa.m 3 / kg, as determined using a universal testing machine according to ISO 844.

[0072] In certain aspects, the foamed polymer composition, or an article formed therefrom, has a compressive strength of 400 kPa to 600 kPa, as determined according to ISO 844 using a universal testing machine.

[0073] In another aspect, the foamable polymer composition has a foam density of 32 kg / m3 (kg / m 3 ) to 65 kg / m 3 , as determined according to ASTM D792. In particular aspects, the foamed polymer composition or an article formed therefrom has a foam density of at least 32 kg / m 3, or at least 32.5, or at least 33, or at least 33.5, or at least 34, or at least 34.5, or at least 35, or at least 35.5, or at least 36, or at least 36.5, or at least 37, or at least 37.5, or at least 38, or at least 38.5, or at least 39, or at least 39.5, or at least 40, or at least 41, or at least 42, or at least 43, or at least 44, or at least 45, or at least 46, or at least 47, or at least 48, or at least 49, or at least 50, or at least 51, or at least 52, or at least 53, or at least 54, or at least 55, or at most 65, or at most 64, or at most 63, or at most 62, or at most 61, or at most 60, or at most 59, or at most 58, or at most 57, or at most 56, or at most 55, or at most 54, or at most 53, or at most 52, or at most 51, or at most 50, or at most 49, or at most 48, or at most 47, or at most 46, or at most 45, or at most 44, or at most 43, or at most 42, or at most 41, or at most 40, or at most 39, or at most 38, or at most 37, or at most 36, or at most 35 kg / m 3 , as determined according to ASTM D792.

[0074] In certain aspects, the foamed polymer composition or an article formed therefrom has a thickness of 12 millimeters (mm) to 55 mm. In a further aspect, the foamed polymer composition has a thickness of at least 13 mm, or at least 14 mm, or at least 15 mm, or at least 16 mm, or at least 17 mm, or at least 18 mm, or at least 19 mm, or at least 20 mm, or at least 21 mm, or at least 22 mm, or at least 23 mm, or at least 24 mm, or at least 25 mm, or at least 26 mm, or at least 27 mm, or at least 28 mm, or at least 29 mm, or at least 30 mm, or at least 32 mm, or at least 35 mm, or at least 38 mm, or at least 40 mm, or at most 55 mm, or at most 54 mm, or at most 53 mm, or at most 52 mm, or at most 51 mm, or at most 50 mm, or at most 48 mm, or at most 45 mm, or at most 42 mm, or at most 40 mm, or at most 38 mm, or at most 35 mm, or at most 32 mm, or at most 30 mm, or at most 28 mm. mm, or at most 25 mm, or at most 22 mm, or at most 20 mm.

[0075] The foamable polymer composition may include any of the polystyrene polymers described herein, including GPPS, polystyrene copolymers, and combinations thereof. The foamable polymer composition may include any of the encapsulating polymers described herein. The foamable polymer composition may include any of the fibrillated fluoropolymers described herein.

[0076] In other aspects, the composition further comprises at least one additional additive including an acid scavenger, an anti-drip agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a de-molding agent, a flow promoter, a lubricant, a mold release agent, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, a foam nucleating agent, a chemical foaming agent, a surfactant, or a combination thereof.

[0077] In particular aspects, the composition does not include fillers, such as reinforcing fillers. Fillers increase the density of the foamed polymer composition, resulting in a corresponding decrease in specific compressive strength, which is undesirable.

[0078] Exemplary blowing agents and chemical blowing agents include, but are not limited to, talc, azodicarbonamide (ADC), sodium bicarbonate (SBC), as well as citric acid, isocyanates, and water. Chemical blowing agents typically undergo some form of chemical change, including a chemical reaction with the material forming the polymer matrix, thereby releasing gases such as nitrogen, carbon dioxide, or carbon monoxide. Water is a common blowing agent.

[0079] Surfactants may be added as cell stabilizers. Exemplary surfactants include, but are not limited to, DC-193, B-8404, and L-5340, which are generally polysiloxane polyoxyalkylene block copolymers, such as those described in U.S. Patent Nos. 2,834,748, 2,917,480, and 2,846,458, and PCT Publication No. WO2014 / 015315, each of which is incorporated herein by reference.

[0080] In particular aspects, the foamable polymer composition further comprises a colorant comprising a dye. The foamable polymer composition can include any of the dyes described herein.

[0081] In some aspects, the foaming composition further includes a flame retardant, which includes a phosphorus-based flame retardant, a halogenated flame retardant, a halogen-free flame retardant, expandable graphite, or a combination thereof. Exemplary flame retardants include, but are not limited to, triphenyl phosphate (TPP), hexaphenoxycyclotriphosphazene (HPCTP), melamine phosphate (MP), and combinations thereof.

[0082] Exemplary halogen-free flame retardants include, but are not limited to, magnesium hydroxide, aluminum hydroxide, expandable black lead, carbon black, melamine, red phosphorus, microcapsule-coated red phosphorus, aluminum hypophosphite, ammonium polyphosphate, isobutyl aluminum hypophosphite, phenyl aluminum hypophosphite, phenyl isobutyl aluminum hypophosphite, diethyl aluminum hypophosphite, triethyl phosphate, tricresyl propyl phosphate, tributyl phosphate, and trioctyl phosphate. Other exemplary flame retardants include tris (2-chloroethyl) -phosphate, tris (2-chloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, diammonium phosphate, various halogenated aromatic compounds, antimony oxide, aluminum trihydrate, polyvinyl chloride, and the like.

[0083] Some aspects of the present disclosure relate to a method for preparing a foamable polymer composition, the method comprising: forming a mixture comprising a matrix polymer component and 0.003 wt% to 0.15 wt% of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; injecting the molten mixture into a mold; and reducing pressure on the mixture to form the foamable polymer composition. The fluoropolymer component comprises a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof. In some aspects, the mold is a recore mold.

[0084] Another aspect of the present disclosure relates to a method for preparing a foamable polymer composition, the method comprising: forming a mixture comprising a matrix polymer component and 0.003 wt% to 0.15 wt% of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; and extruding the mixture in the presence of at least one blowing agent to introduce the at least one blowing agent into the mixture and form the foamable polymer composition. The fluoropolymer component comprises a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof.

[0085] In certain aspects of these methods, the matrix polymer component comprises polybutylene terephthalate (PBT), polyetherimide (PEI), polyethylene terephthalate (PET), polycarbonate (PC), poly(p-phenylene oxide) (PPO), polystyrene (PS), polyphenylene sulfide (PPS), polypropylene (PP), polyamide (PA), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), polylactic acid (PLA), thermoplastic starch (TPS), polycaprolactone (PCL), polyvinyl chloride (PVC), poly(tetramethylene adipate-co-terephthalate), poly-styrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), acrylonitrile-butadiene-styrene (ABS), styrene butadiene rubber (SBR), styrene-grafted natural rubber (SNR), styrene-butadiene-styrene (SBS), ethylene-α-olefin copolymer (POE), copolymers thereof, or combinations thereof.

[0086] The blowing agent may include, but is not limited to, carbon dioxide, pentane, ethanol, dimethyl ether, isobutane, isopentane, cyclopentane, water, propane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, acetone, ethyl acetate, butane, trans-1-chloro-3,3,3-trifluoropropene, one or more halogenated olefins, hydrocarbons (including C1-C4 hydrocarbons), hydrofluorocarbons (HFCs), ethers, alcohols (including C1-C4 alcohols, including methanol, ethanol, propanol, and isopropanol), aldehydes, ketones, methyl formate, formic acid, trans-1,2-dichloroethylene, or combinations thereof.

[0087] Articles comprising polymer compositions or foamed polymer compositions In certain aspects, the present disclosure relates to shaped articles, formed articles, or molded articles comprising a polymer composition or foamed polymer composition. The polymer composition or foamed polymer composition can be molded into useful shaped articles by a variety of means, such as injection molding, injection foaming, extrusion molding, extrusion foaming, rotational molding, blow molding, sheet forming, tube extrusion, and thermoforming, to form articles and structural components such as food trays (e.g., deep-drawn articles for meat trays, food trays, or cups, or articles thermoformed therefrom), components of architectural foam panels (e.g., extruded foam panels for roofing, walls, floors, or enclosures and / or for building construction or vehicle applications), XPS panels as components or layers of composite panels, components of sandwich panels, foam beads, fibers, films, sheets, or molded parts.

[0088] In some aspects, the article has a thickness of 4 millimeters (mm) to 100 mm. In other aspects, the article has a thickness of 4 mm to 90 mm, or 4 mm to 80 mm, or 4 mm to 70 mm, or 4 mm to 60 mm, or 4 mm to 50 mm, or 4 mm to 40 mm, or 4 mm to 30 mm, or 4 mm to 20 mm.

[0089] In certain aspects, the article has a compressive strength of 300 kPa to 400 kPa, as determined using a universal testing machine according to ISO 844. In a specific aspect, the article has a density of 40 kg / m 3 Up to 45 kg / m 3 , as determined according to ASTM D 792. In a specific aspect, the article has a width of 900 mm to 1200 mm.

[0090] The present disclosure encompasses various combinations of elements of the present disclosure, such as combinations of elements from dependent claims dependent upon the same independent claim.

[0091] Aspects of the present disclosure In various aspects, the present disclosure relates to and includes at least the following aspects.

[0092] Aspect 1. A foamed polymer composition comprising, consisting of, or consisting essentially of: a matrix polymer component comprising polystyrene (PS), a copolymer thereof, or a combination thereof; and 0.003 wt% to 0.15 wt% of a fluoropolymer component, based on the weight of the polymer composition, the fluoropolymer component comprising a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof, wherein the composition has a specific compressive strength of 8 kilopascals per cubic meter (kPa.m3 / kg) to 65 kPa.m3 / kg, or optionally 8 kPa.m3 / kg to 35 kPa.m3 / kg, or 12 kPa.m3 / kg to 65 kPa.m3 / kg, or 12 kPa.m3 / kg to 35 kPa.m3 / kg, as determined according to ISO 844 using a universal testing machine.

[0093] Aspect 2. The foamable polymer composition according to aspect 1, wherein the foamable polymer composition has an average cell size of 1 micrometer (µm) to 1000 µm.

[0094] Aspect 3. The foamed polymer composition of aspect 1 or 2, wherein the foamed polymer composition comprises at least 90% closed cells as determined according to EN 13164.

[0095] Aspect 4. The foamed polymer composition according to any one of aspects 1 to 3, wherein the foamed polymer composition has a specific compressive strength of 12 kilopascals per cubic meter (kPa.m 3 / kg) to 65 kPa.m 3 / kg, as determined according to ISO 844 using a universal testing machine.

[0096] Aspect 5. The foamed polymer composition of any one of aspects 1 to 4, wherein the foamed polymer composition has a thickness of 12 millimeters (mm) to 55 mm.

[0097] Aspect 6. The foamable polymer composition of any one of aspects 1 to 5, wherein the polystyrene polymer comprises general-purpose polystyrene (GPPS), wherein the GPPS is derived from styrene monomers, wherein the polystyrene polymer comprises a polystyrene copolymer, wherein the polystyrene copolymer comprises a styrene monomer, a substituted styrene compound, a conjugated 1,3-diene, a metal comonomer, a polar comonomer, a styrene copolymer comprising an alkyl methacrylate, and a styrene monomer comprising one or more of styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, tert-butylstyrene, o-chlorostyrene, and vinylpyridine, or a combination thereof, and wherein the metal comonomer is selected from the group consisting of zinc diacrylate; zinc dimethacrylate; zinc diacetate; ethylzinc difumarate; copper diacrylate; copper dimethacrylate; copper diacetate; ethylcopper difumarate; aluminum (III) isopropoxide; aluminum triacrylate; aluminum trimethacrylate; aluminum triacetate; ethylaluminum trifumarate; zirconium tetraacrylate; zirconium tetramethacrylate; zirconium tetraacetate; ethylzirconium tetrafumarate; zirconium (IV) butoxide; and combinations thereof.

[0098] Aspect 7. The foamable polymer composition of any one of aspects 1 to 6, wherein the fibrillated fluoropolymer encapsulated by the encapsulating polymer comprises styrene-acrylonitrile copolymer encapsulated polytetrafluoroethylene.

[0099] Aspect 8. The foamable polymer composition of any one of aspects 1 to 7, wherein the composition comprises from 0.01 wt% to less than 0.1 wt% of the fluoropolymer component, based on the weight of the polymer composition.

[0100] Aspect 9. The foamable polymer composition of any one of Aspects 1 to 8, wherein the composition further comprises at least one additional additive comprising an acid scavenger, an anti-drip agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a mold release agent, a flow promoter, a lubricant, a mold release agent, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, a foam nucleating agent, a chemical foaming agent, a surfactant, or a combination thereof.

[0101] Aspect 10. The foamable polymer composition of any one of aspects 1 to 9, wherein the composition further comprises a colorant comprising a dye selected from the group consisting of: coumarin 460 (blue); coumarin 6 (green); Nile red; lanthanide complexes; hydrocarbon or substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; oxazole dyes; oxadiazole dyes; aryl or heteroaryl substituted poly (C2-8) olefin dyes; carbocyanine dyes; indanthrone dyes; phthalocyanine dyes; oxazine dyes; carbostyryl dyes; naphthalenetetracarboxylic acid dyes; porphyrin dyes; bis ( Styryl) biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; azo dyes; indigo dyes; thioindigo dyes; diazo dyes; nitro dyes; quinoneimine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes; perylone dyes; bisbenzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioanthene dyes; naphthalimide dyes; lactone dyes; fluorophores; 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenyl) 2,5-Bis(4-biphenyl)oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3",5""-tetra-tert-butyl-p-pentaphenyl; 2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4'-diphenylstilbene; 4-dicyanomethylene-2-methyl-6-(p-dimethylaminophenyl)-4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'- -dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2-ol; 7-dimethylamino-4-methylquinolone-2-ol; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazinium perchlorate; 2-(1-naphthyl)-5-phenyloxazole; 2,2'-p-phenylene-bis(5-phenyloxazole); Rhodamine 700; Rhodamine 800; pyrene; chrysene; rubrene; coronene; and combinations thereof.

