Extruded thermoplastic foams and use in applications requiring strength and light weight

Abstract

Disclosed is an extruded foam comprising an extruded thermoplastic closed cell foam having at least a first surface and comprising: (i) thermoplastic polymer cell walls formed by an extrusion step, the walls consisting of at least about 0.5 wt% of ethylene furanate moieties and optionally one or more comonomer moieties; (ii) a blowing agent contained in at least a portion of the closed cells; and a material different from the thermoplastic closed cell foam attached to and / or integral with at least a portion of the first foam surface.

Description

[0001] Cross-reference to related applications

[0002] This application relates to and claims priority to U.S. Provisional Application 63 / 548,370, filed November 13, 2023, which is incorporated herein by reference. Technical Field

[0003] This invention relates to expandable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles made therefrom, including foam articles such as panels, boards, sheets, blocks, beams, and other shaped articles comprising polyethylene furanate (PEF) and having a surface covered by a thermoplastic foam of sheet, pad, film, woven fabric, or similar surface covering. The invention also relates to the use of such articles in equipment, systems, and methods that require or benefit from relatively lightweight and relatively robust foam forms, particularly environmentally friendly and sustainable lightweight and relatively robust foam forms. Background Technology

[0004] While foams are used in a wide variety of applications, in many applications, the desired but difficult-to-achieve goal is for foam materials to be environmentally friendly while possessing excellent performance properties and being cost-effective. Environmental considerations include not only the recyclability and sustainability of the polymer resins that form the foam structure, but also the low environmental impact of the blowing agents used to form the foam, such as the global warming potential (GWP) and ozone depletion potential (ODP) of the blowing agents.

[0005] From a recyclable and / or sustainable sourcing perspective, the potential advantages of foams based on certain thermoplastic resins, including polyester resins, have been investigated. However, some difficulties have been encountered in developing such materials. For example, developing truly recyclable polyester resins that can be produced from sustainable sources and are compatible with blowing agents (which, when combined with thermoplastic materials, can produce foams with good performance properties) has been a challenge. In many applications, performance characteristics considered highly desirable include the production of high-quality closed-cell foams that are low in density (and therefore lightweight in use) while simultaneously possessing relatively high mechanical integrity and strength.

[0006] There are many important applications that will benefit from the use of covered or finished foam forms, where the foam portion is made from renewable and sustainable materials that are relatively lightweight (i.e., have a relatively low density) and relatively high strength. Such applications include, for example, use in transportation equipment such as cars, trucks, railcars, boats, ships, and airplanes, as the use of lightweight and relatively robust materials is likely advantageous in all such applications. Other examples include sporting equipment such as sleds, skis, ice skates, etc., and fixed building structures, including, for example, as roof and floor slabs in buildings and residences, and as wall components. Encapsulation applications can also benefit from the foam provided by this invention.

[0007] Another important example of applications that would benefit from relatively lightweight and relatively high-strength covered or finished foams made from renewable and sustainable materials is blades, foils, and the like used as fluid energy transfer devices. Examples of such fluid energy transfer devices include blades used on wind turbines. Other types of fluid energy transfer devices include vortex, tidal, ocean current oscillating hydrofoils and kitesurfs, which recover aerodynamic or hydrodynamic energy from stationary or mobile equipment located in the air or water.

[0008] Figure 1 The diagram schematically illustrates an example of one type of wind turbine. In the configuration shown, the wind turbine, generally designated 2, includes a tower 4 that supports a nacelle 6 surrounding a drive system 8. In a typical configuration, wind turbine blades 10 are arranged on a hub to form a "rotor" at one end of the drive system 8 outside the nacelle 6. During operation, wind passing over the blades 10 generates lift and causes the blades to rotate, and the rotating blades 10 drive a gearbox 12 connected to a generator 14 located at the other end of the drive system 8. This generator, along with a control system 16 that receives input from an anemometer 18, is arranged within the nacelle 6. It should be understood that other configurations of wind turbines are directly driven and therefore do not include a gearbox.

[0009] In many wind turbines, the nacelle is located at the top of the tower, which can be 120 meters above the ground or even higher for ground-based turbines, and 150 meters or even higher for offshore applications (offshore turbines). For this and other reasons, it is crucial to construct the various components of the wind turbine blades from materials that are relatively lightweight yet strong enough to withstand the forces the blades will experience. Therefore, in such applications, it is essential to use the lightest possible material that provides the necessary strength properties, as this will not only improve the operating efficiency of the wind turbine but also reduce the construction and maintenance costs of the wind turbine. While thermoplastic foams made from polyethylene terephthalate (PET) have been used in wind turbine blades, the applicant has recognized several significant drawbacks to using this material in such applications. For example, PET is not a sustainable material. Furthermore, some sections of the wind turbine blades use higher-density materials such as balsa wood instead of PET foam because PET foam cannot provide sufficient strength to meet the needs of those areas of the wind turbine blade.

[0010] See details Figure 2 And Figure 3, for example, Figure 1 A typical rotor blade 10 is shown in perspective view, and Figure 3A A cross-sectional view of rotor blade 10 along section 3-3 is shown. As shown, a typical rotor blade 10 generally includes a blade root 30 and a blade tip 32, the blade root being configured to be mounted or otherwise secured to the hub of the wind turbine 2, and the blade tip being disposed opposite to the blade root 30. The thickness of the main body shell 21 of the rotor blade is typically 1 cm to 6 cm, and generally extends along the longitudinal axis 27 between the blade root 30 and the blade tip 32. The main body shell 21 typically serves as the outer shell / covering of the rotor blade 10 and can define a generally aerodynamic profile, such as by defining a cross-section that defines a symmetrical or arched airfoil shape. Due to varying mechanical strength requirements along the length of the turbine blade 10, a core material containing polymer foam such as PET foam combined with balsa wood is typically used to form the main body shell of the blade between section 42 and the root 30, wherein the balsa wood concentration is higher in areas closer to the root where strength requirements are higher.

[0011] refer to Figure 3AIt is noted that the rotor blade 10 typically has a pressure side 34 and a suction side 36 extending between the leading edge 26 and the trailing edge 28 of the rotor blade 10. Further, the rotor blade 10 may also have a span 23 and a chord 25, the span defining the total length between the blade root 30 and the blade tip 32, and the chord defining the total length between the leading edge 26 and the trailing edge 28. As generally understood, the length of the chord 25 may typically vary relative to the span 23 as the rotor blade 10 extends from the blade root 30 to the blade tip 32. Furthermore, the rotor blade 10 may include one or more longitudinally extending structural members configured to provide the rotor blade 10 with increased stiffness, bending drag, and / or strength. For example, the rotor blade 10 may include a pair of longitudinally extending shear webs 24 having spar caps 20, 22 configured to engage opposing inner surfaces 35, 37 abutting against the pressure side 34 and the suction side 36 of the rotor blade 10, respectively. Additionally, one or more shear-resistant webs 24 may be disposed between the spars caps 20, 22 to form a beam configuration. The spars caps 20, 22 are typically designed to resist bending loads during wind turbine 2 operation and to minimize blade tip deflection and / or other loads acting on rotor blade 10 in the general spanwise direction (parallel to the span 23 of rotor blade 10). In some configurations, the spars are designed to also resist shear as well as tension and compression, based on the inclination of the fibers in the laminate constituting our spars caps. Similarly, the spars caps 20, 22 may also be designed to withstand spanwise compression and / or tension that occur during wind turbine 6 operation. In the alternative arrangements shown in Figures 3B and 3C, the spars caps 20A and 22A may be integrated into the structural shell.

[0012] Due to these requirements for the spar caps used in rotor blades, it has been common practice to date not to use PET foam for these parts of the blades, but to form the spar caps from other materials that are considered to have better strength properties, such as balsa wood that has been reinforced with veneer or glass fiber reinforced laminate or carbon fiber reinforced laminate surface.

[0013] Whether the core material is in the shell, in the shear web, or in the spars cap of a wind turbine blade, the core is typically sandwiched between two or more panels made of several layers of fiberglass bonded with epoxy resin. The cladding provides longitudinal stiffness and strength after curing, while the core provides out-of-plane strength and stiffness. The panels bear most of the bending and in-plane loads, while the core primarily bears the shear loads.

[0014] Regarding the selection of thermoplastic resins, EP 3,231,836 acknowledges that while there is interest in thermoplastic resins, particularly polyester-based resins, this interest has encountered difficulties in development, including the difficulty in determining suitable foaming grades for such resins. Furthermore, although EP 3,231,836 notes that certain polyethylene terephthalate (PET) resins (including recycled forms of PET) can be melt-extruded with suitable physical and / or chemical foaming agents to produce closed-cell foams with the potential for low density and good mechanical properties, it does not disclose any such resin capable of simultaneously producing foams with good environmental and performance properties, and also capable of being formed from sustainable sources. The '836 application identifies several possible polyester resins for forming open-cell foams, including polyethylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate, polyethylene naphthalate, polyvinyl furanoate, or mixtures of two or more of these. Although the use of polyester materials to prepare foams that are essentially free of closed cells, as required by EP'836, may be beneficial for some applications, the disadvantage of such structures is that, in general, open-cell foams will exhibit relatively poor mechanical strength properties.

[0015] CN 108484959 discloses that the preparation of foam products based on 2,5-furandimethyl copolyester is problematic because it asserts the issue of the blowing agent dissolving into the polyester, and proposes a combination of liquid and gaseous blowing agents and a specific method involving the sequential use of these different classes of blowing agents.

[0016] US 2020 / 0308363 and US 2020 / 0308396 each disclose the production of amorphous polyester copolymers, which involve starting with recycled polyester (PET being an example only) as the main component, followed by a series of processing steps to obtain an amorphous copolymer, i.e., a copolymer without crystallinity. Various types of blowing agents are mentioned for use in such amorphous polymers.

[0017] Regarding foaming agents, the use of halogenated olefin foaming agents (including hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO)) is generally known, as disclosed, for example, in US 2009 / 0305876, which is assigned to the assignee of this invention and is incorporated herein by reference. While '876 application discloses the use of HFO and HFCO foaming agents with various thermoplastic materials (including PET) for forming foams, it does not disclose or suggest the use of any such foaming agents with any other type of polyester resin.

[0018] The applicant has realized that by using a combination of polyester resins as disclosed herein with a blowing agent comprising one or more hydrohalogenated olefins as disclosed herein, one or more unexpected advantages can be achieved in relation to the formation of thermoplastic foams, particularly extruded thermoplastic foams.

[0019] The applicant has recognized that one or more unexpected advantages can be achieved with respect to the formation of foam articles and components, including covered or finished thermoplastic foams, wherein the foam is based on PEF, preferably such PEF foams formed using a blowing agent comprising one of the various hydrohalogenated olefins as disclosed herein. The articles disclosed herein overcome one or more of the defects of prior art foam articles, including those described above, and provide significant and unexpected advantages over prior art foam articles and components, as described in more detail below. Summary of the Invention

[0020] This invention includes foam articles, which include:

[0021] (a) An extruded thermoplastic closed-cell extruded foam having at least a first foam surface, and being any one of extruded foams 1 to 4 as defined below; and

[0022] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it.

[0023] For convenience, the foam products referred to in this paragraph are referred to as foam products 1.

[0024] For convenience, but not necessarily as a limitation, the material of the present invention that is different from the thermoplastic closed-cell foam and is attached to at least a portion of the surface of the first foam and / or integral therewith is sometimes referred to herein as a “finishing.”

[0025] The present invention also includes extruded foam articles comprising:

[0026] (a) an extruded thermoplastic closed-cell foam having at least a first surface; and

[0027] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it, wherein the thermoplastic closed-cell foam comprises thermoplastic polymer pore walls and HFO-1234ze(E) in the closed cells, the thermoplastic polymer pore walls comprising at least about 0.5% by weight of an ethylene furanate portion and optionally one or more comonomer portions.

[0028] For convenience, the foam products referred to in this paragraph are referred to as foam products 2 in this document.

[0029] The present invention also includes extruded foam articles comprising:

[0030] (a) An extruded thermoplastic closed-cell foam having at least a first foam surface, wherein: (1) the thermoplastic polymer pores are substantially composed of ethylene furanate and ethylene terephthalate portions; (2) the closed cells contain HFO-1234ze(E); and

[0031] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it.

[0032] For convenience, the foam products described in this paragraph are referred to herein as foam products 3A.

[0033] The present invention also includes extruded foam articles comprising:

[0034] (a) an extruded thermoplastic closed-cell foam having at least a first foam surface; and

[0035] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it, wherein:

[0036] (i) The thermoplastic polymer pore includes a pore wall comprising at least about 0.5% by weight of an ethylene furanate portion;

[0037] (ii) The closed pore contains 1234ze(E); and

[0038] (iii) The extruded foam has a foam density of about 130 kg / m3 to about 425 kg / m3.

[0039] For convenience, the foam articles described in this paragraph are referred to herein as foam articles 3B.

[0040] The present invention also includes extruded foam articles comprising:

[0041] (a) an extruded thermoplastic closed-cell foam having at least a first foam surface; and

[0042] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it, wherein:

[0043] (i) The thermoplastic polymer pore includes a pore wall comprising at least about 1% by weight of an ethylene furanate portion; and

[0044] (ii) The foam has a foam density of about 130 kg / m³ to about 400 kg / m³; and

[0045] (iii) The thermoplastic polymer closed-cell contains HFO-1234ze(E).

[0046] For convenience, the foam products mentioned in this paragraph are referred to as foam products 3C in this document.

[0047] The present invention also includes extruded foam articles comprising:

[0048] (a) an extruded thermoplastic closed-cell foam having at least a first foam surface; and

[0049] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it, wherein:

[0050] (i) The thermoplastic polymer pore includes a pore wall comprising at least about 1% by weight of an ethylene furanate portion; and

[0051] (ii) The foam has a foam density of about 130 kg / m³ to about 400 kg / m³ and a compressive strength of about 1 MPa to about 14 MPa; and

[0052] (iii) The closed-cell thermoplastic polymer contains one or more foaming agents.

[0053] For convenience, the foam products described in this paragraph are referred to as Foam Products 3D in this document.

[0054] The present invention also includes extruded foam articles comprising:

[0055] (a) an extruded thermoplastic closed-cell foam having at least a first foam surface; and

[0056] (b) A material different from the thermoplastic closed-cell foam, which is attached to at least a portion of the surface of the first foam and / or integral with it, wherein:

[0057] (i) The thermoplastic polymer pore includes a pore wall containing at least about 1% by weight of an ethylene furanate portion;

[0058] (ii) The foam has a foam density and compressive strength according to the following foam table 3D; and

[0059] (iii) The thermoplastic polymer closed-cell contains HFO-1234ze(E).

[0060] Foam Table 3D

[0061]

[0062]

[0063]

[0064] For convenience, the foam products referred to in this article are referred to as foam products 3E.

[0065] The present invention also provides a wind turbine blade comprising a blade shell and a foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 within the blade shell. For convenience, the method according to this paragraph is referred to herein as wind turbine blade 1.

[0066] The present invention also provides a transport vehicle comprising a vehicle body and a foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 within the vehicle body. For convenience, the method according to this paragraph is referred to herein as vehicle 1.

[0067] The present invention also provides a fixed building structure comprising structural components and foam articles of the present invention, the foam articles comprising foam articles selected from each of foam articles 1 to 3 selected from those incorporated within or otherwise attached to the vehicle body. For convenience, the method according to this paragraph is referred to herein as fixed building structure 1.

[0068] The present invention also provides a sports equipment article comprising the foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 selected from those incorporated within or otherwise attached to the sports equipment vehicle body. For convenience, the method according to this paragraph is referred to herein as sports equipment article 1.

[0069] The present invention also provides a sports equipment article comprising the foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 selected from those incorporated within or otherwise attached to the sports equipment vehicle body. For convenience, the method according to this paragraph is referred to herein as encapsulation 1. Attached Figure Description

[0070] Figure 1 This is a schematic diagram of an exemplary wind turbine.

[0071] Figure 2 This is a half-illustrative diagram of an exemplary wind turbine.

[0072] Figure 3A This is a cross-section of an exemplary wind turbine blade.

[0073] Figure 3B is a cross-section of an exemplary wind turbine blade.

[0074] Figure 3C is a cross-section of an exemplary wind turbine blade.

[0075] Figure 4 This is an exemplary cross-section of the covered foam of the present invention, which is a specific form of sandwich structure.

[0076] Figure 5 This is a partial schematic diagram of an extruder.

[0077] Figure 6 This is a graph showing the results of extrusion Example 1 described in this article.

[0078] Figure 7 This is a graph showing the results of extrusion Example 1 described in this article.

[0079] Figure 8 This is a graph showing the results of extrusion Example 1 described in this article.

[0080] Figure 9 This is a view of the die plate mentioned in Extrusion Example 1 of this article.

[0081] definition

[0082] 1234ze refers to 1,1,1,3-tetrafluoropropylene, and there are no restrictions on isomers.

[0083] Transl234ze, 1234ze(E) and HFO-1234ze(E) each refer to trans-1,3,3,3-tetrafluoropropylene.

[0084] Closed-cell foam refers to foam in which a significant percentage of the volume of pores are closed, for example, about 20% or more by volume.

[0085] The ethylene furanate moiety refers to the following structure:

[0086] .

[0087] FDCA refers to 2,5-furandicarboxylic acid and has the following structure:

[0088]

[0089] MEG refers to monoethylene glycol and has the following structure:

[0090]

[0091] FDME refers to dimethyl 2,5-furandicarboxylate and has the following structure:

[0092]

[0093] PEF homopolymer refers to a polymer having at least 99 mol% ethylene furanate moiety.

[0094] PEF copolymers refer to polymers having at least about 0.5 mol% of an ethylene furanoate moiety and more than 0.5% of a polymer moiety other than the ethylene furanoate moiety.

[0095] PEF:PET copolymer refers to a polymer having at least about 0.5 mol% of ethylene furanoate moiety and at least 0.5% of ethylene terephthalate moiety.

[0096] PEF stands for poly(ethylene furanoate) and encompasses and is intended to reflect the description of PEF homopolymers and PEF copolymers.

[0097] The ethylene terephthalate part refers to the structure in parentheses:

[0098]

[0099] SSP refers to solid-state polymerization.

[0100] PMDA refers to pyromellitic dianhydride with the following structure:

[0101] Detailed Implementation

[0102] Poly(ethylene furanate)

[0103] This invention relates to foams and foam articles comprising pore walls containing PEF portions.

[0104] The PEF forming the pore walls of the foams and foam articles of the present invention can be a PEF homopolymer or a PEF copolymer, and in particular a PEF:PET copolymer.

[0105] PEF homopolymer is a known material that is known to be formed by: (a) esterification and polycondensation of FDCA with MEG; or (b) transesterification and polycondensation of FDME with MEG, as shown below, for example:

[0106]

[0107] A detailed description of such known esterification and condensation polymerization methods is provided in GB Patent 621971 (Drewitt, JGN and Lincoln, J., entitled "Improvements in Polymers"), which is incorporated herein by reference. Detailed descriptions of these known transesterification reactions and condensation polymerization methods are provided in: Gandini, A., Silvestre, AJD, Neto, CP, Sousa, AF and Gomes, M. (2009), "The furan counterpart of poly(ethylene terephthalate): an alternative material based on renewable resources.", Journal of Polymer Science: Polymer Chemistry (J. Polym. Sci. Polym. Chem.) 47, 295–298. doi: 10.1002 / pola.23130, which is incorporated herein by reference.

[0108] Foam

[0109] This invention includes extruded thermoplastic foams comprising the following:

[0110] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer is substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein the polymer comprises about 0.5 mol% to about 100 mol% of the ethylene furanate portion and optionally at least about 1 mol% of the polyethylene terephthalate portion; and

[0111] (b) HFO-1234ze(E) contained in closed pores.

[0112] For convenience, the extruded foam described in this paragraph is referred to herein as extruded foam 1A.

[0113] This invention includes extruded thermoplastic foams comprising the following:

[0114] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has at least about 5% crystallinity and is substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein the polymer comprises about 0.5 mol% to about 100 mol% of the ethylene furanate portion and optionally at least about 0.5 mol% of the polyethylene terephthalate portion; and

[0115] (b) HFO-1234ze(E) contained in closed pores.

[0116] For convenience, the extruded foam described in this paragraph will be referred to herein as extruded foam 1B.

[0117] This invention includes extruded thermoplastic foams comprising the following:

[0118] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and a polyethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% to about 20 mol% of the ethylene furanate moiety and at least about 0.5 mol% of the polyethylene terephthalate moiety; and

[0119] (b) HFO-1234ze(E) contained in closed pores.

[0120] For convenience, the extruded foam described in this paragraph is referred to herein as extruded foam 1C.

[0121] This invention includes extruded thermoplastic foams comprising the following:

[0122] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate moiety and about 80 mol% to about 99 mol% of the ethylene terephthalate moiety; and

[0123] (b) HFO-1234ze(E) contained in closed pores.

[0124] For convenience, the extruded foam described in this paragraph will be referred to as Extruded Foam 1D in this document.

[0125] This invention includes extruded thermoplastic foams comprising the following:

[0126] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate moiety and about 80 mol% to about 99 mol% of the ethylene terephthalate moiety; and

[0127] (b) HFO-1234ze(E) contained in closed pores.

[0128] For convenience, the extruded foam described in this paragraph will be referred to as extruded foam 1E in this document.

[0129] This invention includes extruded thermoplastic foams comprising the following:

[0130] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% to about 5 mol% of the ethylene furanate moiety and about 95 mol% to about 99.5 mol% of the ethylene terephthalate moiety; and

[0131] (b) HFO-1234ze(E) contained in closed pores.

[0132] For convenience, the extruded foam described in this paragraph will be referred to as Extruded Foam 1F in this document.

[0133] This invention includes extruded thermoplastic foams comprising the following:

[0134] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% to about 2 mol% of the ethylene furanate moiety and about 98 mol% to about 99.5 mol% of the ethylene terephthalate moiety; and

[0135] (b) HFO-1234ze(E) contained in closed pores.

[0136] For convenience, the extruded foam referred to in this document is referred to as Extruded Foam 1G.

[0137] This invention includes extruded thermoplastic foams comprising the following:

[0138] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% of the ethylene furanate moiety and about 99 mol% of the ethylene terephthalate moiety; and

[0139] (b) HFO-1234ze(E) contained in closed pores.

[0140] For convenience, the extruded foam referred to in this document is referred to as extruded foam 1H.

[0141] This invention includes a low-density thermoplastic foam comprising the following:

[0142] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% of the ethylene furanate moiety and about 99.5 mol% of the ethylene terephthalate moiety; and

[0143] (b) HFO-1234ze(E) contained in closed pores.

[0144] For convenience, the extruded foam described in this paragraph will be referred to as extruded foam 1I in this document.

[0145] This invention includes extruded thermoplastic foams comprising the following:

[0146] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 5 mol% of the ethylene furanate moiety and about 95 mol% of the ethylene terephthalate moiety; and

[0147] (b) HFO-1234ze(E) contained in closed pores.

[0148] For convenience, the extruded foam referred to in this article is called extruded foam 1J.

[0149] This invention includes extruded thermoplastic foams comprising the following:

[0150] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 10 mol% of the ethylene furanate moiety and about 90 mol% of the ethylene terephthalate moiety; and

[0151] (b) HFO-1234ze(E) contained in closed pores.

[0152] For convenience, the extruded foam referred to in this article is called Extruded Foam 1K.

[0153] This invention includes extruded thermoplastic foams comprising the following:

[0154] (a) A closed-cell thermoplastic polymer formed during extrusion, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 20 mol% of the ethylene furanate moiety and about 80 mol% of the ethylene terephthalate moiety; and

[0155] (b) HFO-1234ze(E) contained in closed pores.

[0156] For convenience, the extruded foam referred to in this article is called extruded foam 1L.

[0157] This invention includes extruded thermoplastic foams comprising the following:

[0158] (a) A thermoplastic polyethylene furanate closed-cell structure formed during extrusion, comprising pore walls containing polyethylene furanate, wherein at least 25% of the pores are closed-cell; and

[0159] (b) 1234ze(E) contained in the closed pore.

[0160] For convenience, the extruded foam described in this paragraph will be referred to as extruded foam 2A in this document.

[0161] This invention includes extruded thermoplastic foams comprising the following:

[0162] (a) A thermoplastic polymer closed-cell structure formed during extrusion, wherein the pore comprises a pore wall comprising about 1 mol% to about 20 mol% of an ethylene furanate moiety and about 0.5 mol% or more of a polyethylene terephthalate moiety; and

[0163] (b) 1234ze(E) contained in the closed pore.

[0164] For convenience, the extruded foam described in this paragraph will be referred to as extruded foam 2B in this document.

[0165] This invention includes extruded thermoplastic foams comprising the following:

[0166] (a) A thermoplastic polymer closed-cell structure formed during extrusion, comprising pore walls containing about 1 mol% to about 20 mol% of an ethylene furanate moiety and about 0.5 mol% or more of a polyethylene terephthalate moiety, wherein at least 50% of the pores are closed-cell; and

[0167] (b) The gas in the closed pore, wherein the gas contains about 25% to 100% by weight of 1234ze(E). For convenience, the extruded foam according to this paragraph is referred to herein as extruded foam 2C.

[0168] The term "numbered extruded foam" (e.g., extruded foam 1) or "numbered extruded foam group" as defined herein will be referred to in various places throughout this document, and such references refer to each of such numbering systems, including each system with in-group numbering, including any suffix numbering system. For example, referring to extruded foam 1 includes individually referring to each of extruded foams 1A, 1B, 1C, 1D, etc., and referring to extruded foams 1 to 2 should be understood to include individually referring to each of extruded foams 1A, 1B, 1C, 1D, etc., and each of extruded foams 2A, 2B, 2C, 2D, etc. Furthermore, this convention applies throughout this specification to other defined materials, including foaming agents.

[0169] This invention includes extruded thermoplastic foams comprising the following:

[0170] (a) A thermoplastic polymer closed-cell structure formed during extrusion, comprising pore walls substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein said thermoplastic polymer: (i) comprises about 0.5 mol% to about 99.5 mol% of an ethylene furanate portion and optionally at least about 0.5 mol% of a polyethylene terephthalate portion; and (ii) has a molecular weight of at least about 25,000; and

[0171] (b) 1234ze(E) contained in the closed pore.

[0172] For convenience, the extruded foam described in this paragraph will be referred to as extruded foam 3 in this document.

[0173] This invention includes extruded thermoplastic foams comprising the following:

[0174] (a) A thermoplastic polymer closed-cell structure formed during extrusion, comprising pore walls substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein said thermoplastic polymer: (i) comprises about 0.5 mol% to about 99.5 mol% of an ethylene furanate portion and optionally at least about 0.5 mol% of a polyethylene terephthalate portion; and (ii) has a molecular weight of about 25,000 to about 140,000; and

[0175] (b) The trans 1234ze contained in the closed pore.

[0176] For convenience, the extruded foam described in this paragraph will be referred to as extruded foam 4 in this document.

[0177] The extruded foams of the present invention (including each of extruded foams 1 to 4) are formed from PEF homopolymers, PEF copolymers, or combinations / mixtures thereof.

[0178] In a preferred embodiment, the extruded foam of the present invention (including each of extruded foams 1 to 4) may be formed from a PEF homopolymer, wherein the polymer has at least 99.5% by weight or at least 99.9% by weight of an ethylene furanate portion.

[0179] The extruded foams of the present invention (including each of extruded foams 1 to 4) are intended to be formed from PEF copolymers in a preferred embodiment, wherein the polymer (including the PEF copolymer) has about 60% to about 99% by weight of ethylene furanoate portion, or about 70% to about 99% by weight of ethylene furanoate portion, or about 80% to about 99% by weight of ethylene furanoate portion, or about 90% to about 99% by weight of ethylene furanoate portion, or about 95% to about 99.5% by weight of ethylene furanoate portion.

[0180] It is anticipated that the extruded foams of the present invention (including each of extruded foams 1 to 4) may be formed from PEF copolymers in a preferred embodiment, wherein the polymer (including the PEF copolymer) has about 40% to about 1% ethylene furanoate portion, or about 30% to about 1% ethylene furanoate portion, or about 20% to about 1% ethylene furanoate portion, or about 10% to about 1% ethylene furanoate portion, or about 5% to about 1% ethylene furanoate portion, or about 5% to about 0.5% ethylene furanoate portion.

