Thermoplastic foams and use in applications requiring strength and light weight

Abstract

A foamed article is disclosed that includes a thermoplastic closed-cell foam having at least a first surface and (i) a thermoplastic polymer cell wall that includes at least about 0.5 weight percent ethylene furanoate moiety and optionally one or more comonomer moieties, and (ii) a blowing agent contained in at least a portion of the closed cells, and a material different from the thermoplastic closed-cell foam that is attached and / or integrated with at least a portion of the first foam surface.

Description

Technical Field

[0001] (Cross - Reference to Related Applications) This application is related to U.S. Provisional Patent Application No. 63 / 343,990, filed on May 19, 2022, claims the benefit of its priority, is incorporated by reference, and also claims the benefit of the priority of U.S. Patent Application No. 18 / 113,605, filed on February 23, 2023.

[0002] (Field of the Invention) The present invention relates to foaming thermoplastic compositions, thermoplastic foams, foaming methods and systems, and articles made therefrom, including foamed articles such as other molded articles including panels, boards, sheets, blocks, beams, and thermoplastic foams having a surface coated with a sheet, mat, film, scrim, or similar surface covering material, and to the use of such articles in devices, systems, and methods that require or benefit from a relatively lightweight and relatively strong foamed form, particularly environmentally advantageous and sustainable lightweight and relatively strong foamed forms.

Background Art

[0003] Foams are used in a wide variety of applications, but it is a desirable yet difficult - to - achieve goal in many applications that the foam material be environmentally friendly, have excellent performance characteristics at the same time, and be cost - effective to produce. Environmental considerations include not only the recyclability and sustainability of the polymer resin forming the structure of the foam, but also the low environmental impact of the blowing agent used to form the foam, such as the Global Warming Potential (GWP) and Ozone Depletion Potential (ODP) of the blowing agent.

[0004] Certain thermoplastic resin-based foams containing polyester resins have been under consideration for potential benefits from the perspective of recyclability and / or sustainable availability. However, difficulties have been encountered in the development of such materials. For example, the development of polyester resins that are truly recyclable, can be produced from sustainable sources, and are compatible with blowing agents capable of producing foams with good performance characteristics when combined with thermoplastic substances has been an issue. In many applications, performance characteristics that are highly desirable include the production of high-quality closed-cell foams that are low in density (and thus lightweight in use), while at the same time having relatively high mechanical integrity and strength.

[0005] There are many important applications that benefit from the use of a coated or surface-finished foam form where the foam portion is made from a renewable and sustainable material that is relatively lightweight (i.e., has a relatively low density) and has relatively high strength. Such applications include, for example, in all such applications where the use of a lightweight and relatively strong material can be beneficial, use in transportation devices such as automobiles, trucks, railway vehicles, boats, ships, aircraft, etc. Other examples include sports equipment such as skis, snowboards, skateboards, and fixed building structures including, for example, roof and floor underlayments and wall components in buildings and homes. Packaging applications can also benefit from the foams provided by the present invention.

[0006] Another example of an important application that benefits from a relatively lightweight and relatively high-strength coated or surface-finished foam made from a renewable and sustainable material is blades, foils, etc. used as fluid energy transfer devices. Examples of such fluid energy transfer devices include blades used in wind turbines. Other types of fluid energy transfer devices include vortices, tides, oceans, oscillating water columns, and kites, which recover the kinetic energy of air or water from fixed or moving devices located in air or water.

[0007] An example of one type of wind turbine is schematically illustrated in FIG. 1. In the illustrated configuration, the wind turbine, generally designated 2, includes a tower 4 that supports a nacelle 6 surrounding a drive train 8. In a typical configuration, wind turbine blades 10 are disposed on a hub to form a “rotor” at one end of the drive train 8 outside the nacelle 6. In operation, wind passing through the blades 10 generates lift to rotate them, and the rotating blades 10 drive a gearbox 12 connected to a generator 14 at the other end of the drive train 8 disposed inside the nacelle 6 along with a control system 16 that receives input from an anemometer 18. It will be appreciated that other configurations of wind turbines are direct drive and thus do not include a gearbox.

[0008] The nacelles of many wind turbines are located on towers that can be located 120 meters above the ground in the case of land-based generators, and in some cases even higher, and in the case of offshore applications, on towers that can be located 150 meters above the water surface in the case of offshore generators, and in some cases even higher. For this and other reasons, it is often important to construct the various components of wind turbine blades from materials that are relatively lightweight while at the same time being strong enough to withstand the forces to which the blades are exposed. Thus, using the lightest materials that can provide the required strength characteristics can not only improve the operating efficiency of the wind turbine, but also result in benefits to the construction and maintenance costs of the wind farm, and is therefore very important in such applications. Thermoplastic foams formed from polyethylene terephthalate (PET) have been used in wind turbine blades, but the applicants have come to recognize that several important drawbacks are associated with the use of such materials in such applications. For example, PET is not a sustainable material. In addition, in certain portions of the wind turbine blade, a higher density material such as balsa wood is used instead of the PET foam because the PET foam does not provide sufficient strength to meet the requirements in those regions of the wind turbine blade.

[0009] Referring particularly to FIGS. 2 and 3, for example, a typical rotor blade 10 of FIG. 1 is illustrated in perspective view, and FIG. 3A illustrates a cross-sectional view of the rotor blade 10 along cutting line 3-3. As shown, a typical rotor blade 10 generally includes a blade root 30 configured to be attached to or otherwise fixed to the hub of the wind turbine 2, and a blade tip 32 disposed on the opposite side of the blade root 30. The body shell 21 of the rotor blade typically has a thickness of 1 to 6 centimeters and generally extends between the blade root 30 and the blade tip 32 along the longitudinal axis 27. The body shell 21 can generally serve as the outer casing / cover of the rotor blade 10 and can define a substantially aerodynamic profile, such as by defining a symmetric or dihedral airfoil cross-section. Due to various mechanical strength requirements along the length of the turbine blade 10, it is common to use a core material containing a polymer foam, such as PET foam, in combination with balsa wood to form the body shell of the blade between the segment 42 and the root 30, and the concentration of balsa wood is higher in the region closer to the root where the strength requirements are higher.

[0010] Regarding FIG. 3A, it should be noted that the rotor blade 10 typically has a pressure side 34 and a suction side 36 that extend 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 that defines the overall length between the blade root 30 and the blade tip 32, and a chord 25 that defines the overall length between the leading edge 26 and the trailing edge 28. As is generally understood, the chord 25 can generally vary in length with respect to the span 23 when the rotor blade 10 extends from the blade root 30 to the blade tip 32. Further, the rotor blade 10 may also include one or more longitudinally extending structural components configured to provide increased rigidity, buckling resistance, and / or strength to the rotor blade 10. For example, the rotor blade 10 may include a pair of longitudinally extending shear webs 24, and the spar caps 20, 22 are each configured to engage the opposing inner surfaces 35, 37 of the pressure side 34 and the suction side 36 of the rotor blade 10, respectively. Also, one or more shear webs 24 may be disposed between the spar caps 20, 22 so as to form a beam-like configuration. The spar caps 20, 22 are generally designed to resist bending loads and minimize tip deflection and / or other loads acting generally in the spanwise direction (a direction parallel to the span 23 of the rotor blade 10) on the rotor blade 10 during operation of the wind turbine 2. In some configurations, the spar is also designed to resist shear as well as tension and compression based on how the fibers are angled within the laminate from which the spar cap is fabricated. Similarly, the spar caps 20, 22 may also be designed to withstand spanwise compression and / or tension that occurs during operation of the wind turbine 6. In alternative configurations such as those shown in FIGS. 3B and 3C, the spar caps 20A and 22A may be integrated into the structural shell.

[0011] Due to these requirements of the spark cap used for the rotor blade, hitherto, PET foam has not generally been used for these parts of the blade. Instead, it has been common to form the spark cap from other materials that are considered to have better strength characteristics, such as balsa wood surface-strengthened with a surface material or a glass fiber-reinforced laminate or a carbon fiber-reinforced laminate.

[0012] Regardless of whether the core material is within the shell, or within the shear web, or within the spark cap of the wind turbine blade, the core is typically sandwiched between two or more surface sheets made of several layers of glass fiber adhered with an epoxy resin. The surface material after stiffening provides longitudinal stiffness and strength, while the core provides out-of-plane strength and stiffness. The surface sheets support most of the bending and in-plane loads, and the core mainly supports the shear loads.

[0013] Regarding the selection of thermoplastic resins, European Patent No. 3,231,836 was interested in thermoplastic resins, particularly polyester-based resins, but recognized that this interest faced development difficulties, including the difficulty of identifying suitable foaming grades of such resins. Furthermore, European Patent No. 3,231,836 mentions that certain polyethylene terephthalate (PET) resins (including recycled versions of PET) can be melt-extruded with suitable physical and / or chemical blowing agents to obtain a closed-cell foam having the potential for low density and good mechanical properties, but it is not disclosed that any of such resins can immediately produce a foam having good environmental properties and good performance properties and can also be formed from a sustainable source. The '836 application identifies several polyester resin candidates for use in the formation of open-cell foams, including polyethylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate, polyethylene naphthalate, polyethylene furanoate, or mixtures of two or more of these. The use of polyester materials for making foams that essentially do not have closed cells, as required by European Patent No. '836, can be beneficial for some applications, but the drawback of such a structure is generally that open-cell foams exhibit relatively poor mechanical strength properties.

[0014] Chinese Patent No. 108484959 discloses that the manufacture of foam products based on 2,5-furandimethyl copolyesters is problematic because the dissolution of blowing agents into the polyester is a problem, and proposes a specific process including the use of a combination of liquid blowing agents and gas blowing agents, and the sequential use of these different classes of blowing agents.

[0015] U.S. Patent Application Publication Nos. 2020 / 0308363 and 2020 / 0308396 each disclose the production of an amorphous polyester copolymer starting from a recycled polyester in which only PET is exemplified as the main component and then obtaining an amorphous copolymer, i.e., a copolymer having no crystallinity, through a series of processing steps. A variety of different classes of blowing agents for use with such amorphous polymers are mentioned.

[0016] Regarding blowing agents, for example, the general use of halogenated olefin blowing agents including hydrofluoroolefins (HFO) and hydrochlorofluorolefins (HCFO) as disclosed in U.S. Patent Application Publication No. 2009 / 0305876, which is assigned to the assignee of the present invention and incorporated herein by reference, is also known. The '876 application discloses the use of HFO and HFCO blowing agents with various thermoplastic materials to form foams containing PET, but there is no disclosure or suggestion regarding the use of any of such blowing agents with any other type of polyester resin.

[0017] Applicants have come to recognize that by using the polyester resins disclosed herein in combination with blowing agents containing one or more hydrohaloolefins disclosed herein, one or more unexpected advantages can be achieved in connection with the formation of thermoplastic foams, particularly extruded thermoplastic foams.

[0018] Applicants have come to recognize that one or more unexpected advantages can be achieved in connection with the formation of foam articles and members including coated or surface-finished thermoplastic foams based on such PEF foams in which the foam is formed using a blowing agent containing one or more hydrohaloolefins disclosed herein. The articles disclosed herein overcome one or more of the disadvantages of prior art foam articles including the above-mentioned disadvantages and provide significant and unexpected advantages over prior art foam articles and members, as will be described in more detail below.

SUMMARY OF THE INVENTION

[0019] The present invention relates to a thermoplastic closed-cell foam having at least a first foam surface and being any one of Foams 1 to 4 defined below, and a material different from the thermoplastic closed-cell foam and attached and / or integrated with at least a part of the first foam surface, and includes a foam article. For convenience, in this specification, the foam article according to this paragraph is referred to as Foam Article 1.

[0020] For convenience, but not necessarily limited thereto, the material of the present invention that is different from the thermoplastic closed-cell foam and is attached and / or integrated with at least a part of the first foam surface may be referred to as a "surface material" in this specification.

[0021] The present invention also relates to a thermoplastic closed-cell foam having at least a first surface, and a material different from the thermoplastic closed-cell foam and attached and / or integrated with at least a part of the first foam surface, wherein the thermoplastic closed-cell foam includes a thermoplastic polymer cell wall containing at least about 0.5 wt% of an ethylene furanoate moiety and optionally one or more comonomer moieties, and includes a foam article. For convenience, in this specification, the foam article according to this paragraph is referred to as Foam Article 2.

[0022] The present invention also relates to (a) a thermoplastic closed-cell foam having at least a first foam surface, wherein the thermoplastic polymer cells consist essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and (b) a material different from the thermoplastic closed-cell foam and attached and / or integrated with at least a part of the first foam surface, and includes a foam article.

[0023] For the sake of convenience, in this specification, the foam article according to this paragraph is referred to as foam article 3A.

[0024] The present invention also relates to (a) a thermoplastic closed-cell foam having at least a first foam surface; and (b) a material different from the thermoplastic closed-cell foam and attached and / or integrated with at least a portion of the first foam surface, (i) the thermoplastic polymer foam contains cell walls containing at least about 0.5 wt% ethylene furanoate moieties, (ii) the foam has a relative foam density (RFD) of about 0.2 or less and a foam density of less than 0.3 g / cc, and includes a foam article.

[0025] For the sake of convenience, in this specification, the foam article according to this paragraph is referred to as foam article 3B.

[0026] As used herein, relative foam density (RFD) means the density of the foamed polymer divided by the density of the polymer before expansion, and is taken as 1.43 g / cc for the sake of simplicity in this specification. Thus, for the purposes used herein, RFD is equal to the density of the foam in g / cc divided by 1.43.

[0027] The present invention also relates to (a) a thermoplastic closed-cell foam having at least a first foam surface; and (b) a material different from the thermoplastic closed-cell foam and attached and / or integrated with at least a portion of the first foam surface, (i) the thermoplastic polymer foam contains cell walls containing at least about 1 wt% ethylene furanoate moieties, (ii) the foam has a relative foam density (RFD) of about 0.2 or less and a foam density of less than 0.25 g / cc, (iii) the independent thermoplastic polymer foam contains one or more blowing agents, and includes a foam article.

[0028] For the sake of convenience, in this specification, the foam article according to this paragraph is referred to as foam article 3C.

[0029] The present invention also relates to (a) a thermoplastic closed-cell foam having at least a first foam surface; and (b) a material different from the thermoplastic closed-cell foam that is attached and / or integrated with at least a portion of the first foam surface, (i) the thermoplastic polymer foam includes cell walls containing at least about 1 wt% ethylene furanoate moieties, (ii) the foam has a relative foam density (RFD) of about 0.2 or less, (iii) the independent thermoplastic polymer foam contains one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms, and includes a foam article.

[0030] For the sake of convenience, in this specification, the foam article according to this paragraph is referred to as foam article 3D.

[0031] The present invention also relates to (a) a thermoplastic closed-cell foam having at least a first foam surface; and (b) a material different from the thermoplastic closed-cell foam that is attached and / or integrated with at least a portion of the first foam surface, (i) the thermoplastic polymer foam includes cell walls containing at least about 0.5 wt% ethylene furanoate moieties, (ii) the foam has a foam density of less than 0.2 g / cc, (iii) the independent thermoplastic polymer foam contains one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms, and includes a foam article.

[0032] For the sake of convenience, in this specification, the foam article according to this paragraph is referred to as foam article 3E.

[0033] The present invention also provides a wind turbine blade including a blade shell and a foam article of the present invention including a foam article selected from each of the foam articles 1 to 3 within the blade shell. For convenience, in this specification, the method according to this paragraph is referred to as wind turbine blade 1.

[0034] The present invention also provides a transport vehicle including a vehicle body and a foam article of the present invention including a foam article selected from each of the foam articles 1 to 3 within the vehicle body. For convenience, in this specification, the method according to this paragraph is referred to as vehicle 1.

[0035] The present invention also provides a fixed building structure including a structural component and a foam article of the present invention including a foam article selected from each of the foam articles 1 to 3 within the vehicle body or attached to the vehicle body by other means. For convenience, in this specification, the method according to this paragraph is referred to as fixed building structure 1.

[0036] The present invention also provides a sports equipment article including a foam article of the present invention including a foam article selected from each of the foam articles 1 to 3 within the sports equipment article vehicle body or attached to the sports equipment article vehicle body by other means. For convenience, in this specification, the method according to this paragraph is referred to as sports equipment article 1.

[0037] The present invention also provides a sports equipment article including a foam article of the present invention including a foam article selected from each of the foam articles 1 to 3 within the sports equipment article vehicle body or attached to the sports equipment article vehicle body by other means. For convenience, in this specification, the method according to this paragraph is referred to as packaging 1.

Brief Description of the Drawings

[0038]

Figure 1

Figure 2

Figure 3A

Figure 3B

Figure 3C

Figure 4

Figure 5

Figure 6

Figure 7

Figure 8

Figure 9

Modes for Carrying Out the Invention

[0039] Definitions 1234ze means 1,1,1,3-tetrafluoropropene and is not limited with respect to isomeric forms.

[0040] trans 1234ze and 1234ze(E) each mean trans 1,3,3,3-tetrafluoropropene.

[0041] cis 1234ze and 1234ze(Z) each mean cis 1,3,3,3-tetrafluoropropene.

[0042] 1234yf means 2,3,3,3-tetrafluoropropene.

[0043] 1233zd means 1-chloro-3,3,3-trifluoropropene and is not limited with respect to isomeric forms.

[0044] Trans 1233zd and 1233zd(E) each mean trans 1-chloro-3,3,3-trifluoropropene.

[0045] 1224yd means cis 1-chloro-2,3,3,3-tetrafluoropropane and is not limited with respect to isomeric forms.

[0046] 1336mzz means 1,1,1,4,4,4-hexafluorobutene and is not limited with respect to isomeric forms.

[0047] Trans 1336mzz and 1336mzz(E) each mean trans 1,1,1,4,4,4-hexafluorobutene.

[0048] Cis 1336mzz and 1336mzz(Z) each mean cis 1,1,1,4,4,4-hexafluorobutene.

[0049] Closed-cell foam means that a substantial volume percentage of the bubbles in the foam, for example, about 20% by volume or more, are independent.

[0050] The ethylene furanoate moiety has the following structure:

[0051]

Chem.

[0052] FDCA means 2,5-furandicarboxylic acid and has the following structure.

[0053]

Chem.

[0054] MEG means monoethylene glycol and has the following structure.

[0055]

Chem.

[0056] FDME means dimethyl 2,5-furandicarboxylate and has the following structure.

[0057] [Chemical formula]

[0058] A PEF homopolymer means a polymer having at least 99 mol% of ethylene furanoate moieties.

[0059] A PEF copolymer means a polymer having at least about 0.5 mol% of ethylene furanoate moieties and polymer moieties other than more than 0.5% of ethylene furanoate moieties.

[0060] A PEF:PET copolymer means a polymer having at least about 0.5 mol% of ethylene furanoate moieties and at least 0.5% of ethylene terephthalate moieties.

[0061] PEF means poly(ethylene furanoate) and is intended to encompass and reflect the description of PEF homopolymers and PEF copolymers.

[0062] The ethylene terephthalate moiety means the structure in parentheses:

[0063] [Chemical formula]

[0064] SSP means solid state polymerization.

[0065] PMDA means pyromellitic dianhydride having the following structure.

[0066] [Chemical formula]

[0067] (Detailed Description) Poly(ethylene furanoate) The present invention relates to a foam and a foam article including a cell wall containing a PEF portion.

[0068] The PEF forming the cell wall of the foam and the foam article of the present invention can be a PEF homopolymer or a PEF copolymer, particularly a PEF:PET copolymer.

[0069] The PEF homopolymer is a known material formed by any of the following. (a) Esterification and polycondensation of FDCA and MEG, or (b) Transesterification and polycondensation of FDME and MEG as illustrated, for example, below.

[0070] [Chemical formula]

[0071] A detailed description of such known esterification and polycondensation synthesis methods is provided in British Patent No. 621971 (Drewitt, J.G.N. and Lincocoln, J., title "Improvements in Polymers"), which is incorporated herein by reference. A detailed description of such known transesterification and polycondensation synthesis methods is provided in Gandini, A., Silvestre, A.J.D., Neto, C.P., Sousa, A.F., and Gomes, M. (2009), "The furan counterpart of poly(ethylene terephthalate): an alternative material based on renewable resources.", J. Polym. Sci. Polym. Chem. 47, 295 - 298. doi:10.1002 / pola.23130, which is incorporated herein by reference.

[0072] Foam The present invention relates to (a) a thermoplastic polymer foam comprising bubble walls forming closed cells, wherein the thermoplastic polymer consists essentially of an ethylene furanoate moiety and optionally an ethylene terephthalate moiety, and the polymer comprises from about 0.5 mol% to about 100 mol% of the ethylene furanoate moiety and optionally at least about 1 mol% of the ethylene terephthalate moiety, and (b) one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells, and a low density thermoplastic foam.

[0073] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 1A.

[0074] The present invention relates to (a) a thermoplastic polymer foam comprising bubble walls forming closed cells, wherein the thermoplastic polymer has a crystallinity of at least about 5% and consists essentially of an ethylene furanoate moiety and optionally an ethylene terephthalate moiety, and the polymer comprises from about 0.5 mol% to about 100 mol% of the ethylene furanoate moiety and optionally at least about 0.5 mol% of the ethylene terephthalate moiety, and (b) one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells, and a low density thermoplastic foam.

[0075] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 1B.

[0076] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, and the polymer comprises from about 0.5 mol% to about 20 mol% ethylene furanoate moieties and at least about 0.5 mol% ethylene terephthalate moieties, a thermoplastic polymer foam; (b) A low density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0077] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 1C.

[0078] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol, consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, and the polymer comprises from about 1 mol% to about 20 mol% ethylene furanoate moieties and from about 80 mol% to about 99 mol% ethylene terephthalate moieties, a thermoplastic polymer foam; (b) A low density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0079] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 1D.

[0080] The present invention relates to (a) A thermoplastic polymer foam comprising a cell wall forming closed cells, 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 consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer comprises from about 1 mol% to about 20 mol% of an ethylene furanoate moiety and from about 80 mol% to about 99 mol% of an ethylene terephthalate moiety, a thermoplastic polymer foam. (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within the closed cells.

[0081] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1E.

[0082] The present invention (a) A thermoplastic polymer foam comprising a cell wall forming closed cells, 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 consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer comprises from about 0.5 mol% to about 5 mol% of an ethylene furanoate moiety and from about 95 mol% to about 99.5 mol% of an ethylene terephthalate moiety, a thermoplastic polymer foam. (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within the closed cells.

[0083] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1F.

[0084] The present invention (a) A thermoplastic polymer foam comprising a cell wall forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer comprises from about 0.5 mol% to about 2 mol% of an ethylene furanoate moiety and from about 98 mol% to about 99.5 mol% of an ethylene terephthalate moiety, a thermoplastic polymer foam; (b) A low density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0085] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1G.

[0086] The present invention relates to (a) A thermoplastic polymer foam comprising a cell wall forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer comprises about 1 mol% of an ethylene furanoate moiety and about 99 mol% of an ethylene terephthalate moiety, a thermoplastic polymer foam; (b) A low density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0087] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1H.

[0088] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls forming closed cells, 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 consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer comprises about 0.5 mol% of an ethylene furanoate moiety and about 99.5 mol% of an ethylene terephthalate moiety, the thermoplastic polymer foam; (b) A low-density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0089] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1I.

[0090] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls forming closed cells, 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 consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer comprises about 5 mol% of an ethylene furanoate moiety and about 95 mol% of an ethylene terephthalate moiety, the thermoplastic polymer foam; (b) A low-density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0091] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1J.

[0092] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, and the polymer comprises about 10 mol% ethylene furanoate moieties and about 90 mol% ethylene terephthalate moieties, the thermoplastic polymer foam; (b) A low-density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0093] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1K.

[0094] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, and the polymer comprises about 20 mol% ethylene furanoate moieties and about 80 mol% ethylene terephthalate moieties, the thermoplastic polymer foam; (b) A low-density thermoplastic foam comprising one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

[0095] For convenience, in this specification, the foam according to this paragraph is referred to as foam 1L.

[0096] The present invention relates to (a) A thermoplastic polymer foam comprising bubble walls containing polyethylene furanoate, wherein at least 25% of the bubbles are closed cells, the thermoplastic polymer foam; (b) A low-density thermoplastic foam comprising 1234ze(E) contained within the closed cells.

[0097] For the sake of convenience, in this specification, the foam according to this paragraph is referred to as foam 2A.

[0098] The present invention relates to (a) a thermoplastic polymer foam including cell walls containing from about 1 mol% to about 20 mol% of an ethylene furanoate moiety and at least about 0.5 mol% of an ethylene terephthalate moiety, and (b) 1234ze(E) contained within the closed cells, and includes a low density thermoplastic foam.

[0099] For the sake of convenience, in this specification, the foam according to this paragraph is referred to as foam 2B.

[0100] The present invention relates to (a) a thermoplastic polymer foam including cell walls containing from about 1 mol% to about 20 mol% of an ethylene furanoate moiety and at least about 0.5 mol% of an ethylene terephthalate moiety, and (b) 1336mzz(Z) contained within the closed cells, and includes a low density thermoplastic foam.

[0101] For the sake of convenience, in this specification, the foam according to this paragraph is referred to as foam 2C.

[0102] The present invention relates to (a) a thermoplastic polymer foam including cell walls containing from about 1 mol% to about 20 mol% of an ethylene furanoate moiety and at least about 0.5 mol% of an ethylene terephthalate moiety, and (b) 1223zd(E) contained within the closed cells, and includes a low density thermoplastic foam.

[0103] For the sake of convenience, in this specification, the foam according to this paragraph is referred to as foam 2D.

[0104] The present invention relates to (a) a thermoplastic polymer foam including cell walls containing a polymer including from about 1 mol% to about 20 mol% of an ethylene furanoate moiety and at least about 0.5 mol% of an ethylene terephthalate moiety, and (b) A low-density thermoplastic foam comprising 1224yd contained within closed cells.

[0105] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 2E.

[0106] The present invention relates to (a) A thermoplastic polymer foam comprising cell walls containing from about 1 mol% to about 20 mol% of an ethylene furanoate moiety and at least about 0.5 mol% of an ethylene terephthalate moiety, wherein at least 50% of the cells are closed cells, (b) A gas within the closed cells, the gas comprising from about 25 wt% to 100 wt% of 1234ze(E), and a low-density thermoplastic foam. For convenience, in this specification, the foam according to this paragraph is referred to as Foam 2F.

[0107] Throughout various places in this specification, reference is made to numbered foams (e.g., Foam 1) or groups of numbered foams as defined herein, and such reference means each of such numbered systems, each system having a number within the group including any subscripted numbered systems. For example, a reference to Foam 1 includes a separate reference to each of Foam 1A, 1B, 1C, 1D, etc., and a reference to Foams 1 - 2 is understood to include a separate reference to each of Foam 1A, 1B, 1C, 1D, etc. and each of Foam 2A, 2B, 2C, 2D, etc. Further, this convention is used throughout this specification for other defined materials including blowing agents.

[0108] The present invention relates to (a) A thermoplastic polymer foam comprising cell walls that form closed cells, wherein the thermoplastic polymer consists essentially of an ethylene furanoate moiety and optionally an ethylene terephthalate moiety, the thermoplastic polymer comprising (i) from about 0.5 mol% to about 99.5 mol% of an ethylene furanoate moiety and optionally at least about 0.5 mol% of an ethylene terephthalate moiety, and (ii) having a molecular weight of at least about 25,000, (b) A low-density thermoplastic foam comprising trans-1,2,3,4-tetrafluoropropene (trans-1234ze) contained within the closed cells.

[0109] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 3.

[0110] The present invention relates to (a) A thermoplastic polymer foam comprising cell walls that form closed cells, wherein the thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, and the thermoplastic polymer: (i) comprises from about 0.5 mol% to about 99.5 mol% of ethylene furanoate moieties and optionally at least about 0.5 mol% of ethylene terephthalate moieties, and (ii) has a molecular weight of at least about 25,000 to about 140,000, and (b) A low-density thermoplastic foam comprising trans-1,2,3,4-tetrafluoropropene (trans-1234ze) contained within the closed cells.

[0111] For convenience, in this specification, the foam according to this paragraph is referred to as Foam 4.

[0112] The foam of the present invention comprising each of Foams 1 to 4 is formed from any of a PEF homopolymer, a PEF copolymer, or a combination / mixture thereof.

[0113] In a preferred embodiment, the foam of the present invention comprising each of Foams 1 to 4 can be formed from a PEF homopolymer in which the polymer has at least 99.5 wt%, or at least 99.9 wt% of ethylene furanoate moieties.

[0114] In a preferred embodiment, the foam of the present invention containing each of Foams 1 to 4 is contemplated to be formed from a PEF copolymer in which the polymer containing the PEF copolymer has an ethylene furanoate moiety of about 60 wt% to about 99 wt%, or about 70 wt% to about 99 wt%, or about 80 wt% to about 99 wt%, or about 90 wt% to about 99 wt%, or about 95 wt% to about 99.5 wt%.

[0115] In a preferred embodiment, the foam of the present invention containing each of Foams 1 to 4 is contemplated to be formed from a PEF copolymer in which the polymer containing the PEF copolymer has an ethylene furanoate moiety of about 40 wt% to about 1 wt%, or about 30 wt% to about 1 wt%, or about 20 wt% to about 1 wt%, or about 10 wt% to about 1 wt%, or about 5 wt% to about 1 wt%, or about 5 wt% to about 0.5 wt%.

[0116] In a preferred embodiment, the foam of the present invention containing each of Foams 1 to 4 is contemplated to be formed from a PEF copolymer in which the polymer containing the PEF copolymer has an ethylene furanoate moiety of about 40 mol% to about 1 mol%, or about 30 mol% to about 1 mol%, or about 20 mol% to about 1 mol%, or about 10 mol% to about 1 mol%, or about 5 mol% to about 1 mol%, or about 5 mol% to about 0.5 mol%.

[0117] In preferred embodiments, the foam of the present invention containing each of foams 1 to 4 is such that the polymer containing the PEF copolymer has from about 40 mol% to about 1 mol% ethylene furanoate moiety and from about 60 mol% to about 99 mol% ethylene terephthalate moiety, or from about 30 mol% to about 1 mol% ethylene furanoate moiety and from about 70 mol% to about 99 mol% ethylene terephthalate moiety, or from about 20 mol% to about 1 mol% ethylene furanoate moiety and from about 80 mol% to about 99 mol% ethylene terephthalate moiety, or from about 10 mol% to about 1 mol% ethylene furanoate moiety and from about 90 mol% to about 99 mol% ethylene terephthalate moiety, or from about 5 mol% to about 1 mol% ethylene furanoate moiety and from about 95 mol% to about 99 mol% ethylene terephthalate moiety, or from about 5 mol% to about 0.5 mol% ethylene furanoate moiety and from about 95 mol% to about 99.5 mol% ethylene terephthalate moiety, and is contemplated to be formed from a PEF copolymer.

[0118] Regarding these embodiments of the present invention involving the use of a PEF copolymer, those skilled in the art, in view of the teachings contained herein, are contemplated to be able to select the type and amount of copolymer materials used within each of the ranges described herein to achieve the desired enhancement / modification of the polymer without undue experimentation.

[0119] Regarding these embodiments of the present invention involving the use of a PEF homopolymer or PEF copolymer, it is contemplated that such materials having a wide variety of molecular weights and physical properties within the scope of the present invention can be formed. In preferred embodiments, the foam containing each of foams 1 to 4 is formed from a PEF having a range of properties specified in Table 1 below, as measured as described in the examples herein.

[0120]

Table 1

[0121] Generally, it is contemplated that one of ordinary skill in the art can compound PEF polymers within the above-described range of properties without undue experimentation in view of the teachings contained herein. However, in preferred embodiments, PEF (including PEF homopolymers and PEF copolymers) having these properties are achieved by using one or more of the above synthetic methods in combination with various known supplemental processing techniques, including treatment with a chain extender such as PMDA (and alternatives and supplements to PMDA such as ADR, pentaerythritol (hereinafter referred to as "PENTA"), and talc described in the examples of the present invention and elsewhere), and / or SSP treatment. In view of the disclosure contained herein, including the polymer synthesis described in the following examples and the use of methods to enhance the crystallization of the polymer, one of ordinary skill in the art would be able to produce PEF polymers within the range of properties described in the above table and elsewhere in this specification. Such processing conditions include the methods for increasing crystallization described herein, such as those disclosed in the examples of this specification.

[0122] Examples of processes for the chain extension treatment of polyesters are provided in the document "Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process", Firas Awaja, Fugen Daver, Edward Kosior, 16 August 2004, https: / / doi.org / 10.1002 / pen.20155, which is incorporated herein by reference. As described in U.S. Patent Application Publication No. 1009 / 0264545, which is incorporated herein by reference, chain extenders are generally, typically, compounds that are at least bifunctional with respect to reactive groups that can react with end groups or functional groups in the polyester to extend the length of the polymer chains. In certain cases, as disclosed herein, such treatment can advantageously increase the average molecular weight of the polyester and improve its melt strength and / or other important properties. The degree of chain extension achieved is related, at least in part, to the structure and functionality of the compounds used. Various compounds are useful as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (hereinafter referred to as pyromellitic dianhydride, PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing polyfunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposite materials such as finely dispersed nanoclay can be optionally used to control the viscosity. Commercially available chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema. The amount of chain extender can vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to treat the polymer can vary widely and, in a preferred embodiment, ranges from about 0.1 to about 5 wt%, or preferably from about 0.1 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.

[0123] An example of a process for the SSP treatment of poly(ethylene furanoate) is provided in the paper "Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase" by Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which is incorporated herein by reference.

[0124] The PEF thermoplastic polymers that are particularly advantageous for making the foams 1 to 4 and the foams containing FC1 to FC11 of the present invention, as well as the foam articles containing the foam articles 1 to 4, are specified in the following thermoplastic polymer table (Table 2A), and all numerical values in the table are understood to be preceded by the word "about".

[0125] [Table 2]

[0126] The PEF thermoplastic polymers that are particularly advantageous for making the foams 1 to 4 and the foams containing FC1 to FC11 of the present invention, as well as the foam articles containing the foam articles 1 to 4, also include the materials specified in the following thermoplastic polymer table (Table 2B), and all numerical values in the table are understood to be preceded by the word "about".

[0127] [Table 3]

[0128] The PEF thermoplastic polymers that are particularly advantageous for making the foams 1 to 4 and the foams containing FC1 to FC11 of the present invention, as well as the foam articles containing the foam articles 1 to 4, also include the materials specified in the following thermoplastic polymer table (Table 2C), and all numerical values in the table are understood to be preceded by the word "about".

[0129]

Table 4-1

[0130]

Table 4-2

[0131]

Table 4-3

[0132] For the purposes of the definitions of the terms used in this specification, at various places in this specification, the thermoplastic polymers identified in the first column of each row of the above TPP table are referred to, and it should be noted that each reference to each of these numbers is a reference to the thermoplastic polymer defined in the corresponding column of that row. References to groups of TPPs defined in the above table by reference to TPP numbers mean each such numbered TPP, including any such numbers with subscripts, separately and individually, each TPP having the indicated number. Thus, for example, a reference to TPP1 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1D, and TPP1E. A reference to TPP1 - TPP2 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1D, TTP1E, TPP2A, TPP2B, TPP2C, TPP2D, and TPP1E. This convention of use is similarly used in the following foaming composition tables and foam tables.

[0133] Foaming agent As will be described 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 a foaming PEF foaming composition, a PEF foam, and foam articles including foam articles 1 - 4 having a difficult and surprising combination of physical properties including low density and good mechanical strength properties.

[0134] The blowing agent used in accordance with the present invention preferably comprises one or more hydrohaloolefins having 3 or 4 carbon atoms. For convenience, in this specification, the blowing agent according to this paragraph may be referred to as blowing agent 1A.

[0135] The blowing agent used in accordance with the present invention preferably consists essentially of one or more hydrohaloolefins having 3 or 4 carbon atoms. For convenience, in this specification, the blowing agent according to this paragraph may be referred to as blowing agent 1B.

[0136] The blowing agent used in accordance with the present invention preferably consists essentially of one or more hydrohaloolefins having 3 or 4 carbon atoms. For convenience, in this specification, the blowing agent according to this paragraph may be referred to as blowing agent 1C.

[0137] The blowing agent used in accordance with the present invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter, for convenience, referred to as blowing agent 2A), or one or more of trans-1234ze, 1336mzz, trans-1233zd, and cis-1224yd (hereinafter, for convenience, referred to as blowing agent 3A), or one or more of trans-1234ze, trans-1336mzz, trans-1233zd, and cis-1224yd (hereinafter, for convenience, referred to as blowing agent 4A), or one or more of trans-1234ze and trans-1336mzz (hereinafter, for convenience, referred to as blowing agent 5A), or contains trans-1234ze (hereinafter, for convenience, referred to as blowing agent 6A), or contains trans-1336mzz (hereinafter, for convenience, referred to as blowing agent 7A), or contains cis-1336mzz (hereinafter, for convenience, referred to as blowing agent 8A), or contains 1234yf (hereinafter, for convenience, referred to as blowing agent 9A), or contains 1224yd (hereinafter, for convenience, referred to as blowing agent 10A), or contains trans-1233zd (hereinafter, for convenience, referred to as blowing agent 11A).

[0138] The blowing 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 blowing agent 2B for convenience), or consists essentially of one or more of trans-1234ze, 1336mzz, trans-1233zd, and cis-1224yd (hereinafter referred to as blowing 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 blowing agent 4B for convenience), or consists essentially of one or more of trans-1234ze and trans-1336mzz (hereinafter referred to as blowing agent 5B for convenience), or consists essentially of trans-1234ze (hereinafter referred to as blowing agent 6B for convenience), or consists essentially of trans-1336mzz (hereinafter referred to as blowing agent 7B for convenience), or consists essentially of cis-1336mzz (hereinafter referred to as blowing agent 8B for convenience), or consists essentially of 1234yf (hereinafter referred to as blowing agent 9B for convenience), or consists essentially of 1224yd (hereinafter referred to as blowing agent 10B for convenience), or consists essentially of trans-1233zd (hereinafter referred to as blowing agent 11B for convenience).

[0139] The blowing agents used in accordance with the present invention preferably consist of one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as blowing agent 2B for convenience), or consist of one or more of trans-1234ze, 1336mzz, trans-1233zd, and cis-1224yd (hereinafter referred to as blowing agent 3B for convenience), or consist of one or more of trans-1234ze, trans-1336mzz, trans-1233zd, and cis-1224yd (hereinafter referred to as blowing agent 4B for convenience), or consist of one or more of trans-1234ze and trans-1336mzz (hereinafter referred to as blowing agent 5B for convenience), or consist of trans-1234ze (hereinafter referred to as blowing agent 6B for convenience), or consist of trans-1336mzz (hereinafter referred to as blowing agent 7B for convenience), or consist of cis-1336mzz (hereinafter referred to as blowing agent 8B for convenience), or consist of 1234yf (hereinafter referred to as blowing agent 9B for convenience), or consist of 1224yd (hereinafter referred to as blowing agent 10B for convenience), or consist of trans-1233zd (hereinafter referred to as blowing agent 11B for convenience).

[0140] Accordingly, it is contemplated that the blowing agents of the present invention containing each of blowing agents 1 to 11 can include a co-blowing agent containing one or more of the optional potential co-blowing agents as described below in addition to each of the blowing agents specified above. In a preferred embodiment, the foaming composition, foam, and foaming method of the present invention contain the blowing agents described herein, and the indicated blowing agents (including the compounds or groups of compounds specifically specified in each of blowing 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 the blowing agents present, based on the sum of all the blowing agent components.

[0141] The blowing agents of the present invention containing each of blowing agents 1 to 11 can include one or more co-blowing agents not included in the indicated selection, provided that the amount of such co-blowing agents used does not interfere with or nullify the ability to achieve a relatively low density foam as described in this specification containing each of foams 1 to 4, and preferably further does not interfere with or nullify the ability to achieve a foam having mechanical strength characteristics as described in this specification, which is contemplated and understood. Thus, considering the teachings contained herein, one of ordinary skill in the art can, for example, without undue experimentation, select one or more of the possible co-blowing agents known in the art, such as one or more saturated hydrocarbons or hydrofluorocarbons (HFCs), particularly C4 to C6 hydrocarbons or C1 to C4 HFCs, for use in a particular application. Examples of such HFC co-blowing 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. With respect to hydrocarbons, the blowing agent composition of the present invention can also, in certain preferred embodiments, include, for example, iso, normal, and / or cyclopentane and butane and / or isobutane.Other materials, such as water, CO2, CFCs (e.g., trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, e.g., dichloroethylene (preferably trans-dichloroethylene), ethyl chloride, and chloropropane), HCFCs, C1-C5 alcohols (e.g., ethanol and / or propanol and / or butanol, etc.), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (e.g., dimethyl ether and diethyl ether), diether (e.g., dimethoxymethane and diethoxymethane)), and methyl formate, organic acids (e.g., but not limited to, formic acid) (including any combination thereof) may be included, but such components are not necessarily preferred in many embodiments due to their adverse environmental impacts.

[0142] Foams and Foaming Processes The foam of the present invention containing each of foams 1 to 4, or the foam made from the PEF polymer of the present invention containing thermoplastic polymers TPP1A to TPP22E, or any of the foams described in Examples 1 to 22 can generally be formed from the foamable composition of the present invention. Generally, the foamable composition of the present invention can be formed by combining the PEF polymer of the present invention containing each of thermoplastic polymers TPP1A to TPP22E with the blowing agent of the present invention containing each of blowing agents 1 to 11.

[0143] The foamable compositions that are within the scope of the present invention and provide certain advantages in relation to the formation of the foam of the present invention are described in the following foamable composition tables (Tables 3A and 3B), and all numerical values in the tables are understood to be preceded by the word "about", and the following terms used in the tables have the following meanings.

[0144] CBAG1 means a co-blowing agent selected from the group consisting of 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf, and combinations of two or more thereof.

[0145] CBAG2 means a co-blowing agent selected from the group consisting of water, CO2, C1-C6 hydrocarbons (HC), HCFC, C1-C5 HFC, C2-C4 hydrohaloolefins, 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.

[0146] CCBAG3 means a co-blowing 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), 1,1,1,2-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.

[0147] NR means not required.

[0148]

Table 5-1

[0149]

Table 5-2

[0150]

Table 5-3

[0151]

Table 5-4

[0152]

Table 5-5

[0153]

Table 5-6

[0154]

Table 5-7

[0155]

Table 5-8

[0156]

Table 6-1

[0157]

Table 6-2

[0158]

Table 6-3

[0159]

Table 6-4

[0160]

Table 6-5

[0161]

Table 6-6

[0162]

Table 6-7

[0163] Foam formation method In order to form the foam of the present invention containing each of Foams 1 to 4, it is contemplated that any one or more of various known techniques for forming thermoplastic foams may be used in view of the disclosure included herein, and all such techniques and all foams and foam articles including Foam Articles 1 to 3 formed thereby are within the broad scope of the present invention. It should be noted that, for the sake of clarity, the definitions of the foams in the following table all start only with the letter F and are contrasted with the foam defined by the paragraph of the summary of the invention starting with the capitalized Foamable Composition.

[0164] Generally, the forming process includes first introducing a blowing agent of the present invention containing each of Blowing Agents 1 to 31 into the PEF polymer of the present invention containing each of TPPs 1 to 22 to form a foamable PEF composition containing PEF and the blowing agent. An example of a preferred method for forming the foamable PEF composition of the present invention is to plasticize the PEF, preferably heating the PEF to its melting temperature, preferably to a temperature higher than its melting temperature, and then exposing the PEF melt to the blowing agent under conditions effective to incorporate (preferably solubilize) the desired amount of the blowing agent into the polymer melt.

[0165] In a preferred embodiment, the foaming method of the present invention includes providing a foamable composition of the present invention containing each of FCs 1 to 13 and foaming the provided foamable composition. In a preferred embodiment, the foaming method of the present invention includes providing a foamable composition of the present invention containing each of FCs 1 to 13, extruding the provided foamable composition to form a foam article of the present invention, and then forming a foam article of the present invention containing each of Foam Articles 1 to 4.

[0166] The foaming process of the present invention can include a batch process, a semi-batch process, a continuous process, and combinations of two or more of these. A batch process generally involves preparing at least a portion of the foamable polymer composition including each of FC1 to FC13 in a storable state, and then using that portion of the foamable polymer composition at a future time to prepare a foam. A semi-batch process includes, in a single process, preparing at least a portion of the foamable polymer composition including each of FC1 to FC13, and intermittently expanding the foamable polymer composition into a foam including each of Foams 1 to 4 and each of Foams F1 to F8. For example, U.S. Patent No. 4,323,528, which is incorporated herein by reference, discloses a process for making a thermoplastic foam via a cumulative extrusion process. Accordingly, the present invention includes: 1) mixing a PEF thermoplastic polymer including each of TPP1 to TPP22 and a blowing agent of the present invention including each of Blowing Agents 1 to 31 under conditions to form 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 at which the foamable composition does not foam, the holding zone preferably including a die defining an orifice that opens into a zone of lower pressure where the foamable polymer composition including each of FC1 to FC13 foams, and a releasable gate for closing the die orifice; 3) periodically opening the gate while substantially simultaneously applying mechanical pressure to the foamable polymer composition including each of FC1 to FC13 by a movable ram to discharge from the holding zone through the die orifice into a zone of lower pressure; and 4) expanding the discharged foamable polymer composition under the influence of the blowing agent to form a foam including each of Foams 1 to 4 and each of Foams F1 to F8.

[0167] The present invention can also use a continuous process to form a foam. By way of example, such a continuous process involves forming a foaming PEF composition comprising each of FC1 to FC13 and then expanding the foaming PEF composition without substantial interruption. For example, a foaming PEF composition comprising each of FC1 to FC13 is prepared by heating a selected PEF polymer resin comprising each of TPP1 to TPP22 to form a PEF melt, and incorporating a blowing agent of the present invention comprising each of blowing agents 1 to 11, preferably by solubilizing the blowing agent in the PEF melt at an initial pressure, to form a foaming PEF composition comprising a substantially homogeneous combination of PEF and a blowing agent comprising each of FC1 to FC13. The foaming PEF composition is then extruded through a die into a zone of a selected foaming pressure and expanded under the influence of the blowing agent to form a foam comprising each of foams 1 to 4 and each of foams F1 to F8 described hereinafter, and can be prepared in an extruder. Optionally, a foaming PEF composition comprising a PEF polymer comprising each of FC1 to FC13 and an incorporated blowing agent comprising each of blowing agents 1 to 11 is cooled before extruding the composition through the die to improve certain desired properties of the resulting foam, comprising each of foams 1 to 6 and each of foams F1 to F8.

[0168] This method can be implemented, for example, using a general type of extrusion equipment disclosed in FIG. 8. Specifically, the extrusion device can include a raw material supply hopper 10 for holding the PEF polymer 15 of the present invention, each of TPP1 to TPP22, and one or more optional components (which can be added with PEF in the hopper or optionally at other locations in the process according to the specific needs of the user). The feedstock 15, excluding the blowing agent, can be charged into the hopper and delivered to the screw extruder 10. The extruder 20 can include thermocouples (not shown) arranged at three points along its length and a pressure sensor (not shown) at the discharge end 20A of the extruder. The mixer section 30 can receive the blowing agent components of the present invention, each of blowing agents 1 to 31, via one or more metering pumps 40A and 40B and can be located at the discharge end 20A of the extruder to mix these blowing agents into the PEF melt within the mixer section. Sensors (not shown) can be included to monitor the temperature and pressure of the mixer section 30. The mixer section 30 can discharge the melt of the blowing agent composition of the present invention, each of FC1 to FC13, into a pair of melt coolers 50 arranged in series, where temperature sensors (not shown) are located in each cooler to monitor the melt temperature. The melt is then extruded through a die 60 that also has temperature sensors and pressure sensors (not shown) for monitoring the pressure and temperature at the die. The die pressure and temperature can be varied according to the needs of each specific extrusion application for producing the foam 70 of the present invention, each of foams 1 to 4 and each of the foams F1 to F8 described below. The foam can then be carried out from the extrusion equipment by a conveyor belt 80.

[0169] The foamable polymer composition of the present invention containing each of FC1 to FC13 may optionally contain additional additives such as nucleating agents, cell control agents, glass and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR attenuators and heat insulation additives. Examples of nucleating agents include, among others, materials such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such as azodicarbonamide or sodium bicarbonate and citric acid. Examples of IR attenuators and heat insulation additives include, among others, carbon black, graphite, silicon dioxide, metal flakes or powders. Examples of flame retardants include, among others, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ethers. Each of the above-mentioned additional optional additives can be introduced into the foam at various times and various locations during the process according to known techniques, and all such additives and addition methods are within the broad scope of the present invention.

[0170] Foam In a preferred embodiment, the foam of the present invention is formed with a commercially available extrusion device and has the characteristics shown in Table 4 below, and the values are measured as described in the examples of this specification.

[0171]

Table 7

[0172] Foams that are included within the scope of the present invention and provide certain advantages are described in Table 5 below, and all numerical values in the table are understood to be preceded by the word "about", and the symbol NR means "not required".

[0173]

Table 8-1

[0174]

Table 8-2

[0175]

Table 8-3

[0176]

Table 8-4

[0177]

Table 8-5

[0178]

Table 8-6

[0179]

Table 8-7

[0180]

Table 8-8

[0181]

Table 8-9

[0182]

Table 8-10

[0183]

Table 8-11

[0184]

Table 8-12

[0185]

Table 8-13

[0186]

Table 8-14

[0187]

Table 8-15

[0188]

Table 8-16

[0189]

Table 8-17

[0190]

Table 8-18

[0191]

Table 8-19

[0192]

Table 8-20

[0193]

Table 8-21

[0194]

Table 8-22

[0195]

Table 8-23

[0196]

Table 8-24

[0197]

Table 8-25

[0198]

Table 8-26

[0199]

Table 8-27

[0200]

Table 8-28

[0201]

Table 8-29

[0202]

Table 8-30

[0203]

Table 8-31

[0204]

Table 8-32

[0205]

Table 8-33

[0206]

Table 8-34

[0207]

Table 8-35

[0208]

Table 8-36

[0209]

Table 8-37

[0210]

Table 8-38

[0211]

Table 8-39

[0212]

Table 8-40

[0213]

Table 8-41

[0214]

Table 8-42

[0215]

Table 8-43

[0216]

Table 8-44

[0217]

Table 8-45

[0218]

Table 8-46

[0219]

Table 8-47

[0220]

Table 8-48

[0221]

Table 8-49

[0222]

Table 8-50

[0223]

Table 8-51

[0224]

Table 8-52

[0225]

Table 8-53

[0226]

Table 8-54

[0227]

Table 8-55

[0228]

Table 8-56

[0229]

Table 8-57

[0230]

Table 8-58

[0231]

Table 8-59

[0232]

Table 8-60

[0233]

Table 8-61

[0234]

Table 8-62

[0235]

Table 8-63

[0236]

Table 8-64

[0237]

Table 8-65

[0238]

Table 8-66

[0239] The foam of the present invention has broad utility. The present foam containing each of Foams 1 to 4 and Foams F1 to F8 has unexpected advantages in applications that require low density and / or good compression and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable procurement, and / or being made from recyclable materials and being recyclable. Specifically, the present foam containing each of Foams 1 to 6 and Foams F1 to F8 has unexpected advantages in wind energy applications (wind turbine blades (shear webs, shells, cores, and roots)), marine applications (ship hulls, decks, superstructures, bulkheads, stringers, and interiors), industrial lightweight applications, automotive and transportation applications (interiors and exteriors of automobiles, trucks, trains, airplanes, and spacecraft).