[0102] Aspect 11. The foamable polymer composition according to any one of aspects 1 to 10, wherein the composition further comprises a polymer component comprising polybutylene terephthalate (PBT), polyetherimide (PEI), polyethylene terephthalate (PET), polycarbonate (PC), poly(p-phenylene oxide) (PPO), polystyrene (PS), polyphenylene sulfide (PPS), polypropylene (PP), polyamide (PA), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polytrimethylene terephthalate (PT), ...butylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (P T), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polylactic acid (PLA), thermoplastic starch (TPS), polycaprolactone (PCL), polyvinyl chloride (PVC), poly(tetramethylene adipate-co-terephthalate), poly-styrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), acrylonitrile-butadiene-styrene (ABS), styrene butadiene rubber (SBR), styrene-grafted natural rubber (SNR), styrene-butadiene-styrene (SBS), ethylene-α-olefin copolymer (POE), copolymers thereof, or combinations thereof.

[0103] Aspect 12. A method for preparing a foamed polymer composition, the method comprising, consisting of, or consisting essentially of: forming a mixture comprising, consisting of, or consisting essentially of: a matrix polymer component and 0.003 wt % to 0.15 wt % of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; injecting the molten mixture into a core-back mold; and reducing the pressure on the mixture to form the foamed polymer composition, wherein the fluoropolymer component comprises a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof.

[0104] Aspect 13. A method for preparing a foamed polymer composition, the method comprising, consisting of, or consisting essentially of: forming a mixture comprising, consisting of, or consisting essentially of: a matrix polymer component and 0.003 wt % to 0.15 wt % of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; and extruding the mixture in the presence of at least one blowing agent to incorporate the at least one blowing agent into the mixture and form the foamed polymer composition, wherein the fluoropolymer component comprises a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof.

[0105] Aspect 14. The method according to aspect 13, wherein the blowing agent comprises carbon dioxide, pentane, ethanol, dimethyl ether, isobutane, isopentane, cyclopentane, water, propane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, acetone, ethyl acetate, butane, trans-1-chloro-3,3,3-trifluoropropene, halogenated olefins, hydrocarbons, hydrofluorocarbons (HFCs), ethers, alcohols, aldehydes, ketones, methyl formate, formic acid, trans-1,2-dichloroethylene, or combinations thereof.

[0106] Aspect 15. The method according to any one of aspects 12 to 14, wherein the matrix polymer component comprises polybutylene terephthalate (PBT), polyetherimide (PEI), polyethylene terephthalate (PET), polycarbonate (PC), poly(p-phenylene oxide) (PPO), polystyrene (PS), polyphenylene sulfide (PPS), polypropylene (PP), polyamide (PA), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethylene terephthalate (PET ... poly(ethylene terephthalate), poly(ethylene glycol naphthalate), poly(butylene naphthalate), poly(lactic acid), poly(PLA), thermoplastic starch (TPS), polycaprolactone (PCL), polyvinyl chloride (PVC), poly(tetramethylene adipate-co-terephthalate), poly-styrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), acrylonitrile-butadiene-styrene (ABS), styrene butadiene rubber (SBR), styrene-grafted natural rubber (SNR), styrene-butadiene-styrene (SBS), ethylene-α-olefin copolymer (POE), copolymers thereof, or combinations thereof.

[0107] Aspect 16. An article comprising the foamed polymer composition of any one of aspects 1 to 15.

[0108] Aspect 17. The article according to aspect 16, wherein the article has a specific compressive strength of 12 kilopascals per cubic meter (kPa.m 3 / kg) to 65 kPa.m 3 / kg, as determined using a universal testing machine in accordance with ISO 844, and having a thickness of 12 millimeters (mm) to 55 mm.

[0109] Aspect 18. The article of aspect 16 or 17, wherein the article comprises an architectural foam board, a composite sandwich panel, a deep-drawn article for a food tray or cup, or foam beads.

[0110] Examples The following examples are presented to provide a person of ordinary skill in the art with a complete disclosure and description of how to make and evaluate the compounds, compositions, articles, devices and / or methods claimed herein, and are intended to be illustrative only and not intended to limit the present disclosure. Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperatures, etc.), but some errors and deviations should be taken into account. Unless otherwise indicated, parts are parts by weight, temperatures are in ° C. or at ambient temperature, and pressures are at or near atmospheric pressure. Unless otherwise indicated, reference to percentages of compositions is in terms of wt%.

[0111] There are many variations and combinations of reaction conditions, such as component concentrations, desired solvents, solvent mixtures, temperature, pressure, and other reaction ranges and conditions that can be used to optimize the purity and yield of the product obtained by the process. Optimization of such process conditions requires only reasonable and routine experimentation.

[0112] The compositions described herein were prepared using the materials listed in Table 1: Table 1 - Components The formulations were dry-blended and extruded using a 26 mm Coperion Werner and Pfleiderer ZSK 40 L / D co-rotating twin-screw extruder with a vacuum-vented mixing screw. A cutout with a die channel designed to maximize extensional flow and fibrillation efficiency was used; the die channel is described in U.S. Patent Application Publication No. 2021 / 0008781, the disclosure of which is incorporated herein by reference in its entirety. The die design used had a D / d ratio of 4 / 1, an inclination angle of 120°, and an L ratio of 9 mm. The temperature settings during compounding tests were: 40-180-220-260-280-280-280-280-280-280°C, and the screw speed was 300 rpm at 10 kg / hr, unless otherwise stated. During the run, the following experimental details were recorded: measured melt temperature, machine-reported melt temperature, specific energy consumption and torque (in %), and melt pressure before the die. The extrudate was cooled using a conveyor belt and water spray before pelletization. The nanofibrillated PS formulation was converted into ISO tensile rods on an ENGEL 45 molding machine using the following process conditions: 2-hour predrying time; 80°C predrying temperature; 70°C hopper temperature; zone 1-3 temperatures of 150-260-260°C (respectively); 260°C nozzle temperature; and 40°C mold temperature.

[0113] Extruded polystyrene (XPS) foam is produced using a KraussMaffei Berstorf Schaumtandex laboratory unit ZE30 / KE60, which comprises a twin-screw extruder as the main extruder (for polymer plasticization, addition, and gas nucleation) and a secondary single-screw extruder for melt cooling and homogenization. Polystyrene (STYRON™ 660) is continuously fed into the melt extruder to produce a total blend of 100 parts of PS. Additionally, additives such as talc (0.4 to 0.7 parts) are metered as a masterbatch (StarCell® PS 60) via a feeder. Propellants (CO2, ethanol, dimethyl ether, and / or isobutane) are injected under pressure into the injection port. The total throughput, including blowing agent and additives, is 35 kg / hr. The propellant-containing melt is cooled in a subsequent cooling extruder and extruded through a slot die. The expanded melt is drawn off via a heating belt and heated by a heated calibration onto a plate with a PTFE surface. Typical panel dimensions before machining are approximately 300 to 350 mm wide (y-direction) and 20 to 40 mm thick (z-direction). The foam extrusion processing parameters for ZE30 are: 40-40-190-190-185-185-180-180°C for zones 0-7 (respectively). The parameters for KE60 are: 80-125-90-180-120-93-93-92-92-92-92-90°C for zones 10-21; 90°C for zone 21.1; 90°C for zone 21.2; 90°C for zone 22; and 80°C for zone 23. The main drive parameters for the ZE30 and KE60 are: speed 250 / 17.5 revolutions per minute (rpm); specific throughput 0.1 / 2.0 kg / hr / rpm; torque 34 / 32%; specific energy 0.165-0.21 / 0.061-0.071 kilowatt-hours per kilogram (kWh / kg); and power 5.8-7 / 2.1-2.5 kW, respectively. Process parameters for the ZE30 are: pressure 1 (P1) of 58 bar; injection pressure 80 bar; P2 of 102 bar; and temperature 1 (T1) of 199°C. Process parameters for the KE60 are: P3 of 22 bar; P4 of 38 bar; and T2 of 107°C. The line speed of the puller is 2.5-5 meters per minute (m / min).

[0114] The foamable polymer melt generally contains at least one blowing agent in an amount ranging from 1% to 15% by weight, preferably from 2% to 10% by weight, and particularly preferably from 3% to 8% by weight, in each case based on the total weight of the foamable polymer melt. Various physical blowing agents are used, such as carbon dioxide (CO2), ethanol (EtOH), dimethyl ether (DME), and isobutane (iBu). The pressure in the extruder is generally in the range of 20 to 500 bar, preferably from 50 to 400 bar, and particularly preferably from 60 to 300 bar.

[0115] XPS foam boards are also produced according to the curves described above on larger XPS production lines with a production capacity of 300 kg / h to 1500 kg / h. Boards are produced at a throughput of 300 kg / hr. The foamable polymer melt includes a blowing agent mixture of 3-8 wt% of carbon dioxide, dimethyl ether, and isobutane, in each case based on the total weight of the foamable polymer melt.

[0116] The melt volume flow rate (MVR) of the pellets is determined according to ISO 1133 at a specific load and temperature.

[0117] The melt viscosity (MV) of the resin was determined according to ISO 11443 at different shear rates (1 / s, s-1) and temperatures.

[0118] Gel permeation chromatography (GPC) was used to determine weight-average molecular weight (Mw), number molecular weight, and dispersity (D) (calculated as the Mw / Mn ratio). A 20 mg sample was dissolved in 20 mL of dichloromethane along with 250 ppm of toluene as a mobile phase marker. The samples were analyzed using GPC at 254 nm and polystyrene standards.

[0119] The tensile properties of the injection molded specimens were evaluated according to ISO 527. Three samples were evaluated at the beginning, middle and end of a 10 kg extrusion run.

[0120] Cell size was determined using scanning electron microscope (SEM) micrographs of XPS foams using Image J software. At least 70 cells were measured to determine the average cell size.

[0121] Foam density is determined by the water displacement technique according to ASTM D792, assuming negligible water absorption.

[0122] The thermal conductivity of the foam samples was determined using a TA Instruments LaserComp FOX 50 heat flow meter. The foam samples were cut into cylinders with a diameter of 60 mm and a thickness (L) between 3 and 8 mm, depending on the thickness of the extruded foam. The samples were positioned between two temperature-controlled plates. These plates established a 10°C temperature differential (DT) between the samples by setting the upper plate to 30°C and the lower plate to 20°C. The heat flux (Q / A) generated through the sample was measured using two proprietary thin-film heat flux sensors. The thermal conductivity was calculated according to the equation: At least five samples of each foam were measured at different locations, and the average value of the thermal conductivity was determined.

[0123] The compressive strength of XPS foam was measured according to ISO 844 using a universal testing machine (Z050, ZwickRoell GmbH and Co. KG, Ulm, Germany). Samples for compression testing were prepared by cutting the foam into rectangular specimens 10 cm in length and 10 cm in width. The compressive load was applied perpendicular to the extrusion direction of the foam sample. The compressive strain limit was 30%, which was sufficient to characterize the modulus and plateau stress values ​​for each sample. The test speed was 1 mm / min, and the preload was 0.5 N to ensure full contact between the sample surface and the testing machine plate. At least five samples were tested.

[0124] The foam thickness was determined using a caliper according to EN 13164.

[0125] The percentage of closed cells was determined according to EN 13164.

[0126] Visually assess the surface quality of both sides of the XPS foam. "Poor" quality indicates that the foam board has a rough, uneven surface with cracks on the surface. "Good" quality indicates that the foam board has a smooth surface on both sides.

[0127] In the past ten years, the PTFE fibrillation of various resins has been studied. Usually, when adding with a loading of 2-5 wt%, fibrillated PTFE reaches its penetration. The melt tension, storage modulus, modulus, intensity, ductility and foam nucleation performance of the matrix reach their optimum state under these levels. As indicated herein, the PTFE loading of 3 wt% is used, unless otherwise indicated.

[0128] Quantifying the degree and consistency of fibrillation during production is challenging. Differential scanning calorimetry (DSC) and SEM methods cannot assess the degree of network fibrillation. Using DSC, it is difficult to quantify and distinguish between PTFE fibril, node, and crystal signals. Furthermore, SEM images, EDS analysis (F-imaging), and CT scans (statistical image analysis) typically only provide a localized view of the fibrillar network state and size of the fibrils, but fail to reveal the consistency and extent of the fibrillar network within the overall material. Therefore, the resulting bulk properties of these fibrillated compositions, such as tensile modulus, must be evaluated to assess the quality and consistency of the fibrillation.

[0129] Example 1 - Nanofibrillated PS Masterbatch Compositions were prepared and tested according to Table 2: Table 2 - Comparative Examples of Nanofibrillated PS As shown in U.S. Patent Application Publication Nos. 2018 / 0057653 and 2021 / 0008781, the disclosures of which are incorporated herein by reference in their entirety, highly nanofibrillated PET materials based on 3 wt% TSAN were produced under the provided composition and process parameters. Screening of various uncoated and coated PTFE feedstocks during extrusion revealed that the uncoated PTFE feedstock exhibited poor processability. When compounding fibrillated PTFE resins, significant die swell, known as the Barus effect, occurs; this is caused by the elastic deformation of the PTFE. This effect makes stranding of the extruded melt difficult. At 3 wt% TSAN, the maximum output was selected to prevent significant material from escaping the vacuum port. Increasing TSAN loading was observed to reduce output. To avoid frequent strand breakage, the output of the PET-based resin was limited to 15 kg / h. To enable extrusion of formulations containing 6 wt% TSAN, the vacuum port had to be closed. It is hypothesized that the fibril network becomes excessively entangled, forming clumps and hindering flow, subsequently reducing fibrillation efficiency. This can lead to pressure variations in the die, resulting in strand breakage and yield loss during manufacturing. When evaluating general-purpose polystyrene under optimal process conditions (see composition CE2 below), a lower throughput of 10 kg / hr was feasible and achieved optimal fibrillation.

[0130] To evaluate the impact of process parameters (throughput, barrel profile / die temperature, and fibrillation die), compositions containing 3 wt% TSAN in a general-purpose polystyrene (GPPS) 2.4 were prepared. It was observed that, at the same throughput, the tensile modulus of the series of products produced using the fibrillation die (compositions CE2 and CE3) was not substantially different from that of a control (composition CE1) produced without the modified die. Similar results were obtained by Bandyopadhyay et al. in ISRN, Vol. 2013, Article ID 837952 (incorporated by reference in its entirety), where the tensile modulus of 4 wt% fibrillated TSAN in a general-purpose polystyrene (GPPS-SupremeSC203EL, MFI 8 g / 10 min) was 3192 ± 50 MPa.

[0131] To achieve industrial use of nanofibrillated PTFE structures in a polystyrene matrix, further optimization and improvements were performed to achieve the highest degree of fibrillation, improved tensile modulus and increased extrusion throughput.

[0132] Therefore, additional compositions were prepared and tested, as shown in Tables 3A and 3B: Table 3A - Nanofibrillated PS Compositions Table 3B - Nanofibrillated PS Compositions Using optimized process settings (10 kg / hr, 300 rpm, 280°C barrel / die temperature) and TSAN type and loading (3 wt% TSAN), various general-purpose polystyrene resins with different melt flow indices (MFIs) were evaluated with or without the fibrillating die described herein and the fibrillating die described in US 2021 / 0008781. Surprisingly, it was found that GPPS resins with higher MFIs, when combined with the fibrillating die, resulted in higher fibrillation and, consequently, higher tensile moduli of up to 3900 MPa (comparing compositions IE1 to IE7 and IE5 to IE10). GPPS resins with an MFI of 7 or higher were found to have improved fibrillation and increased manufacturing throughput (composition IE9).

[0133] According to the following formula, fibrillation is expected to improve when the viscosity of the matrix resin increases with increasing capillary number: The capillary number (Ca) is the ratio of viscous forces, which tend to break up a droplet, to interfacial forces, which tend to keep it spherical. According to the equation, viscous forces tend to break up a droplet, while interfacial tension tends to keep it spherical. cr ), exceeding the above value, the dispersed polymer will deform or break. cr <0:1, the dispersed polymer will not change; when 0:1 <Ca=Ca cr <1, the dispersed polymer begins to deform without breaking; when 1 <Ca=Ca cr <4, the dispersed polymer breaks, and only when Ca=Ca cr The dispersed polymer will deform into fibrils with a high aspect ratio only when the shear field is greater than 4. From a processing perspective, the shear field can promote droplet deformation and determine whether PTFE fibrils are formed.

[0134] According to the present disclosure, surprisingly, the opposite trend is observed as a function of increasing viscosity, as the TSAN type (particle size, interfacial tension), loading, and shear rate are kept constant in these series. However, this increase in shear rate results in variations in die pressure, which leads to frequent strand breakage during extrusion and poor manufacturability.

[0135] Additional compositions were formed and tested as shown in Tables 4A and 4B: Table 4A - Nanofibrillated PS compositions with varying PTFE content and type x = data not available; ND = not determined / evaluated Table 4B - Nanofibrillated PS compositions with varying PTFE content and type x = data not available; ND = not determined / evaluated Various TSAN loadings were evaluated in conjunction with GPPS resins with calculated PTFE contents ranging from 0.5 wt% to 7.5 wt% and an MFI of 7 (compositions IE12-IE15 and CE4). As previously noted, the MVR decreased with increasing TSAN loading. During extrusion, it was observed that higher TSAN loadings resulted in increased strand breakage during production. Additionally, during melt viscosity measurements for samples with TSAN contents of 5 wt% or higher (compositions IE13, IE14, and IE15), some pressure variations were observed due to excessive entanglement of the fibrous network and the formation of clumps, which hindered flow. Furthermore, due to strand breakage and difficulty in chopping the strands into pellets, the composition containing 15 wt% TSAN could not be processed by extrusion combined with fibrillation. Thus, example compositions IE7, IE17, and IE18, comprising 3 wt% TSAN, 2.5 wt% ISAN 60, and 3 wt% ISAN 60, respectively, are the best compositions for enhanced tensile modulus (higher fibrillation) and processability (minimal pressure variation and excellent plying). The calculated PTFE contents for these examples are 1.5 wt%, 1.5 wt%, and 1.8 wt%, respectively. It was observed that higher MFR GPPS resins combined with various coated PTFE additives (TSAN, ISAN 60) with different SAN shell compositions resulted in higher fibrillation compared to PTFE. However, example compositions IE4, IE5, IE9, and IE10, comprising GPPS with an MFR of 20 and a Vicat softening point of 85°C, did not exhibit improved tensile modulus properties. Without being bound by theory, it is believed that there is an optimal PS polymer composition and Mw distribution that provides enhanced PTFE fibrillation, thereby improving modulus properties.

[0136] Thus, in this example, it was found that using a GPPS resin with an MFI of 7 or higher, an optimal loading of the coated PTFE additive, and / or specific process parameters (300 rpm, low shear, high die temperature, and a specific fibrillating die), a GPPS resin with a highly nanofibrillated PTFE network can be produced with high throughput, minimal pressure variation, and limited strand breakage during industrial extrusion. The compositions according to various aspects of the present disclosure have a fibrillated fluoropolymer content ranging from 0.5 wt% to 7.5 wt% in a low viscosity PS matrix. The tensile modulus of the compositions with a molecular weight below 193,000 g / mole is at or above 3300 MPa, which is significantly higher than conventional compositions previously reported.

[0137] Example 2 - Foam Composition Nanofibrillated PTFE PS resins were formed and tested according to Table 5: Table 5 - Nanofibrillated PS resin For this example, two PTFE nanofibrillated PS resins were manufactured, having low and high fibrillation levels, with moduli of 3300 MPa (CE2) and 3800 MPa (IE7). These different resins were used as masterbatches during foam extrusion of XPS foams. The foam compositions described herein include 0.0038 wt% to 0.018 wt% of a highly fibrillated PTFE composition in the XPS foam. The XPS foam compositions have a weight reduction of 4.3% to 9.3% while maintaining mechanical properties (compressive strength) and thermal insulation properties. Further, these foams can be produced using a mixture of blowing agents containing CO2, which is a more environmentally friendly production method that avoids the use of fluorinated blowing agents or alternative blowing agents with a greater potential impact on global warming. The study found that the degree of PTFE fibrillation affects the performance benefits achieved in the XPS foam and the optimal dosage required to achieve the desired properties. Specifically, the use of nanofibrillated masterbatches enabled the production of foams with densities of 33 kg / m 3 , 43 kg / m 3 and 51 kg / m 3 Lighter XPS foam with compressive strengths of 500 kPa, 1100 kPa, and 1500 kPa. 5-10% weight reduction compared to conventional commercially available XPS products.