[0181] It is anticipated that the extruded foams of the present invention (including each of extruded foams 1 to 4) may be formed from PEF copolymers in a preferred embodiment, wherein the polymer (including the PEF copolymer) has about 40 mol% to about 1 mol% of ethylene furanoate portion, or about 30 mol% to about 1 mol% of ethylene furanoate portion, or about 20 mol% to about 1 mol% of ethylene furanoate portion, or about 10 mol% to about 1 mol% of ethylene furanoate portion, or about 5 mol% to about 1 mol% of ethylene furanoate portion, or about 5 mol% to about 0.5 mol% of ethylene furanoate portion.

[0182] In a preferred embodiment, the extruded foams of the present invention (including each of extruded foams 1 to 4) are expected to be formed from PEF copolymers, wherein the polymer (including the PEF copolymer) has about 40 mol% to about 1 mol% of ethylene furanoate portion and about 60 mol% to about 99 mol% of polyethylene terephthalate portion, or about 30 mol% to about 1 mol% of ethylene furanoate portion and about 70 mol% to about 99 mol% of polyethylene terephthalate portion, or about 20 mol% to about 1 mol% of ethylene furanoate portion. The portion and about 80 mol% to about 99 mol% of ethylene terephthalate, or about 10 mol% to about 1 mol% of ethylene furanoate and about 90 mol% to about 99 mol% of ethylene terephthalate, or about 5 mol% to about 1 mol% of ethylene furanoate and about 95 mol% to about 99 mol% of ethylene terephthalate, or about 5 mol% to about 0.5 mol% of ethylene furanoate and about 95 mol% to about 99.5 mol% of ethylene terephthalate.

[0183] For those embodiments of the invention involving PEF copolymers, in light of the teachings contained herein, it is expected that those skilled in the art will be able to select the type and amount of copolymer material to be used within each of the ranges described herein to achieve the desired reinforcement / modification of the polymer without excessive experimentation.

[0184] For embodiments of the invention involving the use of PEF homopolymers or PEF copolymers, it is contemplated that such materials having a variety of molecular weights and physical properties within the scope of the invention can be formed. In a preferred embodiment, the extruded foam (including each of extruded foams 1 to 4) is formed from PEF having the characteristic ranges defined in Table 1 below, which are measured as described in the embodiments herein:

[0185] Table 1

[0186]

[0187] In general, given the teachings contained herein, those skilled in the art will be able to formulate PEF polymers within the aforementioned property range without excessive experimentation. However, in preferred embodiments, PEFs (including PEF homopolymers and PEF copolymers) possessing these properties are prepared using one or more of the above-described synthetic methods, combined with a variety of known supplementary processing techniques, including treatment with chain extenders such as PMDA (and alternatives and supplements to PMDA, such as ADR, pentaerythritol (hereinafter referred to as "PENTA"), and talc as described in this embodiment, and / or SSP processing. It is believed that, given the disclosures contained herein, including the polymer synthesis described in the embodiments below (including methods using enhanced polymer crystallization), those skilled in the art will be able to prepare PEF polymers within the characteristic range described in the table above and elsewhere herein. Such processing conditions include the methods for increasing crystallization described herein and such methods disclosed in the embodiments herein.

[0188] Examples of chain extension treatments for polyesters are provided in the article “Recycled poly(ethylene terephthalate) chain extension by areactive extrusion process,” Firas Awaja, Fugen Daver, Edward Kosior, August 16, 2004, available at https: / / doi.org / 10.1002 / pen.20155, which is incorporated herein by reference. As explained in US 1009 / 0264545, which is also incorporated herein by reference, chain extenders are generally compounds that are at least bifunctional relative to a reactive group, which can react with end groups or functional groups in the polyester to extend the length of the polymer chain. In some cases, as disclosed herein, such treatments can advantageously increase the average molecular weight of the polyester to improve its melt strength and / or other important properties. The degree of chain extension achieved is at least in part related to the structure and functionality of the compound used. A variety of compounds can be used as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (hereinafter referred to as PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing polyfunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposites such as finely dispersed nanoclays may optionally be used to control viscosity. Commercially available chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema. The amount of chain extender may vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to treat the polymer may vary over a wide range, and in a preferred embodiment, is in the range of about 0.1 wt% to about 5 wt%, or preferably about 0.1 wt% to about 1.5 wt%. Examples of chain extenders are also described in U.S. Patent No. 4,219,527, which is incorporated herein by reference.

[0189] An example of the SSP processing method for poly(ethylene furanoate) is provided in the article “Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase”, Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which are incorporated herein by reference.

[0190] The PEF thermoplastic polymers that are particularly advantageous for preparing the extruded foams (including extruded foams 1 to 4 and FC1 to FC11) and extruded foam articles (including extruded foam articles 1 to 4) of the present invention are indicated in the following table of thermoplastic polymers (Table 2A), wherein all values ​​in the table are to be understood as being preceded by the word "about".

[0191] Table 2A - Thermoplastic Polymers

[0192]

[0193] PEF thermoplastic polymers particularly advantageous for the preparation of extruded foams (including extruded foams 1 to 4 and FC1 to FC11) and extruded foam articles (including foam articles 1 to 4) also include those materials listed in the following table of thermoplastic polymers (Table 2B), wherein all values ​​in the table are understood to be preceded by the word "about".

[0194] Table 2B - Thermoplastic Polymers

[0195]

[0196] The PEF thermoplastic polymers particularly advantageous for preparing the extruded foams (including extruded foams 1 to 4 and FC1 to FC11) and extruded foam articles (including foam articles 1 to 4) of the present invention also include those materials indicated in the following table of thermoplastic polymers (Table 2C), wherein all values ​​in the table are understood to be preceded by the word "about".

[0197] Table 2C - Thermoplastic Polymers

[0198]

[0199]

[0200] For the purpose of defining the terminology used herein, it should be noted that throughout this document, references will be made to the thermoplastic polymers shown in the first column of each row in the TPP table above, and references to each of these numbers will be references to the thermoplastic polymer as defined in the corresponding column of that row. Referring to a group of TPPs defined in the table above by referring to a TPP number means referring to each TPP with such a number individually and independently, including each TPP with the number shown, including any such number with a suffix. Thus, for example, referring to TPP1 is referring to TPP1A, TPP1B, TPP1C, TPP1D, and TPP1E individually and independently. Referring to TPP1-TPP2 is referring to TPP1A, TPP1B, TPP1C, TPP1D, TPP1E, TPP2A, TPP2B, TPP2C, TPP2D, and TPP1E individually and independently. This convention of use also applies to the foamable compositions table and extruded foam table below.

[0201] foaming agent

[0202] As explained in detail herein, the present invention includes, but is not limited to, the applicant’s discovery that a selected group of foaming agents can provide foamable PEF foamable compositions and PEF extruded foams and extruded foam articles (including foam articles 1 to 4) with an unattainable and surprising combination of physical properties, including low density and good mechanical strength properties.

[0203] The blowing agent used according to the invention preferably comprises one or more hydrogen halide olefins having three or four carbon atoms. For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1A.

[0204] The blowing agent used according to the invention preferably consists substantially of one or more hydrogen haloolefins having three or four carbon atoms. For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1B.

[0205] The blowing agent used according to the invention preferably consists substantially of one or more hydrogen haloolefins having three or four carbon atoms. For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1C.

[0206] The foaming agent used according to the present invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as foaming agent 2A for convenience); or comprises one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 3A for convenience); or comprises one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 4A for convenience); or comprises trans 1234ze and trans 1 One or more of 336mzz (hereinafter referred to as foaming agent 5A for convenience); or containing trans 1234ze (hereinafter referred to as foaming agent 6A for convenience); or containing trans 1336mzz (hereinafter referred to as foaming agent 7A for convenience); or containing cis 1336mzz (hereinafter referred to as foaming agent 8A for convenience); or containing 1234yf (hereinafter referred to as foaming agent 9A for convenience); or containing 1224yd (hereinafter referred to as foaming agent 10A for convenience); or containing trans 1233zd (hereinafter referred to as foaming agent 11A for convenience).

[0207] The foaming agent used according to the present invention preferably consists essentially of one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as foaming agent 2B for convenience); or consists essentially of one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 3B for convenience); or consists essentially of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 4B for convenience); or consists essentially of trans 1234ze and trans 1336mz It consists of one or more of the following (hereinafter referred to as foaming agent 5B for convenience); or is essentially composed of trans-1234ze (hereinafter referred to as foaming agent 6B for convenience); or is essentially composed of trans-1336mzz (hereinafter referred to as foaming agent 7B for convenience); or is essentially composed of cis-1336mzz (hereinafter referred to as foaming agent 8B for convenience); or is essentially composed of 1234yf (hereinafter referred to as foaming agent 9B for convenience); or is essentially composed of 1224yd (hereinafter referred to as foaming agent 10B for convenience); or is essentially composed of trans-1233zd (hereinafter referred to as foaming agent 11B for convenience).

[0208] The foaming agent used according to the present invention preferably consists of one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as foaming agent 2B for convenience); or consists of one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 3B for convenience); or consists of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 4B for convenience); or consists of trans 1234ze and trans 133 It may consist of one or more of the following 6mzz (hereinafter referred to as foaming agent 5B for convenience); or consist of trans 1234ze (hereinafter referred to as foaming agent 6B for convenience); or consist of trans 1336mzz (hereinafter referred to as foaming agent 7B for convenience); or consist of cis 1336mzz (hereinafter referred to as foaming agent 8B for convenience); or consist of 1234yf (hereinafter referred to as foaming agent 9B for convenience); or consist of 1224yd (hereinafter referred to as foaming agent 10B for convenience); or consist of trans 1233zd (hereinafter referred to as foaming agent 11B for convenience).

[0209] Therefore, it is contemplated that the foaming agents of the present invention (including each of foaming agents 1 to 11) may also include, in addition to each of the aforementioned foaming agents, a co-foaming agent comprising one or more optional potential co-foaming agents as described below. In a preferred embodiment, the foamable compositions, extruded foams, and extrusion methods of the present invention comprise foaming agents as described herein, wherein the indicated foaming agents (including compounds or groups of compounds specifically identified in each of foaming agents 1 to 11) are present in an amount of at least about 50% by weight, or preferably at least about 60% by weight, preferably at least about 70% by weight, or preferably at least about 80% by weight, or preferably at least about 90% by weight, or preferably at least about 95% by weight, or preferably at least about 99% by weight, based on the total weight of all foaming agent components.

[0210] It is anticipated and understood that the foaming agents of the present invention (including each of foaming agents 1 to 11) may include one or more co-foaming agents not included in the illustrated selection, provided that the amount of such co-foaming agents used does not interfere with or eliminate the ability to obtain relatively low-density extruded foams (including each of extruded foams 1 to 4) as described herein, and preferably does not interfere with or eliminate the ability to obtain extruded foams with mechanical strength properties as described herein. Therefore, in consideration of the teachings contained herein, it is anticipated that those skilled in the art will be able to select one or more of the following potential co-foaming agents for a particular application without excessive experimentation: one or more saturated hydrocarbons or hydrofluorocarbons (HFCs) known in the art, particularly C4-C6 hydrocarbons or C1-C4 HFCs. Examples of such HFC co-foaming agents include, but are not limited to, difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and one or a combination of all isomers of all such HFCs. Regarding hydrocarbons, in some preferred embodiments, the foaming agent composition of the present invention may further include, for example, isopentane, n-pentane and / or cyclopentane, and butane and / or isobutane. Other materials may also be included, such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, such as dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (such as ethanol and / or propanol and / or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl ether and diethyl ether), diethers (such as dimethoxymethane and diethoxymethane)) and methyl formate, organic acids (such as, but not limited to, formic acid), including any combination of these, but such components are not necessarily preferred in many embodiments due to their negative environmental impact.

[0211] Extruded foam and extrusion process

[0212] The extruded foams of the present invention (including each of extruded foams 1 to 4) or extruded foams made from the PEF polymers of the present invention (including thermoplastic polymers TPP1A to TPP22E, or any of the extruded PEF foams described in the following examples) can generally be formed from the foamable and extrudable compositions of the present invention. Generally, the foamable compositions of the present invention can be formed by combining the PEF polymers of the present invention (including each of thermoplastic polymers TPP1A to TPP22E) with the foaming agents of the present invention (including each of foaming agents 1 to 11).

[0213] The following tables of expandable compositions (Tables 3A and 3B) describe expandable compositions that are included in the present invention and provide specific advantages in relation to the formation of the foams of the present invention, wherein all numerical values ​​in the tables are understood to be preceded by the word "about", and wherein the following terms used in the tables have the following meanings:

[0214] CBAG1 refers to a foaming agent selected from the group consisting of: 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf, and combinations of two or more of these.

[0215] CBAG2 refers to a foaming agent selected from the group consisting of: water, CO2, C1-C6 hydrocarbons (HC), HCFC, C1-C5 HFC, C2-C4 hydrohalogenated olefins, C1-C5 alcohols, C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers, C1-C4 esters, organic acids, and combinations of two or more of these.

[0216] CCBAG3 refers to a foaming agent selected from the group consisting of: water, CO2, isobutane, n-butane, isopentane, cyclopentane, cyclohexane, trans-dichloroethylene, ethanol, propanol, butanol, acetone, dimethyl ether, diethyl ether, dimethoxymethane, diethoxymethane, methyl formate, difluoromethane (HFC-32), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), trifluoroethane (HFC-143), 1112-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and combinations of any two or more of these.

[0217] NR means not required.

[0218] Table 3A - Foamable Compositions

[0219]

[0220]

[0221]

[0222]

[0223]

[0224]

[0225] Table 3BA - Foamable Compositions

[0226]

[0227]

[0228]

[0229]

[0230] Foam Formation Methods

[0231] In light of the disclosure contained herein, it is contemplated that the extruded foams of the present invention (including each of extruded foams 1 to 4) can be formed using any one or more of a variety of known techniques for forming thermoplastic foams by extruding thermoplastic polymers, and all such techniques, as well as all extruded foams and extruded foam articles (including foam articles 1 to 3) formed thereby, are within the broad scope of the present invention. For clarity, it should be noted that the definitions of foam in the table below all begin with the letter F, in contrast to the foams defined in the paragraphs of the above description of the invention, which begin with the capitalized word Foamable Composition.

[0232] Typically, the forming step involves introducing the inventive foaming agent, comprising each of the foaming agents 1 to 31, into the inventive PEF polymer comprising each of TPP1 to TPP22 to form a foamable PEF composition comprising PEF and a foaming agent. An example of a preferred method for forming the foamable PEF composition of the present invention is plasticizing the PEF, preferably comprising heating the PEF in an extruder barrel to its melt temperature, preferably above its melt temperature, and then introducing the inventive foaming agent into the extruder barrel while the polymer melt travels downwards along the extruder barrel, under conditions that allow the desired amount of foaming agent (preferably by dissolution) to be effectively incorporated into the polymer melt.

[0233] In a preferred embodiment, the foaming method of the present invention includes providing a foamable composition of the present invention (including each of FC1 to FC13) above its melt temperature in an extruder barrel, and foaming the foamable composition by extruding the composition in the extruder barrel through an orifice plate, which preferably forms an extruded foam of the present invention. In a preferred embodiment, the extruded foam is then used to form foam articles of the present invention, including each of foam articles 1 to 4.

[0234] The extrusion method of the present invention may include semi-batch and continuous methods, as well as combinations of both or more of these methods. The semi-batch aspect of the method of the present invention may generally involve preparing at least a portion of a foamable polymer composition (including each of FC1 to FC13) in a storable state (such as a hopper), and then using that portion of the foamable polymer composition as feed for a continuous extrusion process at a future point in time, such as by introducing it into an extruder barrel. Therefore, the present invention includes a method comprising: 1) mixing a PEF thermoplastic polymer including each of TPP1 to TPP22 with an inventive foaming agent including each of foaming agents 1 to 31, under conditions for forming a foamable PEF composition; 2) extruding the foamable PEF composition including each of FC1 to FC13 into a holding zone maintained at a temperature and pressure that does not allow foaming of the foamable composition, wherein the holding zone preferably includes a die plate defining one or more orifices leading to a low-pressure zone, including FC1 to FC13. The foamable polymer composition of each of 13 foams in the low-pressure zone, and the holding zone also includes an openable door that closes the die orifice; 3) periodically opening the door while applying mechanical pressure, for example by a movable pressure head, to the foamable polymer composition including each of FC1 to FC13 to discharge it from the holding zone through the die orifice into the low-pressure zone; and 4) causing the discharged foamable polymer composition to expand under the action of a foaming agent to form foam, including extruding each of foams 1 to 4 and each of foams F1 to F8.

[0235] The present invention can also use a continuous method to form foam. For example, such a continuous method involves forming an expandable PEF composition, comprising each of FC1 to FC13, and then expanding the expandable PEF composition substantially without interruption. For example, a foamable PEF composition comprising each of FC1 to FC13 can be prepared in an extruder as follows: heating a selected PEF polymer resin (comprising each of TPP1 to TPP22) (which can be fed from a hopper) to form a PEF melt, incorporating the foaming agent of the present invention (comprising each of foaming agents 1 to 11) (preferably in the liquid phase) into the PEF melt, preferably by dissolving the foaming agent into the PEF melt under initial pressure, to form a foamable PEF composition comprising a substantially homogeneous combination of PEF and foaming agent (comprising each of FC1 to FC13), and then extruding the foamable PEF composition through a die plate into a zone under a selected foaming pressure, allowing the foamable PEF composition to expand into foam under the influence of the foaming agent, comprising each of foams 1 to 4 and each of foams F1 to F8 described below. Optionally, the foamable PEF composition containing the PEF polymer (including each of FC1 to FC13) and the incorporated foaming agent (including each of foaming agents 1 to 11) may be cooled before the composition is extruded through a die to enhance certain desired properties of the resulting foam (including each of foams 1 to 6 and each of foams F1 to F8).

[0236] This method can be used, for example, by using Figure 5The extrusion is performed using general-type extrusion equipment disclosed herein. Specifically, the extrusion apparatus may include a raw material feed hopper 10 for receiving the PEF polymer 15 of the present invention (including each of TPP1 to TPP22) and one or more optional components (which may be added together with the PEF in the hopper or optionally added elsewhere in the process, depending on the user's specific needs). The feed 15, excluding the blowing agent, may be loaded into the hopper and delivered to the screw extruder 10. The extruder 20 may include thermocouples (not shown) located at three points along its length and a pressure sensor (not shown) located at the discharge end 20A of the extruder. A mixer section 30 may be located at the discharge end 20A of the extruder for receiving the blowing agent components of the present invention (including each of blowing agents 1 to 31) via one or more metering pumps 40A and 40B and mixing those blowing agents into the PEF melt in the mixer section. Sensors (not shown) may be included for monitoring the temperature and pressure of the mixer section 30. The mixer section 30 then discharges the foamable composition melt of the present invention (including each of FC1 to FC13) into a pair of melt coolers 50 oriented in series, wherein temperature sensors (not shown) are located in each cooler to monitor the melt temperature. The melt is then extruded through a die 60, which also has temperature sensors and pressure sensors (not shown) for monitoring temperature and pressure at the die. The die pressure and temperature can be varied according to the needs of each specific extrusion application producing the foam 70 of the present invention (including each of extruded foams 1 to 4 and each of foams F1 to F8 as described below). The foam can then be transported from the extrusion equipment via a conveyor belt 80.

[0237] The foamable polymer compositions of the present invention (including each of FC1 to FC13) may optionally contain additional additives, such as nucleating agents, pore control agents, glass fibers and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR attenuators, and thermal insulating additives. Nucleating agents particularly include materials such as talc, calcium carbonate, and sodium benzoate, as well as chemical foaming agents such as azodicarbonamide or sodium bicarbonate and citric acid. IR attenuators and thermal insulating additives may include carbon black, graphite, silica, metal flakes or powders, etc. Flame retardants particularly include brominated materials such as hexabromocyclodecane and polybrominated diphenyl ethers. According to known techniques, each of the above-mentioned optional additional additives may be introduced into the foam at different times and locations in the process, and all such additives and methods of addition are within the broad scope of the present invention.

[0238] Foam

[0239] In a preferred embodiment, the extruded foam of the present invention is formed in a commercial extrusion apparatus and has the properties shown in Table 4 below, wherein the values ​​are measured as described in the embodiments herein:

[0240] Table 4

[0241]

[0242] Foams included within this invention and providing certain advantages are described in Table 5 below, wherein all values ​​in the table are understood to be preceded by the word "about", and wherein the name NR means "not required".

[0243] Table 5 - Foam Table

[0244]

[0245]

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254]

[0255]

[0256]

[0257]

[0258]

[0259]

[0260]

[0261]

[0262]

[0263]

[0264]

[0265]

[0266]

[0267]

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279] The foams of this invention have a wide range of applications. The foams of this invention (including each of foams 1 to 4 and foams F1 to F8) have unexpected advantages in applications requiring low density and / or good compressive and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recycled materials and recyclable. In particular, the foams of this invention (including each of foams 1 to 6 and each of foams F1 to F8) have unexpected advantages in the following applications: wind energy applications (wind turbine blades (shear webs, shells, cores, and roots)); marine applications (hulls, decks, superstructures, bulkheads, chords, and interior trim); industrial weight reduction applications; and automotive and transportation applications (internal and external parts of cars, trucks, trains, airplanes, and spacecraft).

[0280] The extruded foams of the present invention (including each of extruded foams 1 to 4) are formed from PEF homopolymer, PEF copolymer, PEF:PET copolymer or a combination / mixture thereof.

[0281] In a preferred embodiment, the foam (including each of extruded foams 1 to 4) may be formed from a PEF homopolymer, wherein the polymer has at least 99.5% by weight, or at least 99.9% by weight, an ethylene furanate portion.

[0282] The foams of the present invention (including each of foams 1 to 3) are intended to be formed from PEF copolymers in a preferred embodiment, wherein the polymer (including the PEF copolymer) has about 0.5% by weight to about 99% by weight of ethylene furanate portion. The present invention includes foams (including each of extruded foams 1 to 3) wherein the thermoplastic polymer is substantially composed of the components described in the following table:

[0283]

[0284]

[0285] The extruded foams of the present invention (including each of extruded foams 1 to 4) may include closed-cell walls comprising each of the thermoplastic polymers of the present invention, including each of TMP1 to TMP12 described in the table above.

[0286] For those embodiments of the invention involving PEF copolymers, in light of the teachings included herein, it is expected that those skilled in the art will be able to select the type of amount of copolymer material to be used within each of the ranges described herein to achieve the desired reinforcement / modification of the polymer without excessive experimentation.

[0287] It is anticipated that the TMP of the present invention can form polymers with a variety of physical properties, including the following polymer characteristic ranges, which are measured as described in the examples herein:

[0288]

[0289] In general, given the teachings contained herein, those skilled in the art will be able to formulate PEF polymers within the aforementioned property range without excessive experimentation. However, in preferred embodiments, PEF polymers (including the PEF:PET copolymers of the present invention) having these properties are achieved using one or more of the above-described synthetic methods, combined with various known supplementary processing techniques (including treatment with chain extenders such as PMDA, and / or SSP).

[0290] Examples of chain extension treatments for polyesters are provided in the article “Recycled poly(ethylene terephthalate) chain extension by areactive extrusion process,” Firas Awaja, Fugen Daver, Edward Kosior, August 16, 2004, available at https: / / doi.org / 10.1002 / pcn.20155, which is incorporated herein by reference. As explained in US 1009 / 0264545, which is incorporated herein by reference, chain extenders are generally compounds that are at least bifunctional relative to a reactive group, which can react with end groups or functional groups in the polyester to extend the length of the polymer chain. In some cases, as disclosed herein, such treatments can advantageously increase the average molecular weight of the polyester to improve its melt strength and / or other important properties. The degree of chain extension achieved is at least in part related to the structure and functionality of the compound used. A variety of compounds can be used as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing polyfunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposites such as finely dispersed nanoclays may optionally be used to control viscosity. Commercially available chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema. The amount of chain extender may vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to treat the polymer may vary over a wide range, and in a preferred embodiment, is in the range of about 0.1 wt% to about 5 wt%, or preferably about 0.1 wt% to about 1.5 wt%. Examples of chain extenders are also described in U.S. Patent No. 4,219,527, which is incorporated herein by reference.

[0291] An example of the SSP processing method for poly(ethylene furanoate) is provided in the article “Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase”, Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achillas, and Dimitrios N. Bikiaris, which are incorporated herein by reference.

[0292] foaming agent

[0293] As explained in detail herein, the present invention relates to the applicant’s discovery that a selected set of foaming agents is capable of providing each of expandable PEF compositions (including expandable composition 1) and PEF foams (including extruded foams 1 to 4) with a surprising combination of physical properties that are difficult to achieve, including low density and good mechanical strength properties.

[0294] Foam and foaming methods

[0295] The foam of the present invention is a thermoplastic foam, and in view of the disclosure included herein, it is generally contemplated that any one or more of the various known extrusion techniques for forming thermoplastic foams can be used, and all such techniques and all foams formed therefrom are within the broad scope of the present invention.

[0296] In a preferred embodiment, the extruded foams of the present invention (including each of extruded foams 1 to 4) are prepared in a commercial extruder, and even more preferably in a commercial extruder with a throughput of about 2,000 lbs / h to about 6,000 lbs / h.

[0297] Foam products

[0298] The foams and foam articles of the present invention have a wide range of applications. The foam articles of the present invention, including each of foam articles 1 to 3, including foam articles prepared by extrusion of foams 1 to 4 in a commercial extruder, have unexpected advantages, particularly in applications requiring low density and / or good compressive and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recycled materials and recyclable. In particular, the foam articles of the present invention, including each of foam articles 1 to 3, including foam articles prepared by extrusion of foams 1 to 4 in a commercial extruder, have unexpected advantages in: wind energy applications (wind turbine blades (shear webs, shells, cores, and nacelles); marine applications (hulls, decks, superstructures, bulkheads, chords, and interior trim); industrial low-weight applications; automotive and transportation applications (internal and external components of cars, trucks, trains, airplanes, and spacecraft); fixed building structures; and sports equipment.

[0299] As described above, the foam articles of the present invention (including each of foam articles 1 to 3) generally comprise foam having a finish on at least a portion of its surface. As used herein, references to numbered foam articles or groups of numbered foam articles as defined herein refer to each of such numbered foam articles, including each foam article having a group number, including any number with a suffix. For example, reference to foam article 3 includes references to each of foam articles 3A, 3B, 3C, and 3D.

[0300] Within the scope of this invention, the size and shape of the extruded foam used in the foam articles of this invention can vary widely depending on the intended use of the article, and all such sizes and shapes are within the scope of this invention. In many applications, the foam article will be in a three-dimensional form, wherein the length and / or width are significantly greater than the thickness. In other applications, the form of the article may be characterized as a block, sheet, panel, etc., or a specific shape such as an I-beam, U-shape, or other specific shape.

[0301] For ease of explanation, but not as a limitation, Figure 4One form is shown in which the foam article is in the general shape of a sheet or panel having a facing on each side. In the illustrated embodiment, the foam article according to the invention comprises a core 1 of the PEF foam of the invention, the core comprising each of TMPs 1 to 12 as defined below, and the foam article comprises at least one reinforcing facing 2 and at least one connecting and / or integrating layer 3. In view of the teachings contained herein, those skilled in the art will understand that the connecting / integrating layer may comprise, for example, an adhesive layer, or may be formed by integrating the core material and the facing material without the use of a separate adhesive, for example by melting the surfaces of the two materials together to form a connecting / integrating region. The facing may be any material suitable for the intended use, as described above, but in many applications, the facing 2 is a sheet or film of fibrous material as described above. Preferably, the fibers of the facing 2 may be in the form of, for example, woven or nonwoven mats (or mats comprising a combination of woven and nonwoven fibers), including crimped mats that may be woven or nonwoven, and the fibers may be oriented or nonoriented (i.e., random). In embodiments where the fibers of the finish are oriented, the orientation may include unidirectional orientation, bidirectional orientation, biaxial orientation, triaxial orientation, quadriaxial orientation, and any combination thereof.