[0240] PEF:PET copolymers can be formed by any means known to those skilled in the art, including but not limited to the procedures described in the examples herein.

[0241] The foam of the present invention containing each of Foams 1 to 4 is formed from any one of a PEF homopolymer, a PEF copolymer, a PEF:PET copolymer, or a combination / mixture thereof.

[0242] In a preferred embodiment, the foam containing each of Foams 1 to 4 can be formed from a PEF homopolymer having at least 99.5 wt% or at least 99.9 wt% ethylene furanoate moieties.

[0243] In preferred embodiments, the foam of the present invention comprising each of Foams 1-3 can be formed from a PEF copolymer which is a polymer comprising a PEF copolymer having from about 0.5 wt% to about 99 wt% ethylene furanoate moieties. The present invention includes a foam comprising each of Foams 1-3, and the thermoplastic polymer consists essentially of the components set forth in the following table.

[0244]

Table 9-1

[0245]

Table 9-2

[0246]

Table 9-3

[0247] The foam of the present invention comprising each of Foams 1-3 can include a closed cell wall comprising each of the thermoplastic polymers of the present invention comprising each of TMP1-TMP12 described in the above table.

[0248] With respect to these embodiments of the present invention comprising a PEF copolymer, those skilled in the art, in view of the teachings contained herein, can select the type of copolymer material in the amounts used within each of the ranges described herein to achieve the desired enhancement / modification of the polymer without undue experimentation.

[0249] It is contemplated that the TMP of the present invention can be formed having various physical properties including the following ranges of polymer properties as measured as described in the examples herein.

[0250]

Table 10

[0251] Generally, it is contemplated that one of ordinary skill in the art can compound the PEF polymer within the above-described property ranges without undue experimentation in view of the teachings contained herein. However, in a preferred embodiment, the PEF polymer according to the present invention having these properties (including the PEF:PET copolymer of the present invention) is achieved by using one or more of the above-described synthesis methods in combination with various known auxiliary treatment techniques including those by treatment with a chain extender such as PMDA and / or by SSP treatment.

[0252] Examples of processes for the chain extension treatment of polyesters are provided in the document "Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process", Firas Awaja, Fugen Daver, Edward Kosior, 16 August 2004, https: / / doi.org / 10.1002 / pen.20155, which is incorporated herein by reference. As described in U.S. Patent Application Publication No. 1009 / 0264545, which is incorporated herein by reference, chain extenders are generally, typically, compounds that are at least bifunctional with respect to reactive groups that can react with end groups or functional groups in the polyester to extend the length of the polymer chains. In certain cases, as disclosed herein, such treatment can advantageously increase the average molecular weight of the polyester and improve its melt strength and / or other important properties. The degree of chain extension achieved is related, at least in part, to the structure and functionality of the compound used. A variety of compounds are useful 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. Nanocomposite materials such as finely dispersed nanoclay can be optionally used to control the viscosity. Commercially available chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema. The amount of chain extender can vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to treat the polymer can vary widely and, in a preferred embodiment, is in the range of about 0.1 to about 5 wt%, or preferably about 0.1 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.

[0253] An example of a process for the SSP treatment of poly(ethylene furanoate) is provided in the paper "Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase," by Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which is hereby incorporated by reference.

[0254] Blowing agent As detailed herein, the present invention includes the applicant's discovery that each of the foamed PEF compositions, including foamed PEF compositions 1 and foams 1-3, can provide a foaming composition having a surprising combination of physical properties that are difficult to achieve, including low density and good mechanical strength properties, with a selected group of blowing agents.

[0255] Foams and foaming processes The foams of the present invention are thermoplastic foams, and in general, any one or more of various known techniques for forming thermoplastic foams can be used in view of the disclosure included herein, and it is contemplated that all such techniques and the foams formed thereby, or all foams within the broad scope of the present invention, can be used.

[0256] Foam articles The foams and foam articles of the present invention have broad utility. The foam articles of the present invention, each comprising foam articles 1-3, in particular have unexpected advantages in applications requiring low density and / or good compression and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recyclable materials and being recyclable. Specifically, the foam articles of the present invention, each comprising foam articles 1-3, have unexpected advantages in wind energy applications (wind turbine blades (shear webs, shells, cores, and nacelles), marine applications (hulls, decks, superstructures, bulkheads, stringers, and interiors), industrial lightweight applications, automotive and transportation applications (interiors and exteriors of automobiles, trucks, trains, airplanes, and spacecraft), fixed building structures, and sports equipment).

[0257] As described above, the foam articles of the present invention, each comprising foam articles 1-3, generally comprise a foam having a skin material on at least a portion of its surface. As used herein, reference to a numbered foam article or group of numbered foam articles as defined herein means each of such numbered foam articles, including each foam article having a number within a group including any suffix numbers. For example, reference to foam article 3 includes reference to each of foam articles 3A, 3B, 3C, and 3D.

[0258] The size and shape of the foam used in the foam article can vary widely within the scope of the present invention depending on the application for which the article is made, and all such sizes and shapes are within the scope of the present invention. In many applications, the foam article is in the form of a three-dimensional form where the length and / or width are much larger in dimension than the thickness. In other applications, the form of the article can be characterized as a block, slab, panel, etc., or as a specific shape such as an I-beam, U-shape, or other specific shape.

[0259] By way of illustration and not limitation, FIG. 4 illustrates a form in which the foam article is of a general shape of a sheet or panel having facing materials on each side of the sheet or panel. In the illustrated embodiment, the foam article according to the present invention includes a core 1 of the PEF foam of the present invention containing each of TMP1 to 12 defined below, at least one reinforcing facing material 2, and at least one connecting and / or integrating layer 3. Those skilled in the art will appreciate that, in view of the teachings contained herein, the connecting / integrating layer may include, for example, a layer of adhesive, or may be formed by integrating the core material and the surface material without using a separate adhesive, such as by melting the surfaces of two materials together to form a connecting / integrating region. The facing material may be any material suitable for the intended use as described above, but in many applications, the facing material 2 is a sheet or film of a fibrous material as described above. The fibers of the preferred facing material 2 may be in the form of a woven mat or a non-woven mat (or a mat including a combination of woven and non-woven fibers), including, for example, either a woven calendered mat or a non-woven calendered mat, and the fibers may or may not be oriented (i.e., random). In embodiments where the fibers of the facing material are oriented, the orientation can include one direction, two directions, biaxial, triaxial, tetraaxial, and any combination thereof.

[0260] The connecting / integrating film, layer or region 3 may be of any material and any thickness necessary to attach or integrate the facing 3 to the core 1. Further, although the film or layer 3 is generally shown as being between the facing 2 and the core 1, it will be understood and recognized by those skilled in the art that the connecting layer or film generally extends to each of the foam core 1 and the facing 2. In certain preferred embodiments, the film or layer 3 can include an adhesive material such as an epoxy adhesive that binds the core 1 and the surface sheet 2 together. Other adhesive resins that can be used to bond the facing to the foam include polyurethane, vinyl ester, polyester, cyanate ester, urethane acrylate, bismaleimide, polyimide, silicone, phenolic resin, polypropylene, caprolactam, and any combination of two or more thereof. Generally, the process of forming the foam article of the present invention involves steps that provide a strong chemical and / or physical bond between the facing 2 and the foam 1, and all such steps are within the scope of the present invention.

[0261] In a preferred embodiment, the facing 2 may be the same or different and includes a plurality of interconnected sheets or mats that are bonded to each other by suitable means including an adhesive or resin interconnecting layer or material integration (e.g., melting together to form an integrated region). In such embodiments, the number of interconnected sheets that make up the facing 2 can vary widely, and in a preferred embodiment, the facing is contemplated to include from 2 to 10 interconnected sheets, and even more preferably from about 3 to about 5 interconnected sheets.

[0262] It is understood that the dimensions of the foam articles of the present invention, each including foam articles 1 to 3, can vary widely. However, in a preferred embodiment involving use related to wind turbine applications, the surface sheet can vary from about 0.1 mm to about 3 mm, or from about 0.4 mm to about 1.5 mm. Further, the relative thickness of the foam compared to the surface sheet can vary over a wide range depending on the particular application, and one of ordinary skill in the art can make an appropriate selection considering the teachings contained herein. Generally, it is generally understood that the thickness of the surface sheet is less than the thickness of the foam.

[0263] The preferred materials used to form the foam articles of the present invention, each including foam articles 1 to 3, are described in further detail below.

[0264] Surface material The foam articles of the present invention include a surface material that can have a wide variety of dimensions, and the dimensions used depend on the specific requirements of the application for which the foam article is used. Articles having all such dimensions are within the scope of the present invention.

[0265] The materials forming the surface material can also vary widely depending on the specific use intended for the foam article, and again, all such materials are within the scope of the present invention. For example, the surface material used in the foam articles of the present invention, each including foam articles 1 to 3, can include one or more fiber sheets or mats, and the fiber portion can be, for example, glass fibers (preferably impregnated with a resin and / or polymer), other natural fibers (such as cellulose and other plant-derived materials), mineral fibers (such as quartz), metal fibers or films, carbon fibers (preferably impregnated or reinforced with one or more polymers including a thermoplastic polymer and / or a thermosetting polymer), synthetic fibers such as polyester (including fibers containing furan-based polyesters disclosed in U.S. Patent Application Publication No. 2015 / 0111450, which is incorporated herein by reference), polyethylene, aramid, Kevlar, and any and all combinations thereof, and can be formed from a wide variety of materials.

[0266] Specific use The foam articles of the present invention have broad utility. The present foam articles, each containing foam articles 1-3, have unexpected advantages in applications that require low density and / or good compression and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recyclable materials and being recyclable. In particular, the present foam articles, each containing foam articles 1-3, are fluid energy transfer components, e.g., for wind and water energy transfer applications (e.g., wind turbine blades (shear webs, shells, cores, and nacelles) for transferring wind energy from fixed or moving devices located in air, and vortices, tides, ocean, water current oscillating hydrofoils, and kites for recovering water kinetic energy from fixed or moving devices located in water), marine applications (hulls, decks, superstructures, bulkheads, longitudinal members, and interiors), industrial lightweight applications, automotive and transportation applications (interiors and exteriors of automobiles, trucks, trains, aircraft, and spacecraft), and packaging applications, in terms of having unexpected advantages.

[0267] Referring particularly to FIGS. 2 and 3A, 3B, and 3C, the foam articles of the present invention, each including foam articles 1-3, can be used in rotor blade 10 at any and all positions along the length of the blade from blade root 30 to blade tip 32 disposed on the opposite side of blade root 30, and at any position along the body shell including all positions on pressure side 34, suction side 36, and extending from leading edge 26 to trailing edge 28 of rotor blade 10. Further, the foam articles of the present invention, each including foam articles 1-3, can be used for all or part of the longitudinally extending structural components such as spark caps 20, 22 configured to engage the opposing inner surfaces 35, 37 of the positive pressure surface 34 and negative pressure surface 36 of rotor blade 10, which increase the rigidity, buckling resistance, and / or strength of rotor blade 10, and for one or more shear webs 24 disposed between spark caps 20, 22 to form a beam-like configuration. Spark caps 20, 22 are generally designed to resist bending stresses and generally minimize blade tip deflection and / or other loads acting on rotor blade 10 in the span direction (a direction parallel to the span 23 of rotor blade 16) during operation of wind turbine 10. However, in other applications, it is understood that the spark caps may also be oriented at any angle transverse to the span direction axis, including an angle of about 90 degrees with respect to the span direction axis. Similarly, spark caps 20, 22 may also be designed to resist spanwise compression or tension that occurs during operation of wind turbine 6. Due to the unexpected combination of lightweight and high strength of the foam articles of the present invention, each including the foam and foam articles 1-3, the blade root portion, as well as the spars and caps used in the rotor blade, can advantageously utilize such foam and foam articles.