[0138] The mechanical properties of PS foam are known to be influenced by a variety of factors, including the reinforcing effect of additives, the orientation of fibrous additives, the effect of cell opening, the aspect ratio of the cells, and the gas pressure within the closed-cell foam (see Aksit et al., “Extruded Polystyrene Foams with Enhanced Insulation and Mechanical Properties by a Benzene-Trisamide-Based Additive,” Polymers, 2019, 11, 268). As reported, Benzene-Trisamide was used as a foaming nucleating agent at loadings ranging from 0.1 wt% to 0.5 wt% and included a carbon dioxide (4 wt%) / ethanol (3 wt%) mixture. The compressive strength of the foam increased from 600 kPa to 1600 kPa, corresponding to a decrease in foam density from 52.3 kg / m 3 Increased to 77.8 kg / m 3 The specific compressive strength values ​​obtained are between 11.5 and 20.7 kPa.m 3The specific compressive strength was calculated by dividing the compressive strength by the foam density.

[0139] The XPS foams according to the present disclosure are formed using different nucleating agents at lower dosages, resulting in lighter foam densities. Conventional PTFE-based materials in polystyrene foams include different PTFE contents (0.1 wt% and 3 wt%) and 30 wt% expanded graphite, as described in Amirabadi et al., "Tailoring nanofibrillated polystyrene composite with enhanced fire retarding properties for foam applications," Materials and Design, Vol. 214, February 2022, 110419. The foam density of the foams described in this document was calculated by assuming the solid density of the composition. A density of 1.375 was calculated using the rule for a 30 wt% mixture of EG / PS-based materials by using a density of 2.250 g / cc for expanded graphite (EG) and a density of 1 g / cc for polystyrene. By using the reported expansion ratio (φ) and solid density ( ), calculate the foam density according to the following formula ( ): The density of these 30% EG XPS foams ranges from 85.9 kg / m 3 and 550 kg / m 3 The non-fibrillated PS foam herein has a compressive strength of 500 kPa and a calculated density of 33 kg / m 3 , resulting in a specific compressive strength of 15 kPa.m 3 / kg. In the foams according to aspects of the present disclosure, different reinforcing fibrillating nucleating agents are used, which allows for significantly lower dosages (less than 0.1 wt%), resulting in more efficient nucleation and lower foam density (while maintaining compressive strength properties). In addition, the foams described by Amirabadi et al. are made using a batch foaming process, which is not representative of the extruded polystyrene foams described in the present disclosure (continuous process).

[0140] XPS foams were formed and tested on a 300 kg / hr production line by varying the masterbatch type (CE2 and IE7) and masterbatch loading (0.2 wt% to 5 wt%). The resulting XPS foams contained 0.003 wt% to 0.075 wt% nanofibrillated PTFE. First, comparative foams were formed and tested according to Tables 6A and 6B: Table 6A - Comparative XPS Foams Including Poorly Fibrillated PTFE Masterbatch Mfg = Manufacturing Line Table 6B - Comparative XPS Foams Including Poorly Fibrillated PTFE Masterbatch Mfg = Manufacturing Line Surprisingly, these examples show that even with lower loadings of PTFE fibrils, compressive strength values ​​can be improved (CE10, CE11, CE12, CE13) compared to conventional talc-nucleated foams (CE4, CE5, CE6). However, no significant reduction in foam density was observed. This resulted in poorer "specific" compressive strength values ​​at 7.7 kPa.m 3 / kg to 11.6 kPa.m 3 / kg range (CE9 to CE12). The best specific compressive strength performance (11.9 kPa.m) was obtained with CE6 (talc nucleated PS foam). 3 / kg) of XPS foam. The surface quality of this foam was good. It was observed that at higher talc loadings (CE14, 1.7 wt%), the surface quality of the XPS foam decreased due to unstable foam nucleation behavior during the foam extrusion process, resulting in cracks and a rough surface.

[0141] Additional XPS foams including a highly fibrillated masterbatch (composition IE7 in Table 5 above) were prepared and tested as shown in Tables 7A and 7B: Table 7A - Example XPS Foams with Improved Specific Compressive Strength Mfg = Manufacturing Line Table 7B - Example XPS Foams with Improved Specific Compressive Strength Mfg = Manufacturing Line Surprisingly, it was found that when the highly fibrillated masterbatch IE7 was used to form the XPS foam, improved specific compressive strength values ​​were obtained, in the range of 11.9 kPa.m 3 / kg to 15.5 kPa.m3 / kg (IE4 to IE14). As mentioned above, the foam density of conventional commercial 500 kPa XPS foam is 35 kg / m 3 , which produces 14.3 kPa.m 3 The compressive strength of the example composition IE13 is 520 kPa and the foam density is 33.5 kg / m 3 , thus generating 15.5 kPa.m 3 / kg improved specific compressive strength. This XPS foam composition (IE13) enables a 4.5% weight reduction (=(35 / 33.5*100)-100) compared to a conventional 500 kPa commercial board. Adding the fibrillated masterbatch does not significantly affect thermal insulation properties because the cell size remains on the same order of magnitude. To further improve the thermal insulation properties of XPS foam, cell size may need to reach the nanometer scale (according to Knudsen diffusion law).

[0142] refer to Figure 8 By graphically comparing Tables 6A-7B, it can be observed that the IE7 high modulus PTFE masterbatch (with increased fibrillation) is a highly effective nucleating agent for XPS foam compared to the less fibrillated PTFE masterbatch CE2. It can be observed that the nanofibrillated PTFE nucleating agent is more effective relative to talc, as it is active even at loadings below 0.1 wt% (IE4-IE14).

[0143] To understand the differences in the disclosed XPS foams based on highly fibrillated PTFE masterbatch, Figure 9 The relationship between compressive strength and density is shown in . As previously discussed, the compressive strength of conventional commercial XPS foam increases linearly with foam density due to the increase in cell wall thickness (see Figure 9 Surprisingly, it was observed that the IE7 highly fibrillated PTFE masterbatch enabled the production of lighter XPS foams because the foam produced deviated from the Figure 9 In contrast, the XPS foam derived from composition CE2 was unable to achieve the high specific compressive strength performance of IE7 foam.