[0302] The connecting / integrating membrane, layer, or region 3 can be any material and of any thickness required to attach or integrate the finish 3 to the core 1. Furthermore, although the membrane or layer 3 is shown as typically situated between the finish 2 and the core 1, those skilled in the art will understand and recognize that the connecting layer or membrane typically extends into each of the foam core 1 and the finish 2. In some preferred embodiments, the membrane or layer 3 may comprise an adhesive material, such as an epoxy adhesive, which bonds the core 1 and the finish sheet 2 together. Other adhesive resins that can be used to bond the finish to the foam include polyurethane, vinyl ester, polyester, cyanate ester, polyurethane acrylate, bismaleimide, polyimide, silicone, phenolic resin, polypropylene, caprolactam, and any combination of two or more of these. Generally, the processing of the foam article of the present invention includes steps that provide a strong chemical and / or physical bond between the finish 2 and the foam 1, and all such steps are within the scope of the present invention.

[0303] In a preferred embodiment, the finish 2 comprises a plurality of mutually bonded sheets or pads, which may be identical or different and bonded together by suitable means, including mutually bonded layers of adhesive or resin or mutually bonded regions formed by material integration (e.g., melting together to form an integrated region). In such embodiments, the number of mutually bonded sheets constituting the finish 2 is expected to vary over a wide range, and in a preferred embodiment, the finish comprises from 2 to 10 mutually bonded sheets, and even more preferably from about 3 to about 5 mutually bonded sheets.

[0304] While it should be understood that the dimensions of the foam articles of the present invention (including each of foam articles 1 to 3) can vary within a wide range, in a preferred embodiment relating to uses related to wind turbine applications, the panel can vary from about 0.1 mm to about 3 mm, or from about 0.4 mm to about 1.5 mm. Furthermore, it is generally understood that the relative thickness of the foam compared to the panel can vary within a wide range depending on the specific application, and those skilled in the art will be able to make appropriate selections based on the teachings contained herein, and generally the panel thickness will be less than the foam thickness.

[0305] Preferred materials for forming the foam articles of the present invention (including each of foam articles 1 to 3) are described in further detail below.

[0306] Finish

[0307] The foam articles of the present invention include finishes that can have a wide variety of sizes, the size of which will depend on the specific needs of the application in which the foam articles will be used, and articles having all such sizes are within the scope of the present invention.

[0308] The materials forming the finishing material can also vary widely depending on the specific use of the foam article, and all such materials are within the scope of this invention. For example, the finishing material used in the foam articles of this invention (including each of foam articles 1 to 3) comprises one or more fibrous sheets or pads, wherein the fibrous portion can be formed from a wide variety of materials, including, for example, glass fibers (preferably impregnated with resins and / or polymers), other natural fibers (such as cellulose and other plant-derived materials), mineral fibers (such as quartz), metal fibers or membranes, carbon fibers (preferably impregnated or reinforced with one or more polymers (including thermoplastic polymers and / or thermosetting polymers), synthetic fibers such as polyesters (including fibers comprising furanyl polyesters, as disclosed, for example, in US 2015 / 0111450, which is incorporated herein by reference), polyethylene, aromatic polyamides, Kevlar, and any and all combinations thereof.

[0309] Specific purpose

[0310] The foam articles of the present invention have a wide range of applications. The foam articles of the present invention (including each of foam articles 1 to 3) have unexpected advantages in applications requiring low density and / or good compressive and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made of recycled materials and recyclable. In particular, the foam articles of the present invention (including each of foam articles 1 to 3) have unexpected advantages in the following areas: such as fluid energy transfer components in wind and hydroelectric applications (e.g., wind turbine blades (shear webs, shells, cores, and nacelles) for transferring wind energy from stationary or mobile equipment located in the air, and vortex, tidal, and ocean current oscillating hydrofoils and kitesurfs that recover hydrodynamic energy from stationary or mobile equipment located in the water); marine applications (hulls, decks, superstructures, bulkheads, chords, and interior trim); industrial weight reduction applications; automotive and transportation applications (internal and external parts of cars, trucks, trains, airplanes, and spacecraft); and encapsulation applications.

[0311] Special Reference Figure 2 and Figure 3AFigures 3B and 3C show that the foam articles of the present invention (including each of foam articles 1 to 3) can be used in the rotor blade 10 at any and all locations along the length of the blade from the blade root 30 to the blade tip 32 opposite to the blade root 30, and at any location along the body housing, including on the pressure side 34, on the suction side 36, and at any location extending between the leading edge 26 and the trailing edge 28 of the rotor blade 10. Further, the foam articles of the present invention (including each of foam articles 1 to 3) can be used for all or part of longitudinally extending structural members and for one or more shear webs 24 disposed between spar caps 20, 22 to form a beam configuration. These structural members are configured to provide increased stiffness, bending resistance, and / or strength to the rotor blade 10, such as longitudinally extending spar caps 20, 22, which are configured to engage the opposing inner surfaces 35, 37 of the pressure side 34 and the suction side 36 of the rotor blade 10. The spar caps 20 and 22 are typically designed to resist bending stresses during operation of the wind turbine 10 and to minimize blade tip deflection and / or other loads acting on the rotor blade 10 in the generally spanwise direction (parallel to the span 23 of the rotor blade 16); however, it should be understood that in other applications, the spar caps may also be oriented at any angle transverse to the spanwise axis (including at an angle of approximately 90 degrees relative to the spanwise axis). Similarly, the spar caps 20 and 22 may also be designed to resist spanwise compression or tension that occurs during operation of the wind turbine 6. Due to the unexpected combination of the lightweight and high strength of the extruded foam of the present invention and the foam articles of the present invention (including each of foam articles 1 to 3), the spars and caps used at the blade roots and in the rotor blades are advantageously suited for use with such foams and foam articles.

[0312] The following table of extruded foam uses includes identification of some preferred uses of some preferred products of the present invention, wherein the column heading "Foam Product Number" refers to the foam product as indicated above, and the column heading "Specific Extruded Foam" refers to the extruded foam as indicated above.

[0313]

[0314]

[0315]

[0316]

[0317] Example

[0318] Extrusion Examples

[0319] Extrusion Example 1

[0320] Without limiting the full scope of the invention, the applicant conducted a series of experiments using a twin-screw extruder with a screw diameter of 17.8 mm and a screw length-to-diameter ratio of 40:1. The die plate has approximately as follows: Figure 9 The design and dimensions shown.

[0321] Although a circular die orifice is used, other orifice shapes (such as hexagonal) can also be used. The extruder has 13 barrel sections and operates under the following processing conditions:

[0322] Average temperature in the first 3 / 4 of the barrel: 210℃-250℃

[0323] Average melt temperature (PEF) at the mold plate: 220℃-250℃

[0324] Average melt temperature (PTE) at the mold plate: 240℃-260℃

[0325] Pressure at the mold plate: 500psig-1000psig

[0326] Extruder RPM: 50-1000

[0327] Throughput: 3 lbs / hour - 4 lbs / hour

[0328] Foaming agent flow rate: 1ml-2ml liquid 1234ze(E) / min

[0329] These tests demonstrate the ability to manufacture the extruded PEF foam of the present invention and, by comparison with foam made of PET, demonstrate at least some unexpected results associated with the invention. One difference between the foam prepared and tested in this embodiment and commercially available extruded foam is that commercial foam is typically formed by joining segments of the extruded foam together, and the presence of these seams tends to strengthen the foam overall. In this embodiment, no joined foam is formed; therefore, if joined foam were formed, the strength of the foam produced in these embodiments would be higher than the values ​​reported herein. Due to this and other potential factors, the strength results reported in these embodiments are generally lower than those expected by those skilled in the art when performing foaming methods on commercial extruders. However, as shown in the following embodiments, the strength results reported for the extruded foam of the present invention are unexpectedly higher than those expected by those skilled in the art.

[0330] The tests used herein involved foams made from commercially available PEF and PET polymers. The commercial PET polymer has a molecular weight of 43,000 and a crystallinity of 41%. The PEF polymer has a molecular weight of 32,000 (crystallinity unknown). As the data reported below show, despite certain factors that would lead those skilled in the art to expect lower strength from PEF foams, the PEF foams of this invention unexpectedly outperformed the PET polymers.

[0331] A range of PEF foams and a reference PET foam were prepared using the highly preferred 1234ze(E) of the present invention as a foaming agent and by adding 0.64% by weight of PMDA to the extruder during extrusion. The foams comprised densities ranging from about 130 kg / m³ to less than about 400 kg / m³. 3 The foam.

[0332] For each polymer, unique and narrow-range extrusion conditions were specified for the foaming experiments. The conditions used were determined to obtain optimal results for each polymer.

[0333] The density of the resulting foam was determined using a method generally corresponding to ASTM D71, throughout the examples in this application, except that hexane was used instead of water for displacement. Compressive strength measurements were performed in the extrusion direction in each case, based on guidelines provided in ASTM C297 and ISO 844, respectively.

[0334]

[0335]

[0336] The applicant was surprised to find that the extruded foam of the present invention has excellent strength characteristics, as measured by compressive strength values. In particular, the following graph shows the trend line data of compressive strength as a function of foam density.

[0337] As shown in the data charts below, throughout the density range reported in these embodiments, foams made from PEF homopolymer according to the invention exhibit significantly superior strength properties as a function of density, compared to foams formed from PET homopolymers. One way to illustrate this unexpected performance is to examine the trend lines of the two sets of foam data. By way of example, at the upper end of the tested density range (at approximately 380 kg / m³), the trend line for the PET data shows a compressive strength value of approximately 7 MPa, while the trend line for the PEF data shows a compressive strength value of approximately 11. This represents a compressive strength advantage of approximately 1.6 times compared to PET foam. This advantage is particularly surprising considering that the PEF foam is made from PEF with a molecular weight of 32,000, while the molecular weight of PET foam is approximately 1.35 times that (43,000). This is in... Figure 6 The figure shows data results in the range of approximately 180 kg / m³ to approximately 380 kg / m³.

[0338] Even at the lowest density tested, Figure 6 The trend line also shows that at approximately 135 kg / m³, PET data shows an average compressive strength of approximately 1.4 MPa, while the trend line for PEF data shows a compressive strength of approximately 1.6 MPa. Therefore, even at the lower end of the tested density range, PEF foam exhibits surprisingly excellent performance, such as... Figure 7 The data charts provided are shown in the document.

[0339] Figure 8 The document provides charts showing all the test data.

[0340] Based on all available data in this embodiment, the extruded foam of the present invention achieves an unexpected increase in compressive strength of approximately 1.25 to approximately 1.6 times compared to the average PET homopolymer performance. The foam of the present invention also offers significant advantages over foams formed from PET homopolymers: the same compressive strength as PET foam can be achieved with a significantly lower density. As a specific example, if PET with a density of 250 kg / m³ is used in a given application (e.g., at the root of a wind turbine blade), to achieve a CS strength of 4, based on the trendline data shown herein, the PEF foam of the present invention can be used instead of PET foam. This PEF foam also has a CS strength of 4 MPa but with a much lower foam density, i.e., any density as low as 200 kg / m³. This represents a weight reduction of up to approximately 25% for that given application. These are highly beneficial and unexpected results, as illustrated in the embodiments below for several specific applications, including wind turbine blades.

[0341] As described in the foregoing text description (including examples), the foam of the present invention provides important and unexpected advantages related to a number of uses. These advantages include the ability to obtain extruded PEF foams with the following properties: (1) superior strength compared to PET foam for a given density (even when using the preferred HFO-1234ze(E) blowing agent of the present invention); (2) reduced density compared to foams with the same density as extruded PET foam, thus providing a weight advantage.

[0342] Extrusion Example 2

[0343] Example 1 was repeated, except that a commercial-grade extruder with a throughput of approximately 2,000 psi to approximately 6,000 psi was used. Similar unexpected results were obtained.

[0344] Example of use

[0345] Comparative use of Example 1

[0346] This article has Figure 1 The wind turbine generator of the general type configuration shown in Figure 3 is constructed on land with a nacelle approximately 150 meters above the ground (refer to the nacelle's centerline). Each blade has a blade span of approximately 100 meters from the hub axis to the blade tip, resulting in a rotor diameter of approximately 200 meters. The generator produces approximately 13 MW of electrical power under peak design conditions. Each blade includes a facing PET foam, of which approximately 30% by weight is high-density foam (i.e., a density of 240 kg / m³ (before the facing)). The total weight of all PET foam to be replaced in the wind turbine (excluding the facing material) is approximately 0.03% by weight of the total blade weight.

[0347] Application Example 1—A weight-reduced 13MW wind turbine made with the PEF homopolymer foam of the present invention motor

[0348] A wind turbine generator with the configuration described above in Comparative Example 1 is constructed, except that the high-density PET foam is replaced with the foam of the present invention based on any of extruded foams 1 to 4 and the PEF extruded foam of Extrusion Examples 1 and 2. In this embodiment, the high-density PET foam is replaced with foam made from such extruded PEF foam foamed with 1234ze, as shown by the trend line in the graph above. An alternative substitution is to replace all high-density extruded PET with extruded PEF homopolymer represented by the trend line in the graph above, based on equal strength. On average, this results in the use of the PEF extruded foam of the present invention, with a density of about 100 kg / m³, only about 40% of the density of PET foam, and therefore about 40% lighter than high-density PET foam. The end result is a blade weight reduction of about 0.03%. 0.4, a weight reduction of approximately 1.2%. The unexpected reduction in blade weight achievable through the use of the foam of this invention is significant and commercially viable. This blade weight reduction means that many other components of the wind turbine can be manufactured smaller and / or lighter, which in turn not only provides additional environmental benefits but also significantly reduces construction costs. For example, the nacelle of the wind turbine is designed to be compatible with the blades, including dimensions and weight that balance the torque generated by the blades. Furthermore, this weight reduction will lead to cost savings in tower design and construction.

[0349] Example 2: Using PEE homopolymer in the root region of the blade shell and / or in the non-root region of the blade shell High-output wind turbine generator made using the PEF homopolymer foam of the present invention

[0350] A wind turbine generator with the configuration described in Comparative Example 1 is manufactured, except that the extruded PEF foam of the present invention with the same density is used instead of PET foam. However, due to the increased strength of the foam of the present invention, the blade design can be improved in various ways to achieve power improvement.

[0351] Example 3 – Aircraft using one or more of extruded foam products 1 to 3

[0352] An aircraft includes at least one extruded foam article containing the present invention at one or more locations where structural foam is required (preferably including at least a portion of one or more of the wings, fuselage, tail, doors, bulkheads, interior and / or superstructure). This aircraft achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less than the weight of previously used foam; (2) advantages in size and / or performance compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0353] Example 4 – Land vehicles using one or more of extruded foam products 1 to 3

[0354] The automobile includes at least one foam article containing the present invention in one or more locations where structural foam is required (preferably including side panels, floor panels, roof panels, engine compartment, battery compartment interior and / or at least part of one or more of the superstructure). This includes one or more of foam articles 1 to 3. The automobile achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less than the weight of previously used foam; (2) advantages in size and / or performance compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0355] Example 5 – Railway vehicles using one or more of extruded foam products 1 to 3

[0356] The railway vehicle includes at least one foam article containing the present invention at one or more locations where structural foam is required (preferably including side panels, floor panels, roof panels, and at least a portion of one or more of the superstructure). This includes one or more of foam articles 1 to 3. The railway vehicle achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less than the weight of previously used foam; (2) advantages in size and / or performance compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0357] Example 6 – Construction using one or more of extruded foam products 1 to 3

[0358] A building structure (preferably including at least a portion of one or more of the wall panels, floor structure, and roof structure, and other structures) that includes one or more locations requiring structural foam contains at least one foam article of the present invention, including one or more of foam articles 1 to 3. The building achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less than the weight of previously used foam; (2) advantages in size and / or performance compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0359] Example 7 – Encapsulation using one or more of extruded foam products 1 to 3

[0360] The encapsulation (preferably in the form of a box, insert, partition, sleeve, etc.) that includes one or more locations requiring structural foam contains at least one foam article of the present invention, including one or more of foam articles 1 to 3. The building achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less than the weight of previously used foam; (2) advantages in size and / or performance compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0361] Example 8 – Sporting goods using one or more of extruded foam products 1 to 3

[0362] Sporting goods (preferably including tennis rackets, ice skates, water skis, or skis, etc.) that include one or more locations requiring structural foam contain at least one foam article of the present invention, including one or more of foam articles 1 to 3. The sporting goods achieve: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less than the weight of previously used foam; (2) advantages in size and / or performance compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

Claims

1. A wind turbine blade, the wind turbine blade comprising: a. Blade shell; and b. Extruded foam in the blade casing, the extruded foam having a density of approximately 125 kg / m³ 3 Approximately 425 kg / m 3 The foam density is [specific value], and it comprises thermoplastic foam, said thermoplastic foam comprising: (1) A thermoplastic polymer pore, the thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer (i) comprises about 0.5 mol% to about 99.5 mol% of an ethylene furanoate moiety and about 0.5 mol% to about 99.5 mol% of an ethylene terephthalate moiety; and (ii) has a molecular weight of about 25,000 to about 140,000; and (b) 1234ze(E) contained in the closed pore.

2. The wind turbine blade according to claim 1, wherein at least about 75% of the holes are closed holes.

3. The wind turbine blade according to claim 1, wherein the extruded foam has a foam density of about 125 kg / m3 to about 250 kg / m3.

4. A finished foam, said finished foam comprising: a. An extruded thermoplastic foam core, wherein the extruded thermoplastic foam core has a density of approximately 125 kg / m³. 3 Approximately 425 kg / m 3 The foam density includes polymer pores, the polymer pores comprising pore walls forming closed pores, wherein the thermoplastic polymer comprises an ethylene furanate moiety and 1234ze(E) contained within the closed pores; and b. Finishing material, said finishing material being attached to at least a portion of the first foam and / or integral with it.

5. An article comprising the finished foam according to claim 4.

6. An energy generating device comprising the finished foam according to claim 4.

7. The energy generating device according to claim 4, wherein the energy generating device comprises blades, foils or rotors located in a wind turbine generator.

8. A foam article, said foam article comprising: a. An extruded thermoplastic closed-cell foam, said extruded thermoplastic closed-cell foam having at least a first foam surface; and b. A material different from the thermoplastic closed-cell foam, wherein the material is attached to at least a portion of the surface of the first foam and / or is integral with it, wherein: (i) The thermoplastic polymer pore includes a pore wall comprising at least about 0.5% by weight of an ethylene furanate portion; (ii) The closed pore contains 1234ze(E); and (iii) The extruded foam has a foam density of about 130 kg / m3 to about 425 kg / m3.

9. The foam article of claim 8, wherein the extruded foam has a foam density of about 130 kg / m3 to about 400 kg / m3, a compressive strength of about 1 MPa to about 14 MPa, and wherein at least about 75% of the pores are closed pores.

10. An energy generating device, the energy generating device comprising the foam article according to claim 9.

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