Thermoplastic foams and uses in applications requiring strength and lightweight

Abstract

Disclosed is a foam article comprising a thermoplastic closed cell foam having at least a first surface and comprising: (i) a thermoplastic polymer cell wall comprising at least about 0.5 wt% of an vinylfuranate moiety and optionally one or more comonomer moieties; (ii) a blowing agent contained in at least a portion of the closed cells; and a material different from the thermoplastic closed cell foam, the material attached to and / or integral with at least a portion of the first foam surface.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application is related to, claims the priority benefit of, and is incorporated by reference into, U.S. Provisional Application No. 63 / 343,990, filed on May 19, 2022, and also claims the priority benefit of U.S. Application No. 18 / 113,605, filed on February 23, 2023. Technical Field

[0003] The present invention relates to foamable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles made therefrom, including foam articles, such as panels, boards, sheets, blocks, beams and other shaped articles, which foam articles contain polyethylene furandicarboxylate (PEF) and have a surface covered by a sheet, mat, film, scrim or similar surface covering, and the present invention relates to the use of such articles in equipment, systems and methods that require or benefit from relatively lightweight and relatively strong foam forms, and more particularly to lightweight and relatively strong foam forms that are environmentally beneficial and sustainable. Background Art

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

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

[0006] There are many important applications that would benefit from the use of a covered or faced foam form, wherein the foam portion is made of 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, use in transportation equipment such as cars, trucks, rail cars, boats, ships, airplanes, etc., because in all such applications, the use of lightweight and relatively strong materials may be beneficial. Other examples include sports equipment, such as skis, snowboards, skateboards, etc., and fixed building structures, including, for example, as roof and floor pads in buildings and homes, and as components of walls. Packaging applications may also benefit from the foams provided by the present invention.

[0007] Another important example of an application that would benefit from relatively light and relatively high strength covered or faced foams made from renewable and sustainable materials is in blades, foils, and the like used as fluid energy transfer devices. Examples of such fluid energy transfer devices include blades used on wind turbines. Other types of fluid energy transfer devices include vortex, tidal, ocean current oscillation hydrofoils and kites that recover air or water kinetic energy from fixed or mobile devices located in the air or water.

[0008] Figure 1 An example of one type of wind turbine is schematically shown in FIG. 2 . In the configuration shown, a wind turbine, generally designated 2 , includes a tower 4 supporting a nacelle 6 enclosing a drive train 8. In a typical configuration, wind turbine blades 10 are arranged on a hub to form a "rotor" at one end of the drive train 8 outside the nacelle 6. In operation, wind passing over the blades 10 creates lift and causes the blades to rotate, and the rotating blades 10 drive a gearbox 12 connected to a generator 14 at the other end of the drive train 8, which is arranged within 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 therefore do not include a gearbox.

[0009] The nacelle in many wind turbines is located on top of a tower, which may be 120 meters above the ground, or even higher, for ground-based generators, and 150 meters above the water, or even higher, for offshore applications (offshore generators), and for this and other reasons, it is critical to construct the various components of the wind turbine blades from materials that are relatively lightweight and at the same time strong enough to withstand the forces to which the blades will be subjected. Therefore, in such applications, it is very important to use the lightest material that can provide the necessary strength characteristics, as this will not only improve the operating efficiency of the wind turbine, but also can benefit the construction and maintenance costs of the wind turbine. Although thermoplastic foams formed from polyethylene terephthalate (PET) have been used in wind turbine blades, the applicant has recognized that there are several important disadvantages to using such materials in such applications. For example, PET is not a sustainable material. In addition, certain parts of wind turbine blades use higher density materials such as balsa wood instead of PET foam because PET foam does not provide sufficient strength to meet the needs of those areas of the wind turbine blade.

[0010] See Figure 2 and Figure 3, for example, Figure 1 A typical rotor blade 10 is shown in perspective view, and Figure 3A A cross-sectional view of a rotor blade 10 along section line 3-3 is shown. As shown, a typical rotor blade 10 generally includes a blade root 30 and a blade tip 32, wherein the blade root is configured to be mounted or otherwise fixed to a hub of a wind turbine 2, and the blade tip is disposed opposite the blade root 30. The body shell 21 of the rotor blade is generally 1 cm to 6 cm thick and extends generally along the longitudinal axis 27 between the blade root 30 and the blade tip 32. The body shell 21 can generally serve as a shell / cover for the rotor blade 10 and can define a generally aerodynamic profile, such as by defining a cross-section of a symmetrical or cambered airfoil shape. Due to the different mechanical strength requirements along the length of the turbine blade 10, a core material containing a polymer foam such as PET foam is generally used in combination with balsa wood to form the body shell of the blade between the section 42 and the root 30, wherein the balsa wood is in a higher concentration in the area closer to the root where the strength requirements are higher.

[0011] refer to Figure 3A, it is noted that the rotor blade 10 generally has a pressure side 34 and a suction side 36 extending between a leading end 26 and a trailing end 28 of the rotor blade 10. Further, the rotor blade 10 may also have a span 23, the span defining an overall length between a blade root 30 and a blade tip 32, and a chord 25 defining an overall length between a leading edge 26 and a trailing edge 28. As is generally understood, the length of the chord 25 may generally vary relative to the span 23 as the rotor blade 10 extends from the blade root 30 to the blade tip 32. In addition, the rotor blade 10 may also include one or more longitudinally extending structural components configured to provide increased stiffness, bending 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 having spar caps 20, 22 configured to engage against opposing inner surfaces 35, 37 of the pressure side 34 and the suction side 36 of the rotor blade 10, respectively. Additionally, one or more shear webs 24 may be disposed between the spar caps 20, 22 to form a beam-like configuration. The spar caps 20, 22 may generally be designed to resist bending loads during operation of the wind turbine 2 and to minimize blade tip deflection and / or other loads acting on the rotor blade 10 in a generally spanwise direction (a direction parallel to the span 23 of the rotor blade 10). In some configurations, the spars are designed to also resist shear as well as tension and compression based on the manner in which the fibers are tilted in the laminate that makes up our spar caps. 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 such configurations, 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. Figure 3B and Figure 3C In an alternative arrangement shown in , the spar caps 20A and 22A may be integrated into the structural shell.

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

[0013] Whether the core material is in the shell or in the shear web or in the spar cap of a wind turbine blade, the core is typically sandwiched between two or more facesheets made of several layers of fiberglass adhered with epoxy. The facesheets provide longitudinal stiffness and strength after hardening, while the core provides out-of-plane strength and stiffness. The facesheets carry most of the bending and in-plane loads, while the core carries primarily shear loads.

[0014] With respect to the selection of thermoplastic resins, EP 3,231,836 acknowledges that despite interest in thermoplastic resins, particularly polyester-based resins, such interest has encountered difficulties in development, including difficulty in determining suitable foaming grades for such resins. Furthermore, while EP 3,231,836 notes that certain polyethylene terephthalate (PET) resins (including recycled forms of PET) can be melt extruded with suitable physical and / or chemical blowing agents to produce closed-cell foams having the potential for low density and good mechanical properties, no such resins are disclosed as being capable of producing foams having both good environmental properties and good performance properties, and also capable of being formed from sustainable sources. The '836 application identifies several possible polyester resins for forming open-cell foams, including polyethylene terephthalate, polybutylene terephthalate, polycyclohexyl terephthalate, polyethylene naphthalate, polyethylene furanoate, or mixtures of two or more of these. While the use of polyester materials to prepare foams substantially free of closed cells, as claimed in EP '836, may be beneficial for some applications, a disadvantage of such structures is that, in general, open cell foams will exhibit relatively poor mechanical strength properties.

[0015] CN 108484959 discloses that the preparation of foam products based on 2,5-furandimethyl copolyesters is problematic because of alleged problems with dissolution of the blowing agent into the polyester, and proposes the use of a combination of liquid and gas blowing agents and a specific process involving the sequential use of these different classes of blowing agents.

[0016] US 2020 / 0308363 and US 2020 / 0308396 each disclose the production of an amorphous polyester copolymer, which includes starting with recycled polyester (only PET is exemplified) as the main component, and then performing a series of processing steps to obtain an amorphous copolymer, i.e., a copolymer without crystallinity. A variety of different types of blowing agents are mentioned for such amorphous polymers.

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

[0018] Applicants have recognized that one or more unexpected advantages associated with the formation of thermoplastic foams, particularly extruded thermoplastic foams, can be achieved by using a polyester resin as disclosed herein in combination with a blowing agent comprising one or more hydrohaloolefins as disclosed herein.

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

[0020] The present invention includes a foam article comprising:

[0021] A thermoplastic closed-cell foam having at least a first foam surface and being any of Foams 1 to 4 as defined below; and

[0022] A material different from the thermoplastic closed-cell foam, the material being attached to and / or integral with at least a portion of the first foam surface.For convenience, the foam article according to this paragraph is referred to herein as foam article 1.

[0023] For convenience, but not necessarily by way of limitation, the material of the present invention that is different from the thermoplastic closed-cell foam and that is attached to and / or integral with at least a portion of the first foam surface is sometimes referred to herein as a "facer."

[0024] The present invention also includes a foam article comprising:

[0025] a thermoplastic closed-cell foam having at least a first surface; and

[0026] A material different from the thermoplastic closed-cell foam, the material being attached to and / or integral with at least a portion of the first foam surface, wherein the thermoplastic closed-cell foam comprises thermoplastic polymer cell walls comprising at least about 0.5 weight percent ethylene furanoate moieties and optionally one or more comonomer moieties. For convenience, the foam article according to this paragraph is referred to herein as Foam Article 2.

[0027] The present invention also includes a foam article comprising:

[0028] (a) a thermoplastic closed-cell foam having at least a first foam surface, wherein the thermoplastic polymer cells consist essentially of ethylene furanate moieties and ethylene terephthalate moieties; and

[0029] (b) a material different from said thermoplastic closed-cell foam, said material being attached to and / or integral with at least a portion of said first foam surface.

[0030] For convenience, a foam article according to this paragraph is referred to herein as foam article 3A.

[0031] The present invention also includes a foam article comprising:

[0032] (a) a closed-cell thermoplastic foam having at least a first foam surface; and

[0033] (b) a material different from said thermoplastic closed-cell foam, said material being attached to and / or integral with at least a portion of said first foam surface, wherein:

[0034] (i) the thermoplastic polymer pores include pore walls comprising at least about 0.5 weight percent ethylene furanoate moieties; and

[0035] (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.

[0036] For convenience, the foam article according to this paragraph is referred to herein as foam article 3B.

[0037] As used herein, relative foam density (RFD) refers to the density of the foamed polymer divided by the density of the polymer before expansion, which for simplicity is taken herein as 1.43 g / cc. Therefore, for the purposes used herein, RFD is equal to the foam density in g / cc divided by 1.43.

[0038] The present invention also includes a foam article comprising:

[0039] (a) a closed-cell thermoplastic foam having at least a first foam surface; and

[0040] (b) a material different from said thermoplastic closed-cell foam, said material being attached to and / or integral with at least a portion of said first foam surface, wherein:

[0041] (i) the thermoplastic polymer pores include pore walls comprising at least about 1 weight percent ethylene furanoate moieties; and

[0042] (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. And

[0043] (iii) The thermoplastic polymer closed cells contain one or more blowing agents.