[0268] The following foam usage table includes some specific examples of some preferred uses of the preferred articles of the present invention. The column heading "Foam Article Number" refers to the foam articles identified above, and the specific foams in the column headings refer to the foams identified above.

[0269]

Table 11-1

[0270]

Table 11-2

[0271]

Table 11-3

[0272]

Table 11-4

[0273]

Table 11-5

[0274]

Table 11-6

Example

[0275] Without limiting the full scope of the invention, the applicants have demonstrated the utility of the PEF homopolymers and PEF-based copolymers of the invention and, for the purpose of comparing the performance of the foams of the invention made in accordance with the invention with foams made from PET, conducted a series of experiments using batch process pilot plant facilities. One of ordinary skill in the art will understand that when scaling up such laboratory tests to commercial grade extrusion, many of the strength values reported herein will generally increase substantially for reasons specific to the commercial process and testing. Non-limiting examples of these scale-up factors include that commercially available extruded foams are generally stronger in the extrusion direction due to the impact of being pushed under pressure through an extrusion die, the common use of roll stacks, and the testing of strength in the extrusion direction. Commercially available extruded foams are also generally formed by joining together portions of the foam, and the presence of these seams tends to strengthen the overall foam. As a result of these and potential other factors, the strength results reported in these examples are generally lower than what one of ordinary skill in the art would expect if the foaming process were carried out on a commercial extruder. Nevertheless, it is understood by one of ordinary skill in the art that the results reported herein generally reflect a foam-to-foam comparison benchmark of what would be expected if the process were scaled up to commercial extrusion.

[0276] These tests utilized herein involved the synthesis of a series of reference PET polymers covering a variety of physical properties including molecular weight, crystallinity, melting point, glass transition temperature, and decomposition temperature, followed by foaming under a wide range of processing conditions including melt temperature, melt time, pre-foaming pressure and temperature. The applicants also synthesized a series of PEF polymers (including homopolymers and copolymers) covering a range of physical properties and foamed them under a similarly wide range of processing conditions.

[0277] Polymer Formation A series of polymers were generally synthesized according to the procedures described in Synthesis Examples 1 to 3 below. The polymers produced in accordance with the present invention included homopolymers of PEF and copolymers of PEF and PET in various molar ratios. Homopolymers of PET were also produced for comparison purposes.

[0278] To produce a series of polymers having various polymer physical properties including glass transition temperature (Tg), melt temperature (Tm), decomposition temperature (Td), crystallinity (Cr), and molecular weight, a wide variety of synthesis parameters were used for each type of polymer. These polymers were then used to produce PEF foams according to the present invention and PET foams for comparison purposes. The polymers thus produced are identified in Table PFEx below.

[0279]

Table 12

[0280] Foam formation A series of PEF foams and reference PET foams were prepared using the highly preferred 1234ze(E) of the present invention as a blowing agent. Representative methods for forming the foams are reported in Foam Formation Examples 1 to 3 below. The foams included foam densities classified into the following ranges: (1) a low density range from 0.060 g / cc to 0.115 g / cc, (2) a medium density region above 0.115 g / cc to 0.170 g / cc, and (3) a high density region above 0.170 g / cc to 0.250 g / cc. A consistent set of processing conditions was utilized for comparable polymer properties within a given range. The details of each of these sets of experimental results are described in the examples and tables below.

[0281] For each polymer, a unique narrow range of melting temperature and pre-foaming temperature was identified for the foaming experiment. The foams thus produced through the examples of this application were tested, and the density of the foams was determined generally using a method corresponding to ASTM D71, except that hexane was used in place of water for the substitution. To facilitate comparison of the densities of the foams produced in these examples. In addition, each of the foams produced in these examples was tested to determine the tensile strength (hereinafter referred to as TS), the compressive strength (hereinafter referred to as CS), and the sum of TS and CS (hereinafter referred to as TS+CS). The measurements of the tensile strength and the compressive strength were respectively based on the guidelines specified in ASTM C297 and ISO 844, and the measurements in each case were carried out in the direction of reduced pressure.

[0282] Using the polymers described in Table PFEx above, generally about 1 gram of polymer (shown in Table FFEx below) was placed in a glass container, which was then placed in an autoclave with a capacity of 60 cc and dried under vacuum at a high temperature in the range of 130 °C to 150 °C for 6 hours to generate a series of foams using a foaming process. Then, the dried polymer was cooled to room temperature. For each case in Table FFEx below, the blowing agent consisted of 1234ze(E). The blowing agent was pumped into the autoclave containing the dried polymer, and then the autoclave was heated to melt the polymer. The PET / blowing agent mixture was maintained in the molten state at the pressure and temperature of the molten state for an approximate period (hereinafter referred to as "melting time", MTime) (either 60 minutes or 15 minutes) as shown in the table. Then, the temperature (temperature of the melt / blowing agent, MTemp) and pressure (pressure of the melt / blowing agent, MP) of the melt / blowing agent were reduced to the pre-foaming temperature (PFT) and pre-foaming pressure (PFP) over a period of about 5 to 15 minutes as shown in Table FFEx. Then, the autoclave was maintained at this temperature and pressure for approximately 30 minutes to ensure that the amount of blowing agent incorporated into the melt reached equilibrium under such conditions. Then, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (about 22 °C and 1 atmosphere) (about 10 seconds for the pressure reduction and about 1 to 10 minutes for the temperature reduction using cold water), and foaming occurred. The conditions used, including the amount of blowing agent, melting temperature, and pressure, were determined based on the ability to form acceptable foams with density values in the range of about 0.06 to 0.115 g / cm3 (g / cc), hereinafter referred to as low-density foams for convenience in the following table, or acceptable foams in the range of above 0.115 g / cc to 0.250 g / cc, hereinafter referred to as high-density foams for convenience in the following table, after several tests.

[0283]

Table 13

[0284]

Table 14-1

[0285]

Table 14-2

[0286] Typical methods for forming the foams are reported in the following Foam Formation Examples 1 to 3 below, and all foams used 1234ze(E) as the only blowing agent. In addition, Foam Formation Example 4 reports a series of foams made from a PEF:PET copolymer and blowing agents 1233zd and 1336mzz in addition to the preferred blowing agent 1234ze(E). These foams were prepared using the same general procedure as disclosed in Foam Formation Examples 1 to 3. The foams made using 1234ze(E) were found to be unexpectedly superior to foams foamed with other blowing agents other than 1234zd(E), but as is also apparent from the data reported in Foam Formation Example 3, acceptable foams were produced and had substantial utility when the blowing agent included 1233zd(E) or 1336mzz(Z), or consisted essentially of them, or consisted of them. The Applicants have surprisingly found that the foams of the present invention have excellent strength characteristics, particularly when measured by the combined value of tensile strength and compressive strength, and that this combination also reflects excellent shear strength characteristics. In particular, the following charts show trend line data for the combined value of tensile strength and compressive strength as a function of foam density in each of the low density region (see Figure 5) and high density region (see Figure 6) for the PEF homopolymers and PEF:PET copolymers of the present invention compared to PET homopolymers made using the same procedure.

[0287] As shown in Figure 5, the foams of the present invention in the low-density regions made from both the PEF homopolymer (solid line) and the PEF:PETE copolymer (thick dashed line) of the present invention, on average, exhibit dramatically superior strength performance as a function of density over most of the low-density range compared to foams formed from PET homopolymers. As an example, at approximately the midpoint density of the low-density range (i.e., 0.09 g / cc), the PEF homopolymer and the PEF:PET copolymer of the present invention according to this example have, on average, a TS+CS of about 2.4. This represents an unexpected increase in strength of about 1.25 times compared to the average PET homopolymer performance (i.e., 2 TS+CS). Compared to foams formed from PET homopolymers, the foams of the present invention made from the present PEF homopolymer and the PEF:PET copolymer can also achieve a substantial advantage in that they can achieve the same strength as PET foams while having a substantially lower density by using these foams. As a specific example, if PET having a density of 0.1 is being used in a given application to achieve a TS+CS strength of 2.2, using the average values shown in Figure 5, the PET foam can be replaced with a PEF foam of the present invention having a TS+CS strength of 2.2 Mpa but a much lower foam density, i.e., any density up to a density of 0.065 g / cc. This represents a maximum 35% weight reduction for a given application. These are very beneficial and unexpected results, as shown in the following examples for several specific applications including wind turbine blades.

[0288] As shown in FIG. 6, the foams of the present invention in the high density region made from both the PEF homopolymer (solid line) and the PEF:PETE copolymer (thick dashed line) of the present invention, on average, provide superior strength performance as a function of density over substantially the entire intermediate density range, compared to foams formed from PET homopolymer. By way of example, at approximately the midpoint density of the high density range (i.e., 0.185 g / cc), the PEF homopolymer of the present invention according to this example has, on average, a TS+CS of about 6. This represents an unexpected increase in strength of about 1.9 times compared to the average PET homopolymer performance (i.e., a TS+CS of 3.2). Compared to foams formed from PET homopolymer, the foams of the present invention made from this PEF homopolymer and the PEF:PET copolymer can also achieve a substantial advantage of having a substantially lower density while achieving the same strength as the PET foam by using the foam. As a specific example, if PET having a density of 0.25 (i.e., in the high density region) is being used in a given application to achieve a TS+CS strength of about 3.8, using the average values shown in FIG. 6, it is possible to replace the PET foam with a PEF:PET foam of the present invention having a TS+CS strength of 3.8 Mpa but a much lower foam density, i.e., 0.135 g / cc. This represents a weight reduction of about 46% for that given application. Further, the replacement PEF:PET in the high density range provides such a significant advantage, but it is also frequently possible to obtain even greater advantages by using the PEF homopolymer and / or the PEF:PET copolymer from the low density range of the present invention in place of the PET polymer from the high density range. These are very beneficial and unexpected results, as shown in the following examples for several specific applications including wind turbine blades.

[0289] As described in the above specification including the examples, the foam of the present invention provides important and unexpected advantages in relation to many applications. These advantages include the ability to achieve (1) excellent strength relative to the applied density, (2) a reduction in density, and thus a weight advantage, for foams having the same density as previously used PET foams, and (3) a combination of excellent strength and a reduction in density. Based on the average values illustrated in FIGS. 1 - 3, the following table provides specific examples of such advantages of replacing a PET foam having a specific density and / or strength (measured by TS+CS) with the foam of the present invention:

[0290]

Table 15

[0291]

Table 16

[0292]

Table 17

[0293]

Table 18

[0294] Usage examples A wind turbine generator having a general configuration illustrated in FIGS. 1 to 3 of this specification is constructed on land with a nacelle located approximately 150 meters (based on the center line of the nacelle) away from the ground. The blade span of each blade from the hub axis to the blade tip is approximately 100 meters, and the rotor diameter is approximately 200 meters. The generator generates approximately 13 MW of power under peak design conditions. Each blade includes a surface-finished PET foam, with approximately 30% by weight of the foam being a high-density foam (i.e., a density of 0.24 g / cc before surface finishing), and approximately 70% by weight of the PET foam being a low-density foam (i.e., a density of 0.11 g / cc before surface finishing). The total weight of all PET foam (excluding the surface material) within the wind turbine is approximately 10% by weight of the total blade weight.

[0295] Example 1A - 13 MW Weight-Reduced Wind Turbine Generator Manufactured Using the PEF Homopolymer Foam of the Present Invention A wind turbine generator having the configuration described in Comparative Example 1 is constructed, except that the high-density PET foam and / or low-density PET foam of Comparative Example 1 is replaced with the foam of the present invention based on any one of Foams 1 to 4. In this example, the high-density PET foam and / or low-density PET foam of Comparative Example 1 is replaced by a foam made from a preferred PEF homopolymer foam blown with 1234ze as represented by the above PEF replacement table and the trend lines of FIGS. 5 and 6, and / or by a foam made from a preferred PEFPET copolymer foam blown with 1234ze as represented by the above PEFPET replacement table and the trend lines of FIGS. 5 and 6. One option for replacement is, based on equal strength, (1) to replace all low-density PET using the PEF homopolymer represented by the above PEF replacement table and the trend line of FIG. 5, and (2) to replace all high-density PET foams using the PEFPET copolymer represented by the above PEFPET replacement table and the trend line of FIG. 6. In this option, the PEF homopolymer according to the trend line of FIG. 5 having a density of about 0.09 has a strength substantially matching the TS+CS strength as a low-density PET foam. On average, this results in the ability to use a foam made from the PEF homopolymer of the present invention that is about 22% lower in density and thus about 22% lighter in weight than the low-density PET foam. At the same time, the PEFPET copolymer according to the trend line of FIG. 6 having a density of about 0.16 has a strength substantially matching the TS+CS strength as a high-density PET foam. On average, this results in the ability to use a foam made from the PEFPET copolymer of the present invention that is about 35% lower in density and thus about 35% lighter in weight than the high-density PET foam. The net result is a reduction in blade weight of about 2.5%. The unexpected reduction in blade weight achievable by using the foam of the present invention is substantial and commercially important. The reduced blade weight means that many other components of the wind turbine can be made smaller and / or lighter, thereby not only providing additional environmental benefits but also significantly reducing construction costs.For example, the nacelle of a wind turbine is designed to be compatible with the blades, including being sized and weighted to balance the torque created by the blades. Additionally, this weight reduction results in cost savings for tower design and construction costs.

[0296] Many other advantageous options are possible for replacing the PET foam with the foam of the present invention, and some of these options (along with the options described in the above examples, identified below as Option 1) are illustrated in the following table:

[0297] [Table 19]

[0298] As can be seen from the options shown in the above table, the degree of weight reduction of the blade weight ranges from 2.5% to 3.95%, and for any given case, one of ordinary skill in the art may choose an option that does not provide the highest weight reduction in order to meet other requirements. For example, if the highest priority is to exclude any foam supplied from petroleum products, Option 3 is selected because Option 3 relies on a 100% PEF homopolymer that can be 100% supplied from non-petroleum products. Alternatively, if cost is the main consideration, Option 4 may be of interest as it is expected that a PEF / PET copolymer may be available at a lower cost than a PEF homopolymer. One of ordinary skill in the art will understand that many other advantageous combinations and options are available for any particular replacement case considering the teachings and examples included herein.

[0299] Example 1B - 13 MW wind turbine generator made of PEF homopolymer foam using HFO - 1336MZZ blowing agent A wind turbine generator having the configuration as described in Example 1A is constructed, except that the PET foam core material of Comparative Example 1A is replaced with the PEF polymer foam of the present invention foamed with a blowing agent composed of HFO-1336mzz including those reported in Foam Formation Example 4. Acceptable results are observed.

[0300] 13 MW wind turbine generator made of a PEF homopolymer foam using the Example 1C - HFO-1233zd blowing agent A wind turbine generator having the configuration as described in Example 1A is constructed, except that the PET foam core material of Comparative Example 1A is replaced with the PEF polymer foam of the present invention foamed with a blowing agent composed of HFO-1336mzz including those reported in Foam Formation Example 4. Acceptable results are observed.

[0301] 13 MW wind turbine generator made of a PEF homopolymer foam using the Example 1D - HFO-1224yd blowing agent A wind turbine generator having the configuration as described in Example 1A is constructed, except that the PET foam core material of Comparative Example 1A is replaced with the PEF polymer foam of the present invention foamed with a blowing agent composed of HFO-1224yd. Acceptable results are observed.

[0302] 13 MW wind turbine generator made using a foam formed from a PEF polymer prepared using the Example 1F - ADR additive A wind turbine generator having the configuration as described in Example 1 is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the foam of the present invention prepared from a PEF polymer using an ADR additive as described in Foam Formation Example 5. Acceptable results are observed.

[0303] 13 MW wind turbine generator made using a foam formed from a PEF polymer prepared using the Example 1G - PENTA additive A wind turbine generator having the configuration as described in Example 1 is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the foam of the present invention made from a PEF polymer using the PENTA additive as described in Foam Formation Example 5. Acceptable results are observed.

[0304] Example 1 A 13 MW wind turbine generator made using a foam formed from a PEF polymer made using an H-PMDA + talc additive A wind turbine generator having the configuration as described in Example 1 is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the foam of the present invention made from a PEF polymer using the PMDA + talc additive as described in Foam Formation Example 5. Acceptable results are observed.

[0305] Example 2 A 17 MW wind turbine generator made using the thin PEF homopolymer foam of the present invention in the blade shell A wind turbine generator having the configuration described in Comparative Example 1 is produced, except that the PET foam core is replaced with a foam made from the PEF homopolymer foam of the present invention containing each of Foams 1 to 4, or the PEF copolymer of the present invention containing the thermoplastic polymers TPP1A to TPP22E. The preferred homopolymer foam of the present invention exhibits a tensile strength + compressive strength that is on average approximately 1.3 times higher at approximately the same density comparable to the density of the PET foam of Comparative Example 1, as represented by the above PEF substitution table. The preferred PEF homopolymer foam of the present invention is considered to have a shear strength more advantageous than that of the PET foam at approximately this density. In particular, the shear strength is approximately the average of the tensile strength and the compressive strength, and thus, the shear strength of this copolymer foam has, on average, a shear strength approximately 1.3 times higher than that of the PET foam at a foam density of approximately 0.1 g / cc. This 1.3-fold advantage in shear strength is an unexpectedly very advantageous result because, at least in part, as long as the bending stiffness of the foam core remains acceptable as expected, the thickness of the core foam can be relatively reduced by approximately 30 percent. This is shown by the following calculation described in Chapter 3 of Introduction to Sandwich Structures, Student Edition, 1995, Dan Zenkert. τ c =T x / d In the formula, T x is the direct load in Newton units (per width of the beam, which is 1 cm in this case) that causes bending of the beam (the blade in this case). d is the thickness of the core foam + skin, which is approximately equal to the thickness of the core foam in cm units. τ c is the shear stress that the core foam receives as a result of the direct load. Since the load here is Newton / cm, the stress has the unit of pressure Newton / cm 2 and becomes. A high shear strength means a high shear stress (τ c ) and enables a thinner core foam thickness while still coping with the same direct load on the beam.

[0306] Example 3A: 6MW Weight-Reduced Wind Turbine Generator Example 3: High-Output Wind Turbine Generator Produced by Using a PEF Homopolymer at the Root Portion of a Blade Shell and a Foam of the PET:PEF Copolymer and / or PEF Homopolymer of the Present Invention at Non-Root Portions A wind turbine generator having the configuration described in Comparative Example 1 is fabricated, except that the combination of the PEF homopolymer and PEF-PET copolymer of the present invention described in Example 1 is used for the purpose of increasing the output of the wind turbine instead of reducing the weight. As illustrated in Example 1A above, the use of various combinations of the PEF homopolymer and / or PEF-PET copolymer of the present invention enables a blade weight reduction in the range of 2.5% to about 4% of the blade weight. A weight reduction of 2.5% to 4% is expected to provide a blade that recovers a weight loss of 2.5% to 4%, but this time, by using a longer blade of at least 1.1% to 1.8%, it results in 2.4% to 3.8% more output. The power data used in these calculations are shown in FIGS. 8 and 9.

[0307] In another option, the advantage can also be achieved by using the PEF or PET-PEF foam of the present invention at the same density as that used for the foam of the present invention. However, due to the increase in the strength of the foam, it may be possible to achieve output improvement by improving the blade design in various ways. -

[0308] Example 3B - 6MW Wind Turbine Generator Made of PEF Foam Using HFO-1336MZZ Blowing Agent A wind turbine generator having the configuration described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the PEF polymer foam of the present invention foamed with a blowing agent composed of HFO-1336mzz, including those reported in Foam Formation Example 4. Acceptable results are observed.

[0309] 6 MW Wind Turbine Generator Made of PEF Homopolymer Foam Using Example 3 C-HFO-1233zd Foaming Agent A wind turbine generator having the configuration described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the PEF polymer foam of the present invention foamed with a foaming agent composed of HFO-1336mzz, including those reported in Foam Formation Example 4. Acceptable results are observed.

[0310] 6 MW Wind Turbine Generator Made of PEF Homopolymer Foam Using Example 3 D-HFO-1224yd Foaming Agent A wind turbine generator having the configuration described in each of Example 3A is constructed, except that the PET foam core of Comparative Example 1 is replaced with the PEF polymer foam of the present invention foamed with a foaming agent composed of HFO-1224yd. Acceptable results are observed.

[0311] 6 MW Wind Turbine Generator Made Using a Foam Formed from a PEF Polymer Produced Using Example 3 E ADR Additive A wind turbine generator having the configuration described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the PEF polymer foam of the present invention produced from a PEF polymer using an ADR additive as described in Foam Formation Example 5. Acceptable results are observed.

[0312] 6 MW Wind Turbine Generator Made Using a Foam Formed from a PEF Polymer Produced Using Example 3 F PENTA Additive A wind turbine generator having the configuration described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the PEF polymer foam of the present invention produced from a PEF polymer using a PENTA additive as described in Foam Formation Example 5. Acceptable results are observed.

[0313] 6 MW wind turbine generator fabricated using a foam made from a PEF polymer produced using an Example 3 H-PENTA additive A wind turbine generator having the configuration described in each of Example 3A is constructed, except that the PET foam core material of Comparative Example 1 is replaced with the PEF polymer foam of the present invention produced from a PEF polymer using a PMDA + talc additive as described in Foam Formation Example 5. Acceptable results are observed.

[0314] Aircraft using one or more of Foam Articles 1 to 3 of Example 4 The aircraft includes at least one foam article of the present invention including one or more of Foam Articles 1 to 3, in one or more locations requiring a structural foam, preferably including at least a portion of one or more of a wing, fuselage, tail, door, bulkhead, interior, and / or upper structure. The aircraft achieves (1) a foam weight that is lighter than a previously used structural foam article, preferably at least about 2% less than the weight of the previously used foam, (2) an advantage in size and / or performance compared to using the same foam weight as a previously used structural foam, and / or (3) a combination of (1) and (2).

[0315] Land vehicle using one or more of Foam Articles 1 to 3 of Example 5 The vehicle includes at least one foam article of the present invention including one or more of Foam Articles 1 to 3, in one or more locations requiring a structural foam, preferably including at least a portion of one or more of a side panel, floor panel, roof panel, engine compartment, inside of a battery compartment, and / or upper structure. The vehicle achieves (1) a foam weight that is lighter than a previously used structural foam article, preferably at least about 2% less than the weight of the previously used foam, (2) an advantage in size and / or performance compared to using the same foam weight as a previously used structural foam, and / or (3) a combination of (1) and (2).

[0316] Example 6 - Railway Vehicle Using One or More of Foam Articles 1 to 3 The railway vehicle includes at least a part of one or more locations that require a structural foam, preferably one or more of a side panel, a floor panel, a roof panel, and an upper structure, and includes at least one foam article of the present invention including one or more of each of the foam articles 1 to 3. The railway vehicle achieves (1) a foam weight that is lighter than a previously used structural foam article, preferably at least about 2% less than the weight of the previously used foam, (2) an advantage in size and / or performance compared to using the same foam weight as the previously used structural foam, and / or (3) a combination of (1) and (2).

[0317] Example 7 - Building Using One or More of Foam Articles 1 to 3 A building structure including at least a part of one or more locations that require a structural foam, preferably one or more of a wall panel, a floor structure, and a roof structure, and other structures in the building, includes at least one foam article of the present invention including one or more of each of the foam articles 1 to 3. The building achieves (1) a foam weight that is lighter than a previously used structural foam article, preferably at least about 2% less than the weight of the previously used foam, (2) an advantage in size and / or performance compared to using the same foam weight as the previously used structural foam, and / or (3) a combination of (1) and (2).

[0318] Example 8 - Packaging Using One or More of Foam Articles 1 to 3 Packaging, which is included in one or more locations where a structural foam is required, preferably in the form of boxes, inserts, separators, envelopes, etc., includes at least one foam article of the present invention, which includes one or more of each of the foam articles 1-3. The building achieves (1) a foam weight that is lighter than a previously used structural foam article, preferably at least about 2% less than the weight of the previously used foam, (2) an advantage in size and / or performance as compared to using the same foam weight as the previously used structural foam, and / or (3) a combination of (1) and (2).

[0319] Example 9 - Sporting goods using one or more of the foam articles 1-3 Sporting goods, which are included in one or more locations where a structural foam is required, preferably including tennis rackets, skateboards, water skis, or snow skis, etc., include at least one foam article of the present invention, which includes one or more of each of the foam articles 1-3. The sporting goods achieve (1) a foam weight that is lighter than a previously used structural foam article, preferably at least about 2% less than the weight of the previously used foam, (2) an advantage in size and / or performance as compared to using the same foam weight as the previously used structural foam, and / or (3) a combination of (1) and (2).

[0320] Synthesis example Synthesis example 1A1 - Preparation of a PET homopolymer having an MW of 41.2 kg / mol using PMDA 41.2 kg / mol 1A PEF homopolymer having a molecular weight of was formed by the esterification and polycondensation of 75 grams of 2,5-furandicarboxylic acid (FDCA) and 55 grams of monoethylene glycol (EG). The reactants were added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After evacuating and backfilling with nitrogen, 0.228 grams of titanium (IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180 °C and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature under nitrogen, vacuum was started. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 1 hour. PMDA (0.5732 g) was slowly added dropwise over about 5 minutes under a nitrogen stream. After mixing for an additional 30 minutes at this temperature, the reaction was stopped. To perform SSP, an aliquot of the product was pulverized and heated at 180 °C under vacuum in a rotary evaporator for 3 days to produce a PEF homopolymer having a molecular weight of 41 kg / mol. 1 Throughout these examples, the molecular weights determined and referred to herein refer to the determination of molecular weight by diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY NMR) according to the description contained in "Application of 1H DOSY NMR in Measurement of Polystyrene Molecular Weights" VNU Journal of Science: Natural Sciences and Technology, Vol. 36, No. 2 (2020) 16 - 21 June 2020, Nam et al, except that the solvents used were different. The above reference used 3 mg of polystyrene and 0.5 mL of deuterated chloroform. In these examples, NMR measurements were performed using the dissolved portion of 2 - 3 mg of polymer in a mixture of 0.6 mL of 50 volume % deuterated chloroform + 50 volume % trifluoroacetic acid.

[0321] Synthesis Example 1A Preparation of a 2-PEF Homopolymer Having a MW of 75000 kg / mol A 75 kg / mol PEF homopolymer was formed by the esterification and polycondensation of 350 grams of 2,5-furandicarboxylic acid (FDCA) and 279 grams of monoethylene glycol (EG). The reactants were added to a 1-liter cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After evacuating to vacuum and backfilling with nitrogen, 0.228 grams of titanium(IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180 °C and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature under nitrogen, vacuum was started. After 40 minutes under vacuum, the temperature was raised to 230 °C and continued for 1 hour. Under a nitrogen flow, PMDA (2.73 g - 0.7 wt%) was slowly added over about 5 minutes. After mixing for an additional 30 minutes at this temperature, the reaction was stopped. To perform SSP, an aliquot (30 g) of the product was ground and heated under vacuum at 180 °C in a rotary evaporator for 3 days to produce a PEF homopolymer having a molecular weight of 75 kg / mol.

[0322] Synthesis Example 1A3 - Preparation of a PEF Homopolymer Having an MW Range of Approximately 96 KG / Mol Using PMDA A polymer with a MW of 96,078 g / mol is prepared by combining 75 grams of 2,5-furandicarboxylic acid (FDCA) and 55 grams of monoethylene glycol (EG). The reactants were added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After evacuating to vacuum and backfilling with nitrogen, 0.228 grams of titanium(IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180 °C and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature under nitrogen, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 250 °C and continued for 1 hour. PMDA (0.5732 g) was slowly added dropwise over about 5 minutes under a nitrogen stream. After mixing for an additional 30 minutes at this temperature, the reaction was stopped. To perform SSP, an aliquot of the product was ground and heated at 180 °C under vacuum in a rotary evaporator for 3 days to produce a PEF homopolymer as reported below. The product was removed from the vessel. γ-Valerolactone was added to dissolve the polymer remaining in the reactor and on the impeller. The mixture was stirred at 190 °C for several hours. γ-Valerolactone was distilled from the polymer under vacuum to obtain a solid. To perform SSP, an aliquot of the product was ground and heated at 180 °C under vacuum in a rotary evaporator for 3 days to produce a PEF homopolymer having a molecular weight of 96,078.

[0323] Synthesis Example 2A - Preparation of a PET9:PEF1 copolymer having a MW of approximately 117.9:90.4 KG / mol using PMDA A block copolymer of PET9:PEF1 (9:1 molar ratio) was prepared with a target molecular weight of about 117,900 g / mol and 4 and 4 PET and PEF blocks respectively. Specifically, first, 498 grams of FDCA (2.7 moles) and 417 grams of EG (6.72 moles) were added to a 1000 mL cylindrical glass reactor equipped with an overhead stirrer and a distillation / condensation device, and PEF was prepared by immersing this in a salt bath at 190 °C. After purging with nitrogen, 0.414 grams of Ti(IV) isopropoxide catalyst was added to the flask, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature under N2, vacuum was started. After 40 minutes under vacuum, the temperature was raised to 240 °C and continued for 2 hours, then the reaction was stopped to produce PEF.

[0324] The PEF oligomer was prepared by adding 109 grams of EG and 0.45 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated in a salt bath at 230 °C until boiling. An aliquot (160 grams) of PEF from the above process was added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The resulting mixture was the PEF oligomer.

[0325] The PET oligomer was prepared by adding 103 grams of EG and 0.45 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated in a salt bath at 230 °C. Then, 160 grams of commercially available recycled PET flakes were added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The result was a PET oligomer mixture.

[0326] 12.0 grams of PEF oligomer and 111.7 grams of PET oligomer were rapidly added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus immersed in a salt bath at 220 °C, followed by the addition of 0.9083 grams of Ti(IV) isopropoxide to prepare a copolymer. Immediately thereafter (<2 minutes), a vacuum was applied to remove EG. After 40 minutes, the temperature was raised to 270 °C and the contents of the reactor were maintained under vacuum for 40 minutes. Under a N2 atmosphere, 0.483 grams of PMDA was slowly added. After mixing for an additional 30 minutes at this temperature, the reaction was stopped. An aliquot (30 g) of the above product was pulverized and then subjected to solid-state polymerization by heating at 180 °C under vacuum in a rotary evaporator for 3 days to produce a PET9:PEF1 copolymer having a PET molecular weight of 117.9 kg / mol.

[0327] Synthesis Examples 3A - 3E - Preparation of PET9:PEF1 Copolymers with a MW of Approximately 57 - 69 KG / Mol Using ADR, PMDA + Talc, and PENTA Three PET9:PEF1 block copolymers (9:1 molar ratio) and one PET19:PEF1 block copolymer (19:1 molar ratio) were prepared with a target molecular weight of approximately 10 - approximately 69 kg / mol for the PET portion of the copolymer using the additives and polymer formation procedures generally described in Synthesis Examples 1 - 3, except that PMDA was replaced only with PMDA + talc, chain extender ADR - 4468 (hereinafter referred to as "ADR") 2 and PENTA. 2 ADR 4468 is the trade name of a 2,3 - epoxypropyl methacrylate chain extender sold by BASF under the Joncryl family of trademarks.

[0328] The PET:PEF polymers thus produced were tested using the above measurement protocol and were found to have the properties reported in Table SyEx3 below:

[0329]

Table 20

[0330] Preparation of PET Homopolymers with Molecular Weights in the Range of 80 - 96 kg / mol and Crystallinities of 32 - 43 Using Synthesis Example 4A - 3D - PMDA Using the procedures described in the above Synthesis Example 1, and variations thereof, to achieve polymers having the molecular weights specified in the following SyEx4, polycondensation was carried out to yield polymer products having molecular sizes in the range of about 80 kg / mol to about 96 kg / mol, thereby preparing four PET homopolymers.

[0331] The PET polymers are designated herein as PETC1, PETC2, PETC3, and PETC, and they were tested and found to have the properties as reported in the following Table SyEx4:

[0332] [Table 21] As can be seen from the above table, each of the PET homopolymers was produced using a preferred high - crystallinity embodiment of the present invention.

[0333] Foam Formation Example Foam Formation Example 1 - Preparation of PET Foams Using PETC1, PETC2, PETC3, and PETC4 with 1234zE(E) Blowing Agent In a series of experiments, 1 gram of each polymer (shown in Table SyEx4 above) in a glass container was placed in an autoclave with a capacity of 60 cc and then dried under vacuum at a high temperature in the range of 130°C to 150°C for 6 hours. The dried polymer was then cooled to room temperature. In each case, the blowing agent was then 1234ze(E), and then the blowing agent was pumped into the autoclave containing the dried polymer. Then, the autoclave was heated to melt the polymer, and the temperature, pressure, and time are listed in Table FFeX - Low - density foam and Table FFeX - High - density foam above. After the indicated melt time, the temperature and pressure of the melt / blowing agent were then reduced to the pre - foaming temperature and pre - foaming pressure shown in the above table over about 5 to 15 minutes. Then, the autoclave was maintained at this temperature and pressure for about 30 minutes to ensure that the amount of blowing agent incorporated into the melt reached equilibrium under such conditions. The conditions used, including the amount of blowing agent and the melt temperature and pressure, were determined after several tests based on the ability to form an acceptable foam having an RFD value in the range of about 0.05 to about 0.25. Then, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (about 22°C and 1 atmosphere) (about 10 seconds for the pressure reduction and about 1 to 10 minutes for the temperature reduction using cold water), and foaming occurred.

[0334] The PET foam thus produced has the properties specified in Table FFeX - Low - density foam and Table FFeX - High - density foam above.

[0335] Preparation of Foam Forming Example 2 - PEF1A1 and PEF1A2 Used with Trans 1234ZE Blowing Agent with a Melt Time of 60 Minutes One foam was produced using PEF1 identified in the above Table FFeX - low - density foam and Table FFeX - high - density foam, and four foams were produced using PEF2. A foaming process designed using the same criteria as described in the above SyExC1 was used as described herein. The foams thus produced were tested and reported in the above Table FFeX - low - density foam and Table FFeX - high - density foam, and were found to have the properties shown in the following Table FFEx2.

[0336]

Table 22

[0337] Preparation of PEF foam using Foam Formation Example 3 - PET9PEF1 - EX3A with Trans 1234ZE blowing agent for a melt time of 60 minutes Six foams were produced from PET9PEF1 - EX3A using a foaming process designed using the same criteria as described in Comparative Example 1. The foams thus produced were tested and found to have the properties reported in the following Table E3B.

[0338]

Table 23

[0339] Preparation of PET9:PEF1 foam using Foam Formation Example 4 - PET9:PEF1 along with Trans 1234ZE, Trans 1233ZD, and CIS1336 blowing agents and a melt time of 60 minutes A series of foams were produced using PEF1:PET9 using a foaming process designed using the same criteria as described in Foam Synthesis Examples 1 - 3. The foams thus produced were tested and found to have the properties reported in the following Table FFEx4.

[0340]

Table 24

[0341] As is apparent from the data in the above Table FFEx4 and in other examples presented herein, Applicants have surprisingly found that the PET:PEF foams according to the present invention generally have excellent strength properties when the blowing agent comprises, consists essentially of, or consists of 1234ze(E), as compared to other blowing agents including 1233zd and 1336, as apparent from the data in the above table. Nevertheless, acceptable foams are produced and have substantial utility when the blowing agent comprises, consists essentially of, or consists of 1233zd(E) or 1336mzz(Z).

[0342] Foam Formation Example 5 - Preparation of a PEF Foam Using PET9PEF1-EX3A with a Trans 1234ZE Blowing Agent and PENTA, ADR, and PMDA + Talc Additives Using a foaming process designed using the same criteria as described in Foam Formation Examples 1-3, a foam was made from PET9PEF1 as described above in Synthesis Example 4. The foam thus produced was tested and found to have the properties reported in Table FFEx5 below.

[0343]

Table 25

[0344] As is apparent from the data in the above Table FFEx4, Applicants have surprisingly found that the PET:PEF foams according to the present invention generally have excellent strength properties when a preferred blowing agent comprising, consisting essentially of, or consisting of 1234ze(E) is used with various polymerization additives.

Claims

1. A wind turbine blade, comprising: a. a blade shell; and b. a foam within the blade shell, the foam comprising: (1) a thermoplastic polymer foam comprising cell walls that form closed cells, the thermoplastic polymer comprising an ethylene furanoate moiety and optionally an ethylene terephthalate moiety; and b. a blowing agent contained within the closed cells.

2. The wind turbine blade of claim 1, wherein the thermoplastic polymer comprises from about 0.5 mole % to about 100 mole % of an ethylene furanoate moiety.

3. The wind turbine blade of claim 1, wherein the thermoplastic polymer further comprises at least about 0.5 mole % of an ethylene terephthalate moiety.

4. The wind turbine blade of claim 1, wherein the thermoplastic polymer comprises (i) from about 0.5 mole % to about 99.5 mole % of an ethylene furanoate moiety and from 0.5 mole % to about 99.5 mole % of an ethylene terephthalate moiety, and (ii) has a molecular weight of from about 25,000 to about 140,000.

5. The wind turbine blade of claim 1, wherein at least about 75% of the cells are closed cells.

6. The wind turbine blade of claim 1, wherein the foam has a foam density of from about 0.05 g / cc to about 0.25 g / cc.

7. A surface-finished foam, comprising: a. a thermoplastic foam core comprising polymer foam cells that form closed cells, the thermoplastic polymer comprising an ethylene furanoate moiety and a blowing agent contained within the closed cells; and b. a facing material attached and / or integrated with at least a portion of the first foam.

8. An article of manufacture comprising the surface-finished foam of claim 9.

9. An energy generating device comprising the surface-finished foam of claim 9.

10. The energy generating device of claim 13, comprising a blade, foil, or rotor located within a wind turbine generator.

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