[0144] Thinner XPS foams (thickness 12 mm) were produced using talc (composition CE15) and fibrillated PTFE compositions IE7 (compositions IE15 to IE17) as foam nucleating agents. The foams produced and their properties are shown in Table 8: Table 8 - Thin (12 mm) XPS foam with improved specific compressive strength In conventional thinner and higher-density XPS foams, higher nucleating agent loadings of up to 1.5 wt% are required to ensure a stable foaming process, consistent cell size, and improved mechanical properties. It has been observed that higher talc loadings lead to poorer surface quality, as exemplified by comparative CE15. Surprisingly, studies have found that using PTFE fibrillating foam nucleating agent IE7 allows the production of various 12 mm thick XPS foams with good surface quality on both skins (top and bottom) and improved compressive strength (IE15 to IE17) compared to CE15. The extruded polystyrene foam manufacturing process forms a natural skin that hinders moisture absorption. This characteristic is desirable for thin, hot-wire-sliced ​​XPS boards. Thin XPS foam boards with smooth skins were formed in IE15-IE17. Such compositions are useful in interior construction and furniture, particularly in rooms with high humidity levels. In other applications, the natural skin of these XPS boards may be removed by grinding, sanding, or hot wire sectioning, and then coated on both sides to facilitate bonding / adhesion with mortar or plaster.

[0145] Additional foam compositions were prepared and tested on a laboratory foam extrusion line as shown in Tables 9A and 9B: Table 9A - XPS foam produced on a laboratory production line ND: Not Determined Table 9B - XPS foam produced on a laboratory production line ND: Not Determined Conventional foam compositions (CE16, CE17, and CE18) with compressive strengths of 300 kPa, 500 kPa, and 700 kPa have higher densities than commercially available XPS foams produced on the manufacturing line. Non-talc nucleated XPS foams (CE19, CE20, CE21) have larger cells, compressive strength values ​​below 400 kPa, and specific compressive strength values ​​below 9 kPa.m. 3 / kg.

[0146] Surprisingly, the study found that the use of a highly efficient PTFE fibrillated foam nucleating agent (IE7) resulted in XPS foams with high specific compressive strength properties (IE18 to IE26). More specifically, nanofibrillated PTFE loadings of 0.0075 wt% to 0.15 wt% were sufficient to achieve these benefits in XPS foam while maintaining thermal insulation properties. Compared to the talc nucleation benchmark (CE16, CE17, CE18), the most ideal XPS foams were IE19, IE20, IE21, and IE24. XPS foams according to aspects of the present disclosure deviate from the talc nucleation trend line, as shown in FIG. Figure 10 The results show that the improvement and benefits of its lightweight. 3 / kg and 30.2 kPa.m 3 This is further demonstrated by the high specific compressive strength values ​​of 100 kPa / kg. Furthermore, fibrillated foam nucleating agents according to aspects of the present disclosure can be used to produce XPS foams with compressive strength properties exceeding 700 kPa (see IE21, IE23, IE24, and IE25) and as high as 1530 kPa. These examples demonstrate that, depending on the blowing agent mixture, highly fibrillated PTFE foam nucleating agents can be optimized to achieve the desired weight reduction benefits.

[0147] In summary, by using a highly efficient PTFE fibrillated foam nucleating agent, XPS foams with high specific compressive strength properties were developed. More specifically, very low nanofibrillated PTFE loadings of 0.0075 wt% to 0.15 wt% were sufficient to achieve these benefits in XPS foams while maintaining thermal insulation properties.

[0148] The above description is intended to be illustrative and not limiting. For example, the above examples (or one or more aspects thereof) may be used in combination with each other. Other aspects may be used, as would be appreciated by one of ordinary skill in the art after reviewing the above description. The Abstract is provided to comply with 37 CFR §1.72(b), thereby allowing the reader to quickly ascertain the nature of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. Furthermore, in the above Detailed Description, various features may be grouped together to simplify the disclosure. This should not be interpreted as an intention that unclaimed disclosed features are essential to any claim. Rather, inventive subject matter may lie in fewer than all features of a particular disclosed aspect. Therefore, the following claims are hereby incorporated into the Detailed Description as examples or aspects, with each claim standing alone as a separate aspect, and it is contemplated that such aspects may be combined with each other in various combinations or permutations. The scope of the disclosure should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled.

Claims

1. A foamed polymer composition comprising: a matrix polymer component comprising polystyrene (PS), a copolymer thereof, or a combination thereof; and 0.003 wt% to 0.15 wt% of a fluoropolymer component, based on the weight of the polymer composition, the fluoropolymer component comprising a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof, The specific compressive strength of the composition is 8 kPa / m3 (kPa.m 3 / kg) to 65 kPa.m 3 / kg, as determined using a universal testing machine according to ISO 844. 2 . The foamed polymer composition of claim 1 , wherein the foamed polymer composition has an average cell size of 1 micrometer (µm) to 1000 µm.

3. The foamed polymer composition according to claim 1 or 2, wherein the foamed polymer composition comprises at least 90% closed cells as determined according to EN 13164.

4. The foamed polymer composition according to any one of claims 1 to 3, wherein the foamed polymer composition has a specific compressive strength of 12 kPa / m3 (kPa.m 3 / kg) to 65 kPa.m 3 / kg, as determined using a universal testing machine according to ISO 844. 5 . The foamed polymer composition of claim 1 , wherein the foamed polymer composition has a thickness of 12 millimeters (mm) to 55 mm.

6. The foamable polymer composition of any one of claims 1 to 5, wherein the polystyrene polymer comprises general purpose polystyrene (GPPS), wherein the GPPS is derived from styrene monomers, wherein the polystyrene polymer comprises a polystyrene copolymer, wherein the polystyrene copolymer comprises a styrene monomer, a substituted styrene compound, a conjugated 1,3-diene, a metal comonomer, a polar comonomer, a styrene copolymer comprising an alkyl methacrylate, and a styrene monomer comprising one or more of styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, tert-butylstyrene, o-chlorostyrene, and vinylpyridine, or a combination thereof, and wherein the metal comonomer is selected from the group consisting of zinc diacrylate; zinc dimethacrylate; zinc diacetate; ethylzinc difumarate; copper diacrylate; copper dimethacrylate; copper diacetate; ethylcopper difumarate; aluminum (III) isopropoxide; aluminum triacrylate; aluminum trimethacrylate; aluminum triacetate; ethylaluminum trifumarate; zirconium tetraacrylate; zirconium tetramethacrylate; zirconium tetraacetate; ethylzirconium tetrafumarate; zirconium (IV) butoxide; and combinations thereof.

7. The foamed polymer composition of any one of claims 1 to 6, wherein the fibrillated fluoropolymer encapsulated by the encapsulating polymer comprises styrene-acrylonitrile copolymer encapsulated polytetrafluoroethylene.

8. The foamed polymer composition of any one of claims 1 to 7, wherein the composition comprises from 0.01 wt% to less than 0.1 wt% of the fluoropolymer component, based on the weight of the polymer composition.

9. The foamable polymer composition of any one of claims 1 to 8, wherein the composition further comprises at least one additional additive comprising an acid scavenger, an anti-drip agent, an antioxidant, an antistatic agent, a chain extender, a colorant, a de-molding agent, a flow promoter, a lubricant, a mold release agent, a plasticizer, a quenching agent, a flame retardant, a UV reflecting additive, a foam nucleating agent, a chemical blowing agent, a surfactant, or a combination thereof.

10. The foamable polymer composition of any one of claims 1 to 9, wherein the composition further comprises a colorant comprising a dye selected from the group consisting of: coumarin 460 (blue); coumarin 6 (green); Nile red; lanthanide complexes; hydrocarbon or substituted hydrocarbon dyes; polycyclic aromatic hydrocarbon dyes; oxazole dyes; oxadiazole dyes; aryl or heteroaryl substituted poly (C2-8) olefin dyes; Carbocyanine dyes; Indanthrone dyes; Phthalocyanine dyes; Oxazine dyes; Carbostyryl dyes; Naphthalenetetracarboxylic acid dyes; Porphyrin dyes; Bis(styryl)biphenyl dyes; acridine dyes; anthraquinone dyes; cyanine dyes; methine dyes; arylmethane dyes; Azo dyes; Indigo dyes; Thioindigo dyes; Diazo dyes; nitro dyes; quinoneimine dyes; aminoketone dyes; tetrazolium dyes; thiazole dyes; perylene dyes; perylone dyes; bisbenzoxazolylthiophene (BBOT); triarylmethane dyes; xanthene dyes; thioxanthene dyes; naphthalimide dyes; lactone dyes; fluorophores; 7-amino-4-methylcoumarin; 3-(2'-benzothiazolyl)-7-diethylaminocoumarin; 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole; 2,5-bis(4-biphenylyl)oxazole; 2,2'-dimethyl-p-quaterphenyl; 2,2-dimethyl-p-terphenyl; 3,5,3",5""-tetra-tert-butyl-p-pentaphenyl; 2,5-diphenylfuran; 2,5-diphenyloxazole; 4,4'-diphenylstilbene; 4-diphenyl Cyanomethylidene-2-methyl-6-(p-dimethylaminophenyl)-4H-pyran; 1,1'-diethyl-2,2'-carbocyanine iodide; 3,3'-diethyl-4,4',5,5'-dibenzothiatricarbocyanine iodide; 7-dimethylamino-1-methyl-4-methoxy-8-azaquinolone-2; 7-dimethylamino-4-methylquinolone-2; 2-(4-(4-dimethylaminophenyl)-1,3-butadienyl)-3-ethylbenzothiazolium perchlorate; 3-diethylamino-7-diethyliminophenoxazinium perchlorate; 2-(1-naphthyl)-5-phenyloxazole; 2,2'-p-phenylene-bis(5-phenyloxazole); Rhodamine 700; Rhodamine 800; pyrene; chrysene; rubrene; coronene; and combinations thereof.

11. The foamable polymer composition according to any one of claims 1 to 10, wherein the composition further comprises a polymer component comprising polybutylene terephthalate (PBT), polyetherimide (PEI), polyethylene terephthalate (PET), polycarbonate (PC), poly(p-phenylene oxide) (PPO), polystyrene (PS), polyphenylene sulfide (PPS), polypropylene (PP), polyamide (PA), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polytrimethylene terephthalate (PT), ...butylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (PBT), polybutylene terephthalate (P T), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polylactic acid (PLA), thermoplastic starch (TPS), polycaprolactone (PCL), polyvinyl chloride (PVC), poly(tetramethylene adipate-co-terephthalate), poly-styrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), acrylonitrile-butadiene-styrene (ABS), styrene butadiene rubber (SBR), styrene-grafted natural rubber (SNR), styrene-butadiene-styrene (SBS), ethylene-α-olefin copolymer (POE), copolymers thereof, or combinations thereof.

12. A method for preparing a foamed polymer composition, the method comprising: forming a mixture comprising a matrix polymer component and 0.003 wt % to 0.15 wt % of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; injecting the molten mixture into a core-back mold; and reducing the pressure on the mixture to form the foamed polymer composition, wherein the fluoropolymer component comprises a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof.

13. A method for preparing a foamed polymer composition, the method comprising: forming a mixture comprising a matrix polymer component and 0.003 wt % to 0.15 wt % of a fluoropolymer component, based on the weight of the polymer composition; melting the mixture; and extruding the mixture in the presence of at least one blowing agent to incorporate the at least one blowing agent into the mixture and form the foamed polymer composition, wherein the fluoropolymer component comprises a fibrillated fluoropolymer, a fibrillated fluoropolymer encapsulated by an encapsulating polymer, or a combination thereof.

14. The method of claim 13, wherein the blowing agent comprises carbon dioxide, pentane, ethanol, dimethyl ether, isobutane, isopentane, cyclopentane, water, propane, 1,3,3,3-tetrafluoropropene, 2,3,3,3-tetrafluoropropene, acetone, ethyl acetate, butane, trans-1-chloro-3,3,3-trifluoropropene, a halogenated olefin, a hydrocarbon, a hydrofluorocarbon (HFC), an ether, an alcohol, an aldehyde, a ketone, methyl formate, formic acid, trans-1,2-dichloroethylene, or a combination thereof.

15. The method according to any one of claims 12 to 14, wherein the matrix polymer component comprises polybutylene terephthalate (PBT), polyetherimide (PEI), polyethylene terephthalate (PET), polycarbonate (PC), poly(p-phenylene oxide) (PPO), polystyrene (PS), polyphenylene sulfide (PPS), polypropylene (PP), polyamide (PA), linear low density polyethylene (LLDPE), low density polyethylene (LDPE), high density polyethylene (HDPE), polytrimethylene terephthalate (PTT), polyethylene naphthalate (PEN), polyethylene terephthalate (PET), polyethylene terephthalate (PET ... poly(ethylene terephthalate), poly(ethylene glycol naphthalate), poly(butylene naphthalate), poly(lactic acid), poly(PLA), thermoplastic starch (TPS), polycaprolactone (PCL), polyvinyl chloride (PVC), poly(tetramethylene adipate-co-terephthalate), poly-styrene-block-poly(ethylene-co-butylene)-block-polystyrene (SEBS), acrylonitrile-butadiene-styrene (ABS), styrene butadiene rubber (SBR), styrene-grafted natural rubber (SNR), styrene-butadiene-styrene (SBS), ethylene-α-olefin copolymer (POE), copolymers thereof, or combinations thereof.

16. An article comprising the foamed polymer composition according to any one of claims 1 to 15.

17. The article of claim 16, wherein the article has a specific compressive strength of 12 kPa / m3 (kPa.m 3 / kg) to 65 kPa.m 3 / kg, as determined using a universal testing machine in accordance with ISO 844, and having a thickness of 12 millimeters (mm) to 55 mm.

18. The article of claim 16 or 17, wherein the article comprises a construction foam board, a composite sandwich panel, a deep drawn article for a food tray or cup, or foam beads.

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