[0044] For convenience, a foam article according to this paragraph is referred to herein as foam article 3C.

[0045] The present invention also includes a foam article comprising:

[0046] (a) a closed-cell thermoplastic foam having at least a first foam surface; and

[0047] (b) a material different from said thermoplastic closed-cell foam, said material being attached to and / or integral with at least a portion of said first foam surface, wherein:

[0048] (i) the thermoplastic polymer pores include pore walls comprising at least about 1 weight percent ethylene furanoate moieties; and

[0049] (ii) the foam has a relative foam density (RFD) of about 0.2 or less. And

[0050] (iii) the closed cells of the thermoplastic polymer contain one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms;

[0051] For convenience, a foam article according to this paragraph is referred to herein as foam article 3D.

[0052] The present invention also includes a foam article comprising:

[0053] (a) a thermoplastic closed-cell foam having at least a first foam surface; and

[0054] (b) a material different from said thermoplastic closed-cell foam, said material being attached to and / or integral with at least a portion of said first foam surface, wherein:

[0055] (i) the thermoplastic polymer pores include pore walls comprising at least about 0.5 weight percent ethylene furanoate moieties; and

[0056] (ii) the foam has a foam density of less than 0.2 g / cc; and

[0057] (iii) the closed cells of the thermoplastic polymer contain one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms;

[0058] For convenience, a foam article according to this paragraph is referred to herein as foam article 3E.

[0059] The present invention also provides a wind turbine blade, comprising a blade shell and a foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 in the blade shell. For convenience, the method according to this paragraph is referred to herein as wind turbine blade 1.

[0060] The present invention also provides a transport vehicle, the transport vehicle comprising a vehicle body and a foam product of the present invention, the foam product comprising a foam product selected from each of the foam products 1 to 3 in the vehicle body. For convenience, the method according to this paragraph is referred to herein as vehicle 1.

[0061] The present invention also provides a fixed building structure comprising a structural member and a foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 within or otherwise attached to the vehicle body. For convenience, the method according to this paragraph is referred to herein as fixed building structure 1.

[0062] The present invention also provides a sports equipment article, the sports equipment article comprising the foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 within or otherwise attached to the sports equipment article vehicle body. For convenience, the method according to this paragraph is referred to herein as sports equipment article 1.

[0063] The present invention also provides a sports equipment article, the sports equipment article comprising the foam article of the present invention, the foam article comprising a foam article selected from each of foam articles 1 to 3 within or otherwise attached to the sports equipment article vehicle body. For convenience, the method according to this paragraph is referred to herein as packaging 1. BRIEF DESCRIPTION OF THE DRAWINGS

[0064] Figure 1 is a schematic diagram of an exemplary wind turbine.

[0065] Figure 2 is a semi-schematic diagram of an exemplary wind turbine.

[0066] Figure 3A is a cross-section of an exemplary wind turbine blade.

[0067] Figure 3B is a cross-section of an exemplary wind turbine blade.

[0068] Figure 3C is a cross-section of an exemplary wind turbine blade.

[0069] Figure 4 is a cross section of an exemplary cover foam of the present invention in a specific form of a sandwich structure.

[0070] Figure 5 is a graphical representation of the strength results for low density foams of the Examples.

[0071] Figure 6 is a graphical representation of the strength results for high density foams of the Examples.

[0072] Figure 7 It is a semi-schematic diagram of the extruder.

[0073] Figure 8 and Fig. 9 is a graph of the data used in Example 3 to calculate blade length and power output improvements.

[0074] definition

[0075] 1234ze refers to 1,1,1,3-tetrafluoropropene, with no restriction on the isomeric form.

[0076] Trans-1234ze and 1234ze(E) each refer to trans-1,3,3,3-tetrafluoropropene.

[0077] Cis-1234ze and 1234ze(Z) each refer to cis-1,3,3,3-tetrafluoropropene.

[0078] 1234yf refers to 2,3,3,3-tetrafluoropropene.

[0079] 1233zd refers to 1-chloro-3,3,3-trifluoropropene, with no restriction on the isomeric forms.

[0080] trans-1233zd and 1233zd(E) each refers to trans-1-chloro-3,3,3-trifluoropropene.

[0081] 1224yd refers to cis-1-chloro-2,3,3,3-tetrafluoropropane, with no restriction on the isomeric form.

[0082] 1336mzz refers to 1,1,1,4,4,4-hexafluorobutene, with no restriction on the isomeric form.

[0083] trans-1336mzz and 1336mzz(E) each refer to trans-1,1,1,4,4,4-hexafluorobutene.

[0084] Cis-1336mzz and 1336mzz(Z) each refer to cis-1,1,1,4,4,4-hexafluorobutene.

[0085] Closed cell foam refers to foams in which a substantial volume percentage of the cells are closed, for example, about 20 volume % or more.

[0086] The vinyl furanoate moiety refers to the following structure:

[0087]

[0088] FDCA refers to 2,5-furandicarboxylic acid and has the following structure:

[0089]

[0090] MEG refers to monoethylene glycol and has the following structure:

[0091]

[0092] FDME refers to dimethyl 2,5-furandicarboxylate and has the following structure:

[0093]

[0094] PEF homopolymer refers to a polymer having at least 99 mol % of vinyl furanate moieties.

[0095] A PEF copolymer refers to a polymer having at least about 0.5 mol % of ethylene furanate moieties and greater than 0.5 % of polymer moieties other than ethylene furanate moieties.

[0096] PEF:PET copolymer refers to a polymer having at least about 0.5 mol % of ethylene furanate moieties and at least 0.5 mol % of ethylene terephthalate moieties.

[0097] PEF refers to poly(ethylene furanoate) and encompasses and is intended to reflect the description of PEF homopolymer and PEF copolymer.

[0098] The ethylene terephthalate portion refers to the structure in brackets:

[0099]

[0100] SSP refers to solid state polymerization.

[0101] PMDA refers to pyromellitic dianhydride having the following structure:

[0102] DETAILED DESCRIPTION

[0103] Poly(ethylene furanoate)

[0104] The present invention relates to foams and foam articles comprising cell walls containing PEF moieties.

[0105] The PEF forming the cell walls of the foam and foam article of the present invention may be a PEF homopolymer or a PEF copolymer, and in particular a PEF:PET copolymer.

[0106] PEF homopolymer is a known material that is known to be formed by: (a) esterification and polycondensation of FDCA with MEG; or (b) transesterification and polycondensation of FDME with MEG, for example as shown below:

[0107]

[0108] A detailed description of such known esterification and polycondensation synthesis methods is provided in GB Patent 621971 (Drewitt, JGN and Lincoln, J., entitled "Improvements in Polymers"), which is incorporated herein by reference. A detailed description of these known transesterification and polycondensation synthesis methods is provided in: Gandini, A., Silvestre, AJD, Neto, CP, Sousa, AF and Gomes, M. (2009), "The furan counterpart of poly(ethylene terephthalate): an alternative material based on renewable resources.", J. Polym. Sci. Polym. Chem. 47, 295–298. doi: 10.1002 / pola.23130, which is incorporated herein by reference.

[0109] Foam

[0110] The present invention comprises a low density thermoplastic foam comprising:

[0111] (a) thermoplastic polymer pores comprising pore walls forming closed cells, wherein the thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein the polymer comprises from about 0.5 mol % to about 100 mol % of ethylene furanoate moieties and optionally at least about 1 mol % of ethylene terephthalate moieties; and

[0112] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0113] For convenience, the foam according to this paragraph is referred to herein as Foam 1A.

[0114] The present invention comprises a low density thermoplastic foam comprising:

[0115] (a) thermoplastic polymer pores comprising pore walls forming closed cells, wherein the thermoplastic polymer has a crystallinity of at least about 5% and consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein the polymer comprises from about 0.5 mol % to about 100 mol % of ethylene furanoate moieties and optionally at least about 0.5 mol % of ethylene terephthalate moieties; and

[0116] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0117] For convenience, the foam according to this paragraph is referred to herein as Foam 1B.

[0118] The present invention comprises a low density thermoplastic foam comprising:

[0119] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises from about 0.5 mol % to about 20 mol % of ethylene furanoate moieties and at least about 0.5 mol % of ethylene terephthalate moieties; and

[0120] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0121] For convenience, the foam according to this paragraph is referred to herein as Foam 1C.

[0122] The present invention comprises a low density thermoplastic foam comprising:

[0123] (a) thermoplastic polymer pores comprising pore walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and consists essentially of ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 80 mol % to about 99 mol % of ethylene terephthalate moieties; and

[0124] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0125] For convenience, the foam according to this paragraph is referred to herein as foam ID.

[0126] The present invention comprises a low density thermoplastic foam comprising:

[0127] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 80 mol % to about 99 mol % of ethylene terephthalate moieties; and

[0128] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0129] For convenience, the foam according to this paragraph is referred to herein as Foam IE.

[0130] The present invention comprises a low density thermoplastic foam comprising:

[0131] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises from about 0.5 mol % to about 5 mol % of ethylene furanoate moieties and from about 95 mol % to about 99.5 mol % of ethylene terephthalate moieties; and

[0132] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0133] For convenience, the foam according to this paragraph is referred to herein as Foam 1F.

[0134] The present invention comprises a low density thermoplastic foam comprising:

[0135] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises from about 0.5 mol % to about 2 mol % of ethylene furanoate moieties and from about 98 mol % to about 99.5 mol % of ethylene terephthalate moieties; and

[0136] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0137] For convenience, a foam according to this paragraph is referred to herein as Foam 1G.

[0138] The present invention comprises a low density thermoplastic foam comprising:

[0139] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises about 1 mol % of ethylene furanoate moieties and about 99 mol % of ethylene terephthalate moieties; and

[0140] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0141] For convenience, the foam according to this paragraph is referred to herein as Foam 1H.

[0142] The present invention comprises a low density thermoplastic foam comprising:

[0143] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises about 0.5 mol % of ethylene furanoate moieties and about 99.5 mol % of ethylene terephthalate moieties; and

[0144] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0145] For convenience, the foam according to this paragraph is referred to herein as foam II.

[0146] The present invention comprises a low density thermoplastic foam comprising:

[0147] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises about 5 mol% of ethylene furanoate moieties and about 95 mol% of ethylene terephthalate moieties; and

[0148] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0149] For convenience, the foam according to this paragraph is referred to herein as Foam 1J.

[0150] The present invention comprises a low density thermoplastic foam comprising:

[0151] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises about 10 mol% of ethylene furanoate moieties and about 90 mol% of ethylene terephthalate moieties; and

[0152] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0153] For convenience, the foam according to this paragraph is referred to herein as foam 1K.

[0154] The present invention comprises a low density thermoplastic foam comprising:

[0155] (a) thermoplastic polymer pores comprising pore 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 ethylene furanoate moieties and ethylene terephthalate moieties, wherein the polymer comprises about 20 mol% of ethylene furanoate moieties and about 80 mol% of ethylene terephthalate moieties; and

[0156] (b) one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained in the closed cells.

[0157] For convenience, a foam according to this paragraph is referred to herein as Foam 1L.

[0158] The present invention comprises a low density thermoplastic foam comprising:

[0159] (a) thermoplastic polymer pores comprising pore walls comprising polyethylene furanoate, wherein at least 25% of the pores are closed cells; and

[0160] (b) 1234ze(E) contained in closed pores.

[0161] For convenience, the foam according to this paragraph is referred to herein as Foam 2A.

[0162] The present invention comprises a low density thermoplastic foam comprising:

[0163] (a) thermoplastic polymer pores, the thermoplastic polymer pores comprising pore walls, the pore walls comprising from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 0.5 mol % or more of ethylene terephthalate moieties; and

[0164] (b) 1234ze(E) contained in closed pores.

[0165] For convenience, the foam according to this paragraph is referred to herein as Foam 2B.

[0166] The present invention comprises a low density thermoplastic foam comprising:

[0167] (a) thermoplastic polymer pores, the thermoplastic polymer pores comprising pore walls, the pore walls comprising from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 0.5 mol % or more of ethylene terephthalate moieties; and

[0168] (b) 1336mzz(Z) contained in closed pores.

[0169] For convenience, the foam according to this paragraph is referred to herein as Foam 2C.

[0170] The present invention comprises a low density thermoplastic foam comprising:

[0171] (a) thermoplastic polymer pores, the thermoplastic polymer pores comprising pore walls, the pore walls comprising from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 0.5 mol % or more of ethylene terephthalate moieties; and

[0172] (b) 1223zd (E) contained in closed pores.

[0173] For convenience, foam according to this paragraph is referred to herein as Foam 2D.

[0174] The present invention comprises a low density thermoplastic foam comprising:

[0175] (a) thermoplastic polymer pores, the thermoplastic polymer pores comprising pore walls, the pore walls comprising a polymer comprising from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 0.5 mol % or more of ethylene terephthalate moieties; and

[0176] (b) 1224 yd contained in closed cells.

[0177] For convenience, the foam according to this paragraph is referred to herein as Foam 2E.

[0178] The present invention comprises a low density thermoplastic foam comprising:

[0179] (a) thermoplastic polymer pores comprising pore walls comprising from about 1 mol % to about 20 mol % of ethylene furanoate moieties and from about 0.5 mol % or more of ethylene terephthalate moieties, wherein at least 50% of the pores are closed cells; and

[0180] (b) a gas in the closed cells, wherein the gas comprises about 25 wt % to 100 wt % 1234ze(E).For convenience, the foam according to this paragraph is referred to herein as Foam 2F.

[0181] Reference will be made to numbered foams (e.g., Foam 1) or groups of numbered foams defined herein at various locations herein, and such references refer to each of such numbering systems, including each system with numbers within the group, including any suffix numbering systems. For example, reference to Foam 1 includes reference to each of Foams 1A, 1B, 1C, 1D, etc. individually, and reference to Foams 1 to 2 should be understood to include reference to each of Foams 1A, 1B, 1C, 1D, etc. individually, as well as each of Foams 2A, 2B, 2C, 2D, etc. In addition, this convention is used throughout this specification for other defined materials, including blowing agents.

[0182] The present invention comprises a low density thermoplastic foam comprising:

[0183] (a) thermoplastic polymer pores comprising pore walls forming closed cells, wherein the thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein 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; and

[0184] (b) trans-1234ze contained in closed pores.

[0185] For convenience, the foam according to this paragraph is referred to herein as Foam 3.

[0186] The present invention comprises a low density thermoplastic foam comprising:

[0187] (a) thermoplastic polymer pores comprising pore walls forming closed cells, wherein the thermoplastic polymer consists essentially of ethylene furanoate moieties and optionally ethylene terephthalate moieties, wherein 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 from about 25,000 to about 140,000; and

[0188] (b) trans-1234ze contained in closed pores.

[0189] For convenience, the foam according to this paragraph is referred to herein as Foam 4.

[0190] The foams of the present invention (including each of Foams 1 to 4) are formed from a PEF homopolymer, a PEF copolymer, or a combination / mixture of these.

[0191] In preferred embodiments, the foams of the present invention, including each of Foams 1 to 4, may be formed from a PEF homopolymer, wherein the polymer has at least 99.5 wt. % or at least 99.9 wt. % of ethylene furanoate moieties.

[0192] It is contemplated that the foams of the present invention (including each of Foams 1 to 4) can be formed from PEF copolymers in preferred embodiments, wherein the polymer (including PEF copolymers) has from about 60 wt % to about 99 wt % of ethylene furanoate moieties, or from about 70 wt % to about 99 wt % of ethylene furanoate moieties, or from about 80 wt % to about 99 wt % of ethylene furanoate moieties, or from about 90 wt % to about 99 wt % of ethylene furanoate moieties, or from about 95 wt % to about 99.5 wt % of ethylene furanoate moieties.

[0193] It is contemplated that the foams of the present invention, including each of Foams 1 to 4, may be formed from PEF copolymers in preferred embodiments, wherein the polymer (including the PEF copolymer) has from about 40 wt % to about 1 wt % of ethylene furanoate moieties, or from about 30 wt % to about 1 wt % of ethylene furanoate moieties, or from about 20 wt % to about 1 wt % of ethylene furanoate moieties, or from about 10 wt % to about 1 wt % of ethylene furanoate moieties, or from about 5 wt % to about 1 wt % of ethylene furanoate moieties, or from about 5 wt % to about 0.5 wt % of ethylene furanoate moieties.

[0194] It is contemplated that the foams of the present invention (including each of Foams 1 to 4) may be formed from PEF copolymers in preferred embodiments, wherein the polymer (including PEF copolymers) has from about 40 mol % to about 1 mol % of ethylene furanoate moieties, or from about 30 mol % to about 1 mol % of ethylene furanoate moieties, or from about 20 mol % to about 1 mol % of ethylene furanoate moieties, or from about 10 mol % to about 1 mol % of ethylene furanoate moieties, or from about 5 mol % to about 1 mol % of ethylene furanoate moieties, or from about 5 mol % to about 0.5 mol % of ethylene furanoate moieties.

[0195] It is contemplated that the foams of the present invention (including each of Foams 1 to 4) may be formed from PEF copolymers in preferred embodiments, wherein the polymer (including PEF copolymers) has from about 40 mol% to about 1 mol% of ethylene furanate moieties and from about 60 mol% to about 99 mol% of ethylene terephthalate moieties, or from about 30 mol% to about 1 mol% of ethylene furanate moieties and from about 70 mol% to about 99 mol% of ethylene terephthalate moieties, or from about 20 mol% to about 1 mol% of ethylene furanate moieties. and about 80 mol % to about 99 mol % of ethylene terephthalate moieties, or about 10 mol % to about 1 mol % of ethylene furanoate moieties and about 90 mol % to about 99 mol % of ethylene terephthalate moieties, or about 5 mol % to about 1 mol % of ethylene furanoate moieties and about 95 mol % to about 99 mol % of ethylene terephthalate moieties, or about 5 mol % to about 0.5 mol % of ethylene furanoate moieties and about 95 mol % to about 99.5 mol % of ethylene terephthalate moieties.

[0196] For those embodiments of the invention involving PEF copolymers, it is expected that those skilled in the art, given the teachings contained herein, will be able to select the type and amount of copolymer material to be used within each of the ranges described herein to achieve the desired reinforcement / modification of the polymer without undue experimentation.

[0197] For those embodiments of the invention involving the use of PEF homopolymers or PEF copolymers, it is contemplated that such materials may be formed having a variety of molecular weights and physical properties within the scope of the invention. In a preferred embodiment, the foams (including each of Foams 1 to 4) are formed from PEF having the characteristic ranges identified in Table 1 below, as measured as described in the Examples herein:

[0198] Table 1

[0199] Wide range First intermediate range Second intermediate range Narrow range Polymer properties Molecular weight 25,000-150,000 45,000-130,000 45,000-130,000 55,000-120,000 <![CDATA[Glass transition temperature, T g , °C]]> 75-100 75-95 75-95 75-95 <![CDATA[Melting temperature, T m , °C]]> 180-250 190-240 190-240 200-230 <![CDATA[Decomposition temperature, T d , °C]]> 300-420 320-400 320-400 330–380 Crystallinity, % 5-75 25-75 30-60 40-50

[0200] In general, given the teachings contained herein, it is expected that one skilled in the art will be able to formulate PEF polymers within the above-described range of properties without undue experimentation. However, in preferred embodiments, one or more of the above-described synthetic methods are used in combination with a variety of known supplemental processing techniques, including by treating with a chain extender such as PMDA (and alternatives and supplements to PMDA, such as ADR, pentaerythritol (hereinafter referred to as "PENTA") and talc, as described in this example, among others) and / or SSP processing of PEF (including PEF homopolymers and PEF copolymers) having these properties. It is believed that given the disclosure contained herein, including the polymer syntheses described in the examples below, one skilled in the art will be able to prepare PEF polymers within the range of characteristics described in the above table and elsewhere herein, including using methods to enhance polymer crystallization. Such processing conditions include methods for increasing crystallization described herein and such methods disclosed in the examples herein.

[0201] Examples of chain extension treatments for polyesters are provided in the article "Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process," Firas Awaja, Fugen Daver, Edward Kosior, August 16, 2004, available at https: / / doi.org / 10.1002 / pen.20155The chain extender is obtained by using a polymerizable polymer, which is incorporated herein by reference. As explained in US1009 / 0264545, which is incorporated herein by reference, a chain extender is generally a compound that is at least difunctional relative to a reactive group, which can react with an end group or functional group in a polyester to extend the length of the polymer chain. In some cases, as disclosed herein, such treatments can advantageously increase the average molecular weight of the polyester to improve its melt strength and / or other important properties. The degree of chain extension achieved is at least partially related to the structure and functionality of the compound used. A variety of compounds can be used as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (hereinafter referred to as PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing multifunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposites such as finely dispersed nanoclays can optionally be used to control viscosity. Commercial 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 over a wide range, and in a preferred embodiment, ranges from about 0.1 wt % to about 5 wt %, or preferably from about 0.1 wt % to about 1.5 wt %. Examples of chain extenders are also described in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.

[0202] Examples of SSP processing methods for poly(ethylene furanoate) are provided in the article "Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase", Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias and Dimitrios N. Bikiaris, which is incorporated herein by reference.

[0203] PEF thermoplastic polymers that are particularly useful for preparing the foams (including Foams 1-4 and FC1-FC11) and foam articles (including Foam Articles 1-4) of the present invention are identified in the following Thermoplastic Polymer Table (Table 2A), wherein all numerical values ​​in the table are to be understood as being preceded by the word "about".

[0204] Table 2A - Thermoplastic Polymers

[0205]

[0206]

[0207] PEF thermoplastic polymers that are particularly useful for preparing (including Foams 1-4 and FC1-FC11) and foam articles (including Foam Articles 1-4) also include those materials identified in the following Thermoplastic Polymer Table (Table 2B), wherein all numerical values ​​in the table are to be understood as being preceded by the word "about".

[0208] Table 2B - Thermoplastic Polymers

[0209]

[0210]

[0211] PEF thermoplastic polymers that are particularly useful for preparing the present invention (including Foams 1-4 and FC1-FC11) and foam articles (including Foam Articles 1-4) also include those materials identified in the following Thermoplastic Polymer Table (Table 2C), wherein all numerical values ​​in the table are understood to be preceded by the word "about".

[0212] Table 2C - Thermoplastic Polymers

[0213]

[0214]

[0215] For the purpose of defining the terms used herein, it should be noted that the thermoplastic polymer shown in the first column of each row in the above TPP table will be mentioned in various positions of this article, and each of these numbers is mentioned as a thermoplastic polymer defined in the corresponding column of the row. A group of TPPs defined in the above table is mentioned by mentioning the TPP number, which refers to each TPP individually and independently mentioned, including each TPP with the number shown, including any such numbering with a suffix. Therefore, for example, mentioning TPP1 is to individually and independently mention TPP1A, TPP1B, TPP1C, TPP1D and TPP1E. Mentioning TPP1-TPP2 is to individually and independently mention TPP1A, TPP1B, TPP1C, TPP1D, TTP1E, TPP2A, TPP2B, TPP2C, TPP2D and TPP1E. This usage convention is also used for the following foamable composition table and foam table.

[0216] Foaming agent

[0217] As explained in detail herein, the present invention includes, but is not limited to, Applicants' discovery that a group of selected blowing agents can provide foamable PEF foamable compositions and PEF foams and foam articles (including Foam Articles 1-4) having an unattainable and surprising combination of physical properties, including low density and good mechanical strength properties.

[0218] The blowing agent used according to the present invention preferably comprises one or more hydrohaloolefins having three or four carbon atoms.For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1A.

[0219] The blowing agent used according to the present invention preferably consists essentially of one or more hydrohaloolefins having three or four carbon atoms.For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1B.

[0220] The blowing agent used according to the present invention preferably consists essentially of one or more hydrohaloolefins having three or four carbon atoms.For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1C.

[0221] The blowing agent used according to the present invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (hereinafter referred to as blowing agent 2A for convenience); or comprises one or more of trans-1234ze, 1336mzz, trans-1233zd and cis-1224yd (hereinafter referred to as blowing agent 3A for convenience); or comprises one or more of trans-1234ze, trans-1336mzz, trans-1233zd and cis-1224yd (hereinafter referred to as blowing agent 4A for convenience); or comprises trans-1234ze and trans-1336mzz. One or more of 1336mzz (hereinafter referred to as blowing agent 5A for convenience); or trans-1234ze (hereinafter referred to as blowing agent 6A for convenience); or trans-1336mzz (hereinafter referred to as blowing agent 7A for convenience); or cis-1336mzz (hereinafter referred to as blowing agent 8A for convenience); or 1234yf (hereinafter referred to as blowing agent 9A for convenience); or 1224yd (hereinafter referred to as blowing agent 10A for convenience); or trans-1233zd (hereinafter referred to as blowing agent 11A for convenience).

[0222] The blowing agent used according to the present invention is preferably composed essentially of one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (hereinafter referred to as blowing agent 2B for convenience); or essentially of one or more of trans-1234ze, 1336mzz, trans-1233zd and cis-1224yd (hereinafter referred to as blowing agent 3B for convenience); or 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 essentially of trans-1234ze and trans-1336mzz. or consists essentially of one or more 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).

[0223] The blowing agent used according to the present invention is preferably composed of one or more of 1234ze, 1234yf, 1336mzz, 1233zd and 1224ydf (hereinafter referred to as blowing agent 2B for convenience); or composed of one or more of trans-1234ze, 1336mzz, trans-1233zd and cis-1224yd (hereinafter referred to as blowing agent 3B for convenience); or composed of one or more of trans-1234ze, trans-1336mzz, trans-1233zd and cis-1224yd (hereinafter referred to as blowing agent 4B for convenience); or composed of one or more of trans-1234ze, trans-1336mzz, trans-1233zd and cis-1224yd (hereinafter referred to as blowing agent 4B for convenience); or cis-1336mzz (hereinafter referred to as blowing agent 8B for convenience); or 1234yf (hereinafter referred to as blowing agent 9B for convenience); or 1224yd (hereinafter referred to as blowing agent 10B for convenience); or trans-1233zd (hereinafter referred to as blowing agent 11B for convenience).

[0224] Therefore, it is contemplated that the blowing agent of the present invention (including each of blowing agents 1 to 11) may include, in addition to each of the above-mentioned blowing agents, a co-blowing agent, which is included in one or more optional potential co-blowing agents as described below. In a preferred embodiment, the foamable composition, foam and foaming method of the present invention include a blowing agent as described herein, wherein the blowing agent (including the compound or compound group specifically identified in each of blowing agents 1 to 11) is 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 blowing agent components.

[0225] It is contemplated and understood that the blowing agents of the present invention (including each of blowing agents 1 to 11) may include one or more co-blowing agents not included in the selections shown, provided that the amount of such co-blowing agents does not interfere with or eliminate the ability to obtain a relatively low density foam as described herein (including each of foams 1 to 4), and preferably also does not interfere with or eliminate the ability to obtain a foam having mechanical strength properties as described herein. Thus, given the teachings contained herein, it is contemplated that one skilled in the art will be able to select, for example, one or more of the following potential co-blowing agents for a particular application without undue experimentation: one or more saturated hydrocarbons or hydrofluorocarbons (HFCs) known in the art, particularly C4-C6 hydrocarbons or C1-C4 HFCs. Examples of such HFC auxiliary 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 regard to hydrocarbons, in certain preferred embodiments, the blowing agent composition of the present invention may also include, for example, isopentane, n-pentane and / or cyclopentane as well as butane and / or isobutane. Other materials may also be included, such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, such as dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (such as ethanol and / or propanol and / or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl ether and diethyl ether), diethers (such as dimethoxymethane and diethoxymethane)) and methyl formate, organic acids (such as but not limited to formic acid), including any combination of these, but such components are not necessarily preferred in many embodiments due to negative environmental impact.

[0226] Foam and foaming methods

[0227] The foam of the present invention (including each of foams 1 to 4) or foams made from the PEF polymer of the present invention (including 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. In general, the foamable composition of the present invention can be formed by combining the PEF polymer of the present invention (including each of thermoplastic polymers TPP1A to TPP22E) with the blowing agent of the present invention (including each of blowing agents 1 to 11).

[0228] Foamable compositions encompassed within the present invention and providing particular advantages associated with forming the foams of the present invention are described in the following foamable composition tables (Table 3A and Table 3B), wherein all numerical values ​​in the tables are to be understood as being preceded by the word "about", and wherein the following terms used in the tables have the following meanings:

[0229] CBAG1 refers to a co-blowing agent selected from the group consisting of 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf and a combination of two or more of these.

[0230] CBAG2 refers to a co-blowing agent selected from the group consisting of water, CO2, C1-C6 hydrocarbons (HC) HCFCs, C1-C5 HFCs, 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.

[0231] CCBAG3 refers to 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 any combination of two or more of these.

[0232] NR means not required.

[0233] Table 3A - Table of Foamable Compositions

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245] Table 3 BA-Foamable Composition Table

[0246]

[0247]

[0248]

[0249]

[0250]

[0251]

[0252]

[0253]

[0254] Foam formation method

[0255] In view of the disclosure contained herein, it is contemplated that the foams of the present invention (including each of Foams 1 to 4) may be formed using any one or more of a variety of known techniques for forming thermoplastic foams, and all such techniques and all foams and all foam articles formed thereby (including Foam Articles 1 to 3) are within the broad scope of the present invention. For clarity, it should be noted that the definitions of foams in the following table all begin with the letter F only, in contrast to the foams defined in the paragraphs in the Summary of the Invention above, which begin with the capitalized word Foamable Composition.

[0256] Typically, the forming step involves first introducing a blowing agent of the present invention including each of blowing agents 1 to 31 into a PEF polymer of the present invention including each of TPP1 to TPP22 to form a foamable PEF composition comprising PEF and blowing agent. One example of a preferred method of forming a foamable PEF composition of the present invention is to plasticize the PEF, preferably including heating the PEF to its melting temperature, preferably above its melting temperature, and then exposing the PEF melt to the blowing agent under conditions effective to incorporate the desired amount of blowing agent (preferably by dissolution) into the polymer melt.

[0257] In a preferred embodiment, the foaming method of the present invention comprises providing a foamable composition of the present invention, which comprises each of FC1 to FC13, and foaming the provided foamable composition. In a preferred embodiment, the foaming method of the present invention comprises providing a foamable composition of the present invention (including each of FC1 to FC13), and extruding the provided foamable composition to form a foam of the present invention, and then forming a foam article of the present invention (including each of foam articles 1 to 4).

[0258] The foaming methods of the present invention may include batch, semi-batch, continuous methods, and combinations of two or more of these methods. Batch methods generally involve preparing at least a portion of a foamable polymer composition in a storable state, including each of FC1 to FC13, and then using the portion of the foamable polymer composition to prepare foam at a future point in time. Semi-batch methods involve preparing at least a portion of a 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, all in a single process. For example, U.S. Pat. No. 4,323,528, incorporated herein by reference, discloses a method for preparing thermoplastic foam by a cumulative extrusion process. Thus, the present invention includes a method comprising: 1) mixing a PEF thermoplastic polymer including each of TPP1 to TPP22 with a blowing agent of the present invention including each of blowing agents 1 to 31 under conditions that 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 that does not allow the foamable composition to foam, wherein the holding zone preferably includes a die and an openable door, the die defining an orifice leading to a low pressure zone, including F The foamable polymer composition of each of C1 to FC13 is foamed under the low pressure, and the openable door closes the die orifice; 3) periodically opening the door and substantially simultaneously applying mechanical pressure to the foamable polymer composition including each of FC1 to FC13 through a movable pressure head to discharge it from the holding zone through the die orifice into the low pressure zone, and 4) allowing the discharged foamable polymer composition to expand under the action of a blowing agent to form foams, including each of foams 1 to 4 and each of foams F1 to F8.

[0259] The present invention may also use a continuous process to form foams. For example, such a continuous process involves forming a foamable PEF composition, including each of FC1 to FC13, and then expanding the foamable PEF composition without substantial interruption. For example, a foamable PEF composition including each of FC1 to FC13 may be prepared in an extruder by heating a selected PEF polymer resin (including each of TPP1 to TPP22) to form a PEF melt, incorporating a blowing agent of the present invention (including each of blowing agents 1 to 11) into the PEF melt, preferably by dissolving the blowing agent into the PEF melt under an initial pressure to form a foamable PEF composition including a substantially uniform combination of PEF and blowing agent (including each of FC1 to FC13), then extruding the foamable PEF composition through a die head into a zone at a selected foaming pressure, and allowing the foamable PEF composition to expand into a foam under the influence of the blowing agent, including each of Foams 1 to 4 and each of Foams F1 to F8 described below. Optionally, the foamable PEF composition comprising a PEF polymer (including each of FC1 to FC13) and an incorporated blowing agent (including each of blowing agents 1 to 11) can be cooled prior to extruding the composition through a die to enhance certain desirable properties of the resulting foam (including each of foams 1 to 6 and each of foams F1 to F8).

[0260] This method can be used, for example, Figure 8In particular, the extrusion apparatus may include a raw material feed hopper 10 for containing the PEF polymer 15 of the present invention (including each of TPP1 to TPP22) and one or more optional components (which may be added in the hopper with the PEF or optionally added elsewhere in the process, depending on the specific needs of the user). Feed 15 other than the blowing agent may be loaded into the hopper and delivered to the screw extruder 10. The extruder 20 may include thermocouples (not shown) located at three points along its length and a pressure sensor (not shown) located at the discharge end 20A of the extruder. The mixer section 30 may be located at the discharge end 20A of the extruder for receiving the blowing agent component of the present invention (including each of blowing agents 1 to 31) via one or more metering pumps 40A and 40B, and mixing those blowing agents into the PEF melt in the mixer section. A sensor (not shown) may be included for monitoring the temperature and pressure of the mixer section 30. The mixer section 30 can then discharge the foamable composition melt of the present invention (including each of FC1 to FC13) into a pair of melt coolers 50 oriented in series, wherein a temperature sensor (not shown) is located in each cooler to monitor the melt temperature. The melt is then extruded through a die 60, which also has a temperature sensor and a pressure sensor (not shown) for monitoring the temperature and pressure at the die. The die pressure and temperature can vary according to the needs of each specific extrusion application that produces the foam 70 of the present invention (including each of the foams 1 to 4 described below and each of the foams F1 to F8). The foam can then be transported away from the extrusion equipment by a conveyor belt 80.

[0261] The foamable polymer composition of the present invention (including each of FC1 to FC13) may optionally contain additional additives such as nucleating agents, cell control agents, glass fibers and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR attenuators and thermal insulation additives. Nucleating agents include materials such as talc, calcium carbonate, sodium benzoate and chemical foaming agents such as azodicarbonamide or sodium bicarbonate and citric acid. IR attenuators and thermal insulation additives may include carbon black, graphite, silica, metal flakes or powders, etc. Flame retardants may include brominated materials such as hexabromocyclodecane and polybrominated diphenyl ethers. Each of the above-mentioned additional optional additives can be introduced into the foam at different times and different locations in the process according to known techniques, and all such additives and addition methods are within the broad scope of the present invention.

[0262] Foam

[0263] In a preferred embodiment, the foam of the present invention is formed in a commercial extrusion apparatus and has the properties shown in Table 4 below, wherein the values ​​are measured as described in the Examples herein:

[0264] Table 4

[0265] Wide range Low density range High density range Foam properties Foam density, g / cc (ISO 845) 0.04-.25 .06-0.115 0.115-0.25 Compression strength (perpendicular to the plane) (ISO 844), Mpa 0.5-15 0.5-5 1-14 Tensile strength perpendicular to the plane (ASTM C297), MPa 1.0-6 1.-3 2-6 Tensile strength + compression strength, Mpa 1.5-21 1.5-8 3-20 Average pore size (SEM) 20-300 20-100 30-300

[0266] Foams included within the present invention and providing particular advantages are described in Table 5 below, and all numerical values ​​therein are to be understood as being preceded by the word "about," and wherein the designation NR means "not required."

[0267] Table 5 - Foam Table

[0268]

[0269]

[0270]

[0271]

[0272]

[0273]

[0274]

[0275]

[0276]

[0277]

[0278]

[0279]

[0280]

[0281]

[0282]

[0283]

[0284]

[0285]

[0286]

[0287]

[0288]

[0289]

[0290]

[0291]

[0292]

[0293]

[0294]

[0295]

[0296]

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310]

[0311]

[0312]

[0313]

[0314]

[0315]

[0316]

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329] The foams of the present invention have a wide range of uses. The foams of the present invention (including each of foams 1 to 4 and foams F1 to F8) have unexpected advantages in applications requiring low density and / or good compression and / or tension and / or shear properties, and / or long-term stability, and / or sustainable sources, and / or made from recycled materials and recyclable. In particular, the foams of the present invention (including each of foams 1 to 6 and each of foams F1 to F8) have unexpected advantages in the following applications: wind energy applications (wind turbine blades (shear webs, shells, cores and roots)); marine applications (hulls, decks, superstructures, bulkheads, chords and interiors); industrial low-weight applications; automotive and transportation applications (interiors and exteriors of cars, trucks, trains, airplanes and spacecraft).

[0330] The PEF:PET copolymers may be formed by any means known to those skilled in the art, including but not limited to those procedures described in the Examples herein.

[0331] The foams of the present invention (including each of Foams 1 to 4) are made of PEF homopolymer, PEF copolymer, PEF:PET copolymer or combinations / mixtures of these.

[0332] In a preferred embodiment, the foam (including each of Foams 1 to 4) may be formed from a PEF homopolymer, wherein the polymer has at least 99.5 wt%, or at least 99.9 wt%, of ethylene furanoate moieties.

[0333] It is contemplated that the foams of the present invention, including each of Foams 1 to 3, can be formed from PEF copolymers in preferred embodiments, wherein the polymer, including PEF copolymers having from about 0.5 wt % to about 99 wt % of ethylene furanate moieties. The present invention includes foams, including each of Foams 1 to 3, wherein the thermoplastic polymer consists essentially of the components described in the following table:

[0334]

[0335]

[0336]

[0337]

[0338] The foams of the present invention, including each of Foams 1 to 3, may include closed cell walls including each of the thermoplastic polymers of the present invention, including each of TMP1-TMP12 described in the table above.

[0339] For those embodiments of the invention involving PEF copolymers, it is expected that those skilled in the art, given the teachings contained herein, will be able to select the type of amount of copolymer material to be used within each of the ranges described herein to achieve the desired reinforcement / modification of the polymer without undue experimentation.

[0340] It is contemplated that the TMPs of the present invention may be formed to have a variety of physical properties, including the following ranges of polymer characteristics, measured as described in the Examples herein:

[0341] Wide range Middle range Narrow range Polymer properties <![CDATA[Glass transition temperature, T g , °C]]> 80-100 85-95 90-95 <![CDATA[Melting temperature, T m , °C]]> 190-250 200-240 210-230 <![CDATA[Decomposition temperature, T d , °C]]> 300-420 320-400 330-370 Crystallinity, % 25-75 30-60 40-50

[0342] In general, given the teachings contained herein, it is expected that one skilled in the art will be able to formulate PEF polymers within the above-described range of properties without undue experimentation. However, in preferred embodiments, PEF polymers according to the present invention (including PEF:PET copolymers of the present invention) having these properties are achieved using one or more of the above-described synthesis methods, in combination with various known complementary processing techniques (including by treatment with a chain extender such as PMDA, and / or SSP processing).

[0343] Examples of chain extension treatments for polyesters are provided in the article "Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process," Firas Awaja, Fugen Daver, Edward Kosior, August 16, 2004, available at https: / / doi.org / 10.1002 / pen.20155 The chain extender is obtained by using a polymerizable polymer, which is incorporated herein by reference. As explained in US1009 / 0264545, which is incorporated herein by reference, a chain extender is generally a compound that is at least difunctional relative to a reactive group, which can react with an end group or functional group in a polyester to extend the length of the polymer chain. In some cases, as disclosed herein, such treatments can advantageously increase the average molecular weight of the polyester to improve its melt strength and / or other important properties. The degree of chain extension achieved is at least partially related to the structure and functionality of the compound used. A variety of compounds can be used as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing multifunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposites such as finely dispersed nanoclays can optionally be used to control viscosity. Commercial 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 over a wide range, and in a preferred embodiment, ranges from about 0.1 wt % to about 5 wt %, or preferably from about 0.1 wt % to about 1.5 wt %. Examples of chain extenders are also described in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.

[0344] Examples of SSP processing methods for poly(ethylene furanoate) are provided in the article "Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase", Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias and Dimitrios N. Bikiaris, which is incorporated herein by reference.

[0345] Foaming agent

[0346] As explained in detail herein, the present invention relates to Applicants' discovery that a group of selected blowing agents can provide each of foamable PEF compositions (including foamable composition 1) and PEF foams (including foams 1 to 3) having a surprising combination of difficult to achieve physical properties, including low density and good mechanical strength properties.

[0347] Foam and foaming methods

[0348] The foams of the present invention are thermoplastic foams, and in view of the disclosure contained herein, it is generally contemplated that any one or more of a variety of known techniques for forming thermoplastic foams may be used, and that all such techniques and all foams formed thereby may be within the broad scope of the present invention.

[0349] Foam products

[0350] The foams and foam products of the present invention have a wide range of uses. The foam products of the present invention (including each of foam products 1 to 3) have unexpected advantages, particularly in applications requiring low density and / or good compression and / or tension and / or shear properties, and / or long-term stability, and / or sustainable sources and / or made from recycled materials and recyclable. In particular, the foam products of the present invention (including each of foam products 1 to 3) have unexpected advantages in the following aspects: wind energy applications (wind turbine blades (shear webs, shells, cores and nacelles); marine applications (hulls, decks, superstructures, bulkheads, chords and interiors); industrial low-weight applications; automotive and transportation applications (interiors and exteriors of cars, trucks, trains, airplanes and spacecraft); fixed building structures; and sports equipment.

[0351] As described above, the foam articles of the present invention (including each of foam articles 1 to 3) generally comprise a foam having a facing on at least a portion of its surface. As used herein, reference to a numbered foam article or group of numbered foam articles defined herein refers to each of such numbered foam articles, including each foam article having a number within the group, including any suffixed numbers. For example, reference to foam article 3 includes reference to each of foam articles 3A, 3B, 3C, and 3D.

[0352] Within the scope of the present invention, the size and shape of the foam used in the foam article of the present invention can vary over a wide range depending on the use of the article, and all such sizes and shapes are within the scope of the present invention. In many applications, the foam article will be in a three-dimensional form, where the length and / or width are much greater in size than the thickness. In other applications, the form of the article can be characterized as a block, a plate, a panel, etc., or a specific shape such as an I-beam, a U-shape, or other specific shapes.

[0353] For the purpose of illustration and not limitation, Figure 4 A form is shown in which the foam article is in the general shape of a sheet or panel having a facing on each side thereof. In the embodiment shown, the foam article according to the invention comprises a core 1 of a PEF foam of the invention, the core comprising each of TMPs 1 to 12 as defined below, and the foam article comprises at least one reinforcing facing 2 and at least one connecting and / or integrating layer 3. In view of the teachings contained herein, it will be understood by those skilled in the art that the connecting / integrating layer may comprise, for example, an adhesive layer, or may be formed by integrating the core material and the facing material without the use of a separate adhesive, for example by melting the surfaces of the two materials together to form a connecting / integrating area and the connecting / integrating layer appears. The facing may be any material suitable for the intended use, as described above, but in many applications, the facing 2 is a sheet or film of a fibrous material as described above. The fibers of the preferred facing 2 may, for example, be in the form of a woven or non-woven mat (or a mat comprising a combination of woven and non-woven fibers), including a curled mat that may be woven or non-woven, and the fibers may be oriented or non-oriented (i.e., random). In embodiments where the fibers of the facing are oriented, the orientation may include unidirectional orientation, bidirectional orientation, biaxial orientation, triaxial orientation, quadaxial orientation, and combinations of any of these.

[0354] The connecting / integrating film, layer or region 3 can be any material and any thickness required to attach or integrate the facing 3 to the core 1. In addition, although the film or layer 3 is shown as being generally located between the facing 2 and the core 1, it should be understood and recognized by those skilled in the art that the connecting layer or film generally extends into each of the foam core 1 and the facing 2. In certain preferred embodiments, the film or layer 3 may include an adhesive material, such as an epoxy adhesive, which bonds the core 1 and the facing sheet 2 together. Other adhesive resins that can be used to bond the facing to the foam include polyurethanes, vinyl esters, polyesters, cyanate esters, polyurethane acrylates, bismaleimides, polyimides, silicones, phenolic resins, polypropylene, caprolactams, and combinations of any two or more of these. Typically, the processing to form the foam article of the present invention includes steps to 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.

[0355] In a preferred embodiment, the facing 2 comprises a plurality of mutually bonded sheets or mats, which may be the same or different and are bonded to each other by suitable means, including mutually bonded layers of adhesive or resin or mutually bonded areas formed by material integration (e.g., melting together to form an integrated area). In such embodiments, it is contemplated that the number of mutually bonded sheets making up the facing 2 may vary over a wide range, and in a preferred embodiment, the facing comprises from 2 to 10 mutually bonded sheets, and even more preferably from about 3 to about 5 mutually bonded sheets.

[0356] While it is understood that the dimensions of the foam articles of the present invention (including each of the foam articles 1 to 3) can vary over a wide range, in preferred embodiments involving uses associated with wind turbine applications, the panel can vary from about 0.1 mm to about 3 mm, or from about 0.4 mm to about 1.5 mm. In addition, it is generally understood that the relative thickness of the foam compared to the panel can vary over a wide range depending on the specific application, and those skilled in the art will be able to make appropriate selections based on the teachings contained herein, and generally the panel thickness will be less than the thickness of the foam.

[0357] Preferred materials for forming the foam articles of the present invention, including each of Foam Articles 1-3, are described in further detail below.

[0358] Finishes

[0359] The foam articles of the present invention include facings that may have a wide variety of sizes, the size used will depend on the specific needs of the application in which the foam article will be used, and articles of all such sizes are within the scope of the present invention.

[0360] The materials forming the facing material may also vary over a wide range depending on the specific use of the foam article, and all such materials are also within the scope of the present invention. For example, the facing used in the foam articles of the present invention (including each of the foam articles 1 to 3) comprises one or more fiber sheets or mats, wherein the fiber portion may be formed from a variety of materials, including, for example, glass fibers (preferably impregnated with resins and / or polymers), other natural fibers (such as cellulose and other plant-derived materials), mineral fibers (such as quartz), metal fibers or films, carbon fibers (preferably impregnated or reinforced with one or more polymers (including thermoplastic polymers and / or thermosetting polymers)), synthetic fibers such as polyesters (including fibers comprising furan-based polyesters, as disclosed, for example, in US 2015 / 0111450, which is incorporated herein by reference), polyethylene, aramids, Kevlar, and any and all combinations of these.

[0361] Specific Applications

[0362] The foam products of the present invention have a wide range of uses. The foam products of the present invention (including each of the foam products 1 to 3) have unexpected advantages in applications requiring low density and / or good compression and / or tension and / or shear properties, and / or long-term stability, and / or sustainable sources, and / or made of recycled materials and recyclable. In particular, the foam products of the present invention (including each of the foam products 1 to 3) have unexpected advantages in the following aspects: such as, for example, fluid energy transfer components in wind and water energy transfer applications (for example, wind turbine blades (shear webs, shells, cores and nacelles) for transferring wind energy from fixed or mobile devices located in the air, and vortex, tide, ocean current oscillation hydrofoils and kites that recover water kinetic energy from fixed or mobile devices located in the water); marine applications (hulls, decks, superstructures, bulkheads, chords and interiors); industrial low-weight applications; automotive and transportation applications (interiors and exteriors of cars, trucks, trains, airplanes and spacecraft); and packaging applications.

[0363] Special References Figure 2 and Figure 3A , Figure 3B and Figure 3CThe foam articles of the present invention, including each of foam articles 1-3, may be used in the rotor blade 10 at any and all locations along the length of the blade from the blade root 30 to the blade tip 32 disposed opposite the blade root 30, and at any location along the main body shell, including any location on the pressure side 34, on the suction side 36, and at all locations extending between the leading edge 26 to the trailing edge 28 of the rotor blade 10. Further, the foam articles of the present invention, including each of foam articles 1-3, may be used in all or a portion of longitudinally extending structural components configured to provide increased stiffness, bending resistance, and / or strength to the rotor blade 10, such as longitudinally extending spar caps 20, 22 configured to engage against opposing inner surfaces 35, 37 of the pressure side 34 and suction side 36 of the rotor blade 10, and in one or more shear webs 24 disposed between the spar caps 20, 22 to form a beam-like configuration. The spar caps 20, 22 may generally be designed to resist bending stresses during operation of the wind turbine 10 and to minimize blade tip deflection and / or other loads acting on the rotor blade 10 in a generally spanwise direction (a direction parallel to the span 23 of the rotor blade 16); however, it should be understood that in other applications, the spar caps may also be oriented at any angle transverse to the spanwise axis (including at an angle of approximately 90 degrees relative to the spanwise axis). Similarly, the spar caps 20, 22 may also be designed to resist spanwise compression or tension occurring during operation of the wind turbine 6. Due to the unexpected combination of light weight and high strength of the foams and foam articles of the present invention (including each of the foam articles 1 to 3), the root of the blade and the spars and caps used in the rotor blades may be advantageously used with such foams and foam articles.

[0364] The following foam use table includes identification of some of the preferred uses of some of the preferred products of the present invention, wherein the column heading "Foam Product Number" refers to the foam product as identified above, and the column heading "Specific Foam" refers to the foam as identified above.

[0365]

[0366]

[0367]

[0368]

[0369]

[0370]

[0371]

[0372]

[0373]

[0374] Example

[0375] Without limiting the full scope of the invention, the applicant has carried out a series of experiments using intermittent method laboratory equipment to demonstrate the practicality of the PEF homopolymer of the present invention and the copolymer based on PEF, and the performance of the foam of the present invention made according to the present invention is compared with the foam made of PET. It will be appreciated by those skilled in the art that scaling up such laboratory tests to commercial-grade extrusion will generally result in a significant increase in many of the strength values ​​reported herein, due to inherent reasons in commercial processes and tests. As a non-limiting example of these amplification factors, commercial extruded foams are generally stronger in the extrusion direction, because of the impact of being forced to pass through the extrusion die head under pressure, the common use of the roll stack, and the strength test performed in the extrusion direction. Extruded commercial foams are also generally formed by sewing the parts of the foam together, and the presence of these seams tends to enhance the overall strength of the foam. Due to these and potential other factors, the strength results reported in these embodiments are generally lower than the results expected by those skilled in the art when performing the foaming method on a commercial extruder. However, it will be appreciated by those skilled in the art that the results reported herein are generally reflected in the results on the basis of the comparison of the foam and the foam expected when the process is scaled up to commercial extrusion.

[0376] The tests used herein involve the synthesis of a series of reference PET polymers covering a range 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. Applicants have 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.

[0377] Polymer formation

[0378] A series of polymers were synthesized generally according to the procedures described in Synthesis Examples 1 to 3 below. The polymers produced according to the present invention included homopolymers of PEF and copolymers of PEF and PET at various molar ratios. Homopolymers of PET were also produced for comparative purposes.

[0379] A variety of synthesis parameters were used for each type of polymer to produce a range of polymers having a variety of polymer physical properties, including glass transition temperature (Tg), melting temperature (Tm), decomposition temperature (Td), crystallinity (Cr) and molecular weight. These polymers were then used to produce PEF foams according to the present invention and PET foams for comparative purposes. The polymers thus produced are identified in the following table PFEx.

[0380] Table PFEx

[0381]

[0382] *- For PEF:PET foams, the molecular weight reported is that of the fraction present in the higher molar concentration.

[0383] Foam formation

[0384] The 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 include foam densities that, for convenience, are divided into the following ranges: (1) in the low density range of 0.060 g / cc up to 0.115 g / cc; (2) in the medium density range of greater than 0.115 g / cc up to 0.170 g / cc and (3) in the high density region of greater than 0.170 g / cc up to 0.250 g / cc. For a given range of comparable polymer properties, a consistent set of processing conditions was used. The details of each of these sets of experimental results are explained in detail in the following examples and tables.

[0385] For each polymer, a unique and narrow range of melting temperature and pre-foaming temperature are indicated for the foaming experiment. The foam thus produced in the entire example of the present application is tested using a method generally corresponding to ASTM D71 to determine the density of the foam, except that hexane is used instead of water for displacement. For ease of comparison, the density of the foam produced in these embodiments is compared. In addition, each of the foams produced in these embodiments is tested to determine tensile strength (hereinafter referred to as TS) and compressive strength (hereinafter referred to as CS) and the sum of TS and CS (hereinafter referred to as TS+CS). Tensile strength and compressive strength measurements are based on the guidelines provided in ASTM C297 and ISO 844, respectively, and are measured in the decompression direction in each case.

[0386] Using the polymers described in the above table PFEx, a series of foams were prepared using a foaming process that generally includes placing approximately 1 gram of polymer (as shown in the following table FFEx) in a glass container, which is then loaded into a 60cc volume autoclave and dried in a vacuum at an elevated temperature ranging from 130°C to 150°C for six (6) hours. The dried polymer is then cooled to room temperature. For each case in the following table FFEx, the blowing agent consists of 1234ze (E). The blowing agent is pumped into the autoclave containing the dried polymer, and the autoclave is then heated to bring the polymer to a molten state. The PET / blowing agent mixture is kept in a molten state at the molten state pressure and temperature for about a period of time (hereinafter referred to as the "melting time", MTime), as shown in the table (60 minutes or 15 minutes). The temperature (MTemp) and pressure (MP) of the melt / blowing agent are then reduced to a pre-foaming temperature (PFT) and pre-foaming pressure (PFP) over a period of about 5 minutes to 15 minutes, as shown in the table FFEx. The autoclave is then maintained at about this temperature and pressure for about 30 minutes to ensure that the amount of blowing agent introduced into the melt under such conditions reaches equilibrium. The temperature and pressure in the autoclave are then rapidly reduced (the pressure is reduced in about 10 seconds and the temperature is reduced in about 1 minute to 10 minutes using cold water) to ambient conditions (about 22°C and 1 atmosphere), and foaming occurs. The conditions used, including the amount of blowing agent and the melt temperature and pressure, are determined after several trials based on the ability to form acceptable foams with density values ​​in the range of about 0.06 grams per cubic centimeter (g / cc) to 0.115 g / cc or in the range of greater than 0.115 g / cc to 0.250 g / cc, for convenience, acceptable foams with density values ​​in the range of about 0.06 g / cc to 0.115 g / cc are referred to as low density foams in the following table, and for convenience, acceptable foams with density values ​​in the range of greater than 0.115 g / cc to 0.250 g / cc are referred to as high density foams in the following table.

[0387]

[0388]

[0389] Representative methods of forming foams are reported in Foam Formation Examples 1 to 3 below, all of which use 1234ze(E) as the sole blowing agent. In addition, Foam Formation Example 4 reports a series of foams made from PEF:PET copolymers and blowing agents 1233zd and 1336mzz in addition to the preferred blowing agent 1234ze(E). These foams were prepared using the same general procedures disclosed in Foam Formation Examples 1 to 3. While it was found that foams made using 1234ze(E) unexpectedly outperformed foams foamed with other blowing agents other than 1234zd(E), acceptable foams were made and had significant utility when the blowing agent comprised, consisted essentially of, or consisted of 1233zd(E) or 1336mzz(Z), as revealed by the data reported in Foam Formation Example 3. Applicants surprisingly found that the foams of the present invention had excellent strength characteristics, particularly as measured by the combined tensile and compressive strength values, which combination also reflected excellent shear strength properties. In particular, the following graphs show the low density region (see Figure 5 ) and high-density areas (see Figure 6 ) are trend line data for the combined values ​​of tensile strength and compressive strength as a function of foam density in each of the ).

[0390] like Figure 5 As shown in , the foams of the present invention in the low density region made from both the PEF homopolymer of the present invention (solid line) and the PEF:PETE copolymer (large dashed line) produce significantly superior strength properties as a function of density over most of the low density range, on average, compared to foams formed from PET homopolymers. For example, at about the midpoint density in the low density range (i.e., 0.09 g / cc), the PEF homopolymer of the present invention and the PEF:PET copolymer according to this embodiment have, on average, a TS plus 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., TS plus CS of 2). The substantial advantages of the foams of the present invention made from the PEF homopolymer of the present invention and the PEF:PET copolymer of the present invention, compared to foams formed from PET homopolymers, can also be achieved by using the foams of the present invention to achieve the same strength as PET foams but with significantly lower densities. As a specific example, if PET with a density of 0.1 is used in a given application to achieve a TS plus CS strength of 2.2, then Figure 5The average values ​​shown in replace the PET foam with the present PEF foam, which also has a TS plus CS strength of 2.2 MPa, but has a much lower foam density, i.e., any density down to a density of 0.065 g / cc. This represents a weight reduction of up to 35% for this given application. These are very beneficial and unexpected results, as shown in the examples below for several specific applications, including wind turbine blades.

[0391] like Figure 6 As shown, the inventive foams in the high density regions made from both the inventive PEF homopolymer (solid line) and the PEF:PETE copolymer (large dashed line) also produce superior strength properties, on average, as a function of density over substantially the entire mid-density range, compared to foams formed from PET homopolymers. For example, at about the midpoint density in the high density range (i.e., 0.185 g / cc), the inventive PEF homopolymer according to this embodiment has, on average, a TS plus 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., TS plus CS of 3.2). The substantial advantages of the inventive foams made from the inventive PEF homopolymer and PEF:PET copolymer compared to foams formed from PET homopolymers can also be achieved by using the inventive foams to achieve the same strength as PET foams but with significantly lower densities. As a specific example, if PET having a density of 0.25 (i.e., in the high density regions) is used in a given application to achieve a TS plus CS strength of about 3.8, then Figure 6 The average values ​​shown in replace the PET foam with the PEF:PET foam of the present invention, which has a TS plus CS strength of 3.8 MPa, but has a much lower foam density (i.e., 0.135 g / cc). This represents a weight reduction of about 46% for this given application. Moreover, while replacing PEF:PET in the high density range provides such significant advantages, it is often also possible to use the PEF homopolymer and / or PEF:PET copolymer of the present invention from the low density range to replace the PET polymer from the high density range and provide even greater advantages. These are very beneficial and unexpected results, as shown in the examples below for several specific applications, including wind turbine blades.

[0392] As described in the above text specification (including the examples), the foams of the present invention provide important and unexpected advantages relevant to many uses. These advantages include the ability to achieve: (1) excellent strength for a given density; (2) reduced density and therefore weight advantages for foams of the same density as previously used PET foams; and (3) a combination of excellent strength and reduced density. Figure 13, the following table provides specific examples of such advantages of replacing PET foam of a particular density and / or strength (measured by TS plus CS) with the foam of the present invention:

[0393] PEF substitution table - strength advantage at constant density

[0394]

[0395] PEF substitution table - minimum density advantage at constant strength

[0396]

[0397] *- Lowest density within the specified range to achieve PET strength

[0398] PEF:PET substitution table - strength advantage at constant density

[0399]

[0400] PEF:PET substitution chart - density advantage at constant strength

[0401]

[0402] *- Lowest density within the specified range to achieve PET strength

[0403] Use Example

[0404] With this article Figure 1 A wind turbine generator of the general type of configuration shown in FIG. 3 is constructed on land with a nacelle approximately 150 meters above the ground (referenced to the centerline of the nacelle). Each of the blades has a blade span from the hub axis to the blade tip of approximately 100 meters, resulting in a rotor diameter of approximately 200 meters. The generator produces approximately 13 MW of electrical power under peak design conditions. Each blade includes a faced PET foam, wherein approximately 30% by weight of the foam is a high density foam (i.e., a density of 0.24 g / cc (before facing)) and approximately 70% by weight of the PET foam is a low density foam (i.e., a density of 0.11 g / cc (before facing)). The total weight of all PET foams in the wind turbine (excluding facing materials) is approximately 10% by weight of the total blade weight.

[0405] Example 1A - Reduced Weight 13 MW Wind Turbine Power Generation Made with PEF Homopolymer Foam of the Invention machine

[0406] A wind turbine generator having a configuration as described in Comparative Example 1 was constructed, except that the high-density PET foam and / or the low-density PET foam of Comparative Example 1 was replaced with a foam of the present invention based on any one of Foams 1 to 4. For this embodiment, the high-density PET foam and / or the low-density PET foam of Comparative Example 1 was replaced with a foam of the present invention based on any one of Foams 1 to 4, as described in the PEF Replacement Table and Figure 5 and Figure 6 The trend line in FIG. 1 shows the preferred PEF homopolymer foams, and / or the foams made from 1234ze foams as shown in the PEFPET replacement table above and Figure 5 and Figure 6 One option for replacement is to use, on an equal strength basis: (1) the foam made from the PEF replacement table above and Figure 5 The PEF homopolymer in the low-density PET replaces all the low-density PET in the low-density PET as indicated by the trend line in (2) the PEFPET replacement table and Figure 6 The trend line in the figure shows that the PEFPET copolymer replaces all the high-density PET foam in the high-density PET foam. Figure 5 A PEF homopolymer having a density of about 0.09 in the middle trend line will have a strength that substantially matches the TS+CS strength of 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 has a density about 22% lower than, and therefore weighs about 22% less than, a low density PET foam. At the same time, according to Figure 6 The PEFPET copolymer with a density of about 0.16 in the middle trend line will have a strength that substantially matches the TS+CS strength of 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, which has a density about 35% lower than a high-density PET foam and is therefore about 35% lighter than the high-density PET foam. The end result is a blade weight reduction of about 2.5%. The unexpected reduction in blade weight that can be achieved by using the foam of the present invention is significant and commercially significant. Blade weight reduction means that many other parts of a wind turbine can be made smaller and / or lighter, which in turn not only has additional environmental benefits, but also significantly reduces construction costs. For example, the nacelle of a wind turbine is designed to be compatible with the blades, including having a size and weight that balances the torque generated by the blades. In addition, this weight reduction will result in cost savings in tower design and construction costs.

[0407] Many other advantageous options for replacing PET foam with the foam of the present invention are possible, and several of these options (along with the options described above in this example, hereinafter designated as Option 1) are exemplified in the following table:

[0408]

[0409]

[0410] As can be seen from the options shown in the table above, the extent of weight reduction in blade weight ranges from 2.5% to 3.95%, and for any given situation, one skilled in the art may select the option that does not provide the highest weight reduction in order to meet other requirements. For example, for those situations where the highest priority is to eliminate any foam derived from petroleum products, then option 3 would be selected because it relies on 100% PEF homopolymer, which can be 100% derived from non-petroleum products. Alternatively, for those situations where cost is a major consideration, then it is expected that option 4 may be of interest because it is expected that PEFPET copolymer may be available at a lower cost than PEF homopolymer. In view of the teachings and embodiments contained herein, one skilled in the art will understand that many other advantageous combinations and options may be used for any particular replacement situation.

[0411] Example 1B - 13 MW Wind Turbine Made with PEF Homopolymer Foam Using HFO-1336MZZ Blowing Agent Turbine generator

[0412] A wind turbine generator having the configuration as described in Example 1A was constructed, except that the PET foam core material of Comparative Example 1A was replaced with a PEF polymer foam of the present invention foamed with a blowing agent consisting of HFO-1336mzz (including as reported in Foam Formation Example 4). Acceptable results were observed.

[0413] Example 1C - 13 MW wind turbine made with PEF homopolymer foam using HFO-1233zd blowing agent dynamo

[0414] A wind turbine generator having the configuration as described in Example 1A was constructed, except that the PET foam core material of Comparative Example 1A was replaced with a PEF polymer foam of the present invention foamed with a blowing agent consisting of HFO-1336mzz (including as reported in Foam Formation Example 4). Acceptable results were observed.

[0415] Example 1D - 13 MW wind turbine made with PEF homopolymer foam using HFO-1224yd blowing agent dynamo

[0416] A wind turbine generator having the configuration as described in Example 1A was constructed, except that the PET foam core material of Comparative Example 1A was replaced with a PEF polymer foam of the present invention foamed with a blowing agent consisting of HFO-1224yd. Acceptable results were observed.

[0417] Example 1F - 13 MW Wind Turbine Made from Foam Formed from PEF Polymer Made with ADR Additive Turbine generator

[0418] A wind turbine generator having the configuration as described in Example 1 was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a foam of the present invention made from a PEF polymer using an ADR additive as described in Foam Formation Example 5. Acceptable results were observed.

[0419] Example 1G - 13 MW wind turbine made from foam formed from PEF polymer made with PENTA additive Turbine generator

[0420] A wind turbine generator having the configuration as described in Example 1 was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a foam of the present invention made from a PEF polymer using a PENTA additive as described in Foam Formation Example 5. Acceptable results were observed.

[0421] Example 1H - 13 MW foam made from PEF polymer made with PMDA plus talc additive Wind turbine generator

[0422] A wind turbine generator having the configuration as described in Example 1 was constructed except that the PET foam core material of Comparative Example 1 was replaced with a foam of the present invention made from a PEF polymer using PMDA plus a talc additive as described in Foam Formation Example 5. Acceptable results were observed.

[0423] Example 2: 17 MW wind turbine power generation using thin PEF homopolymer foam of the present invention in blade shells machine

[0424] A wind turbine generator having a configuration as described in Comparative Example 1 was made, except that the PET foam core was replaced with a PEF homopolymer foam of the present invention (including each of foams 1 to 4) or a foam made of a PEF polymer of the present invention, including thermoplastic polymers TPP1A to TPP22E. As indicated in the PEF substitution table above, the preferred homopolymer foam of the present invention exhibits, on average, a tensile strength + compressive strength that is approximately 1.3 times higher at about the same density as the density of the PET foam of Comparative Example 1. It is believed that the preferred PEF homopolymer foam of the present invention has a shear strength superior to that of PET foam at about this density. In particular, shear strength is approximately the average of tensile strength and compressive strength, so the shear strength of the copolymer foam of the present invention is, on average, about 1.3 times the shear strength of a PET foam having a foam density of about 0.1 g / cc. This 1.3-fold advantage in shear strength is an unexpected and highly advantageous result, at least in part, because it can reduce the core foam thickness by about 30 relative percentages, which is an expected situation, as long as the flexural rigidity of the foam core is still acceptable. This is shown by calculations described in: Introduction to Sandwich Structures, Chapter 3, Student Edition, 1995, Dan Zenkert.

[0425] τ c =T x / d

[0426] in:

[0427] T x is the direct load in Newtons (per beam width, in this case 1 cm) that causes the beam (in this case the blade) to bend;

[0428] d is the thickness of the core foam + skin, which is approximately equal to the thickness of the core foam (in cm);

[0429] τ c is the shear stress experienced by the core foam due to direct loading. Since the load here is Newtons / cm, the stress becomes Newtons / cm 2 , which has the unit of pressure. High shear strength means high shear stress (τ c ), making it possible to reduce the core foam thickness while still addressing the same direct loads on the beam.

[0430] Example 3A: 6MW wind turbine generator with reduced weight

[0431] Example 3: Composition of PEF homopolymer in the root region and PET:PEF according to the invention in the non-root region of the blade shell Higher output wind turbine generators made from copolymer and / or PEF homopolymer foams

[0432] A wind turbine generator was made having a configuration as described in Comparative Example 1, except that a combination of the PEF homopolymer and PEFPET copolymer of the present invention as described in Example 1 was used, but with the goal of increasing the power output of the wind turbine rather than reducing weight. As shown in Example 1A above, the use of various combinations of the PEF homopolymer and / or PEFPET copolymer of the present invention resulted in blade weight reductions in the range of 2.5% to about 4% of the blade weight. It is expected that the 2.5% to 4% weight reduction will allow the blade to regain 2.5% to 4% of the weight lost, but this time, the blade will be at least 1.1% to 1.8% longer, resulting in a 2.4% to 3.8% increase in power. The power data used for these calculations are shown in Figure 8 and Fig. 9 middle.

[0433] In another option, advantages may also be realized by using the present PEF or PETPEF foam of the same density as used in the PET foam invention, but due to the increased strength of the foam of the present invention, the blade design may be modified in various ways to achieve power improvements.

[0434] –

[0435] Example 3B - 6 MW wind turbine generator made with PEF foam using HFO-1336MZZ blowing agent

[0436] A wind turbine generator having a configuration as described in each of Example 3A was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a PEF polymer foam of the present invention foamed with a blowing agent consisting of HFO-1336mzz (including as reported in Foam Formation Example 4). Acceptable results were observed.

[0437] Example 3C - 6 MW wind turbine made with PEF homopolymer foam using HFO-1233zd blowing agent dynamo

[0438] A wind turbine generator having a configuration as described in each of Example 3A was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a PEF polymer foam of the present invention foamed with a blowing agent consisting of HFO-1336mzz (including as reported in Foam Formation Example 4). Acceptable results were observed.

[0439] Example 3D - 6 MW wind turbine made with PEF homopolymer foam using HFO-1224yd blowing agent dynamo

[0440] A wind turbine generator having the configuration as described in each of Example 3A was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a PEF polymer foam of the present invention foamed with a blowing agent consisting of HFO-1224yd. Acceptable results were observed.

[0441] Example 3E - 6 MW wind turbine made from foam formed from PEF polymer made with ADR additive dynamo

[0442] A wind turbine generator having the configuration as described in each of Example 3A was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a PEF polymer foam of the present invention made from a PEF polymer using an ADR additive as described in Foam Formation Example 5. Acceptable results were observed.

[0443] Example 3F - 6 MW Wind Turbine Made from Foam Formed from PEF Polymer Made with PENTA Additive Turbine generator

[0444] A wind turbine generator having the configuration as described in each of Example 3A was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a PEF polymer foam of the present invention made from a PEF polymer using a PENTA additive as described in Foam Formation Example 5. Acceptable results were observed.

[0445] Example 3H - 6 MW Wind Turbine Made from Foam Formed from PEF Polymer Made with PENTA Additive Turbine generator

[0446] A wind turbine generator having the configuration as described in each of Example 3A was constructed, except that the PET foam core material of Comparative Example 1 was replaced with a PEF polymer foam of the present invention made from a PEF polymer using PMDA plus a talc additive as described in Foam Formation Example 5. Acceptable results were observed.

[0447] Example 4 - Aircraft using one or more of the foam articles 1 to 3

[0448] An aircraft includes at least one foam article of the present invention, including one or more of each of foam articles 1 to 3, at one or more locations where structural foam is desired (preferably including at least a portion of one or more of the wings, fuselage, tail, doors, bulkheads, interior, and / or superstructure). The aircraft achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less weight than previously used foams; (2) a size and / or performance advantage over using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0449] Example 5 - Land Vehicle Using One or More of Foam Articles 1 to 3

[0450] An automobile includes at least one foam article of the present invention, including one or more of each of foam articles 1 to 3, in one or more locations where structural foam is desired (preferably including at least a portion of one or more of the side panels, floor panels, roof panels, engine compartment, battery compartment interior, and / or superstructure). The automobile achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less weight than previously used foams; (2) size and / or performance advantages compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0451] Example 6 - Railway Vehicles Using One or More of Foam Articles 1 to 3

[0452] A railway vehicle includes at least one foam article of the present invention, including one or more of each of foam articles 1 to 3, at one or more locations where structural foam is desired, preferably including at least a portion of one or more of the side panels, floor panels, roof panels, and superstructure. The railway vehicle achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less weight than previously used foams; (2) size and / or performance advantages compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0453] Example 7 - Construction using one or more of the foam articles 1 to 3

[0454] A building structure including one or more locations where structural foam is desired (preferably including at least a portion of one or more of wall panels, floor structures, and ceiling structures and other structures in a building) contains at least one foam product of the present invention, including one or more of each of foam products 1 to 3. The building achieves: (1) a lighter foam weight than previously used structural foam products, preferably at least about 2% less weight than previously used foams; (2) size and / or performance advantages compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0455] Example 8 - Packaging using one or more of the foam articles 1 to 3

[0456] A package (preferably in the form of a box, insert, partition, envelope, etc.) that includes one or more locations where structural foam is desired contains at least one foam article of the present invention, including one or more of each of foam articles 1 to 3. The building achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less weight than previously used foams; (2) size and / or performance advantages compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0457] Example 9 - Sporting goods using one or more of foam articles 1 to 3

[0458] A sporting good (preferably a tennis racket, skateboard, water ski, or snow sled, etc.) that includes one or more locations where structural foam is desired contains at least one foam article of the present invention, including one or more of each of foam articles 1 to 3. The sporting good achieves: (1) a lighter foam weight than previously used structural foam articles, preferably at least about 2% less weight than previously used foams; (2) size and / or performance advantages compared to using the same foam weight as previously used structural foam; and / or (3) a combination of (1) and (2).

[0459] Synthesis Example

[0460] Synthesis Example 1A1 - Preparation of PEF Homopolymer with MW of 41.2 kg / mol Using PMDA

[0461] Molecular weight is 41.2 kg / mol 1The PEF homopolymer is formed by esterification and polycondensation of 75 g of 2,5-furandicarboxylic acid (FDCA) and 55 g of monoethylene glycol (EG). The reactants are added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation device. After evacuation and backfilling with nitrogen, 0.228 g of titanium (IV) isopropoxide catalyst is added to the flask. The flask is then lowered into a 180 ° C salt bath and top mixing is started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature is raised to 220 ° C. After 30 minutes at this temperature and nitrogen, evacuation is started. After 40 minutes under vacuum, the temperature is raised to 250 ° C and continued for 1 hour. Under a nitrogen stream, PMDA (0.5732 g) is slowly added over about 5 minutes. Before stopping the reaction, mixing is allowed to proceed for another 30 minutes at this temperature. For SSP, an aliquot of the product was ground and heated on a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer with a molecular weight of 41 kg / mol.

[0462] Synthesis Example 1A2 - Preparation of PEF Homopolymer with MW of 75000 kg / mol

[0463] 75kg / mol of PEF homopolymer was formed by 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 device. After evacuation and backfilling with nitrogen, 0.228 grams of titanium (IV) isopropoxide catalyst were added to the flask. The flask was then lowered into a 180°C salt bath and top mixing was started at 200rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. After 30 minutes at this temperature and under nitrogen, evacuation was started. After 40 minutes under vacuum, the temperature was raised to 230°C and continued for 1 hour. Under a nitrogen stream, PMDA (2.73g-0.7% by weight) was slowly added over about 5 minutes. Before stopping the reaction, mixing was allowed to proceed for another 30 minutes at this temperature. For SSP, an aliquot (30 g) of the product was ground and heated on a rotary evaporator under vacuum at 180° C. for 3 days to produce a PEF homopolymer with a molecular weight of 75 kg / mol.

[0464] Synthesis Example 1A3 - Preparation of PEF Homopolymer with MW Range of About 96 KG / MOL Using PMDA

[0465] 96,078g / molMW polymer is made by mixing 75 grams of 2,5-furandicarboxylic acid (FDCA) with 55 grams of monoethylene glycol (EG). Reactant is added to a 500mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation device. After vacuuming and backfilling with nitrogen, 0.228 grams of titanium isopropoxide (IV) catalyst are added to the flask. Then the flask is dropped into a 180°C salt bath and top mixing is started at 200rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature is raised to 220°C. After 30 minutes at this temperature and under nitrogen, vacuuming is started. After 40 minutes under vacuum, the temperature is raised to 250°C and continued for 1 hour. Under a nitrogen stream, PMDA (0.5732g) is slowly added in about 5 minutes. Before stopping the reaction, it is allowed to mix for another 30 minutes at this temperature. For SSP, an aliquot of the product was ground and heated on a rotary evaporator at 180°C under vacuum for 3 days to produce a PEF homopolymer as described below. The product was removed from the container. 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. For SSP, an aliquot of the product was ground and heated on a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer with a molecular weight of 96,078.

[0466] Synthesis Example 2A - Preparation of PET9:PEF1 Copolymer with MW of about 117.9:90.4 KG / MOL Using PMDA

[0467] A block copolymer of PET9:PEF1 (mol ratio of 9:1) with a target molecular weight of about 117,900 g / mol was prepared, with PET blocks and PEF blocks of 4 and 4, respectively. Specifically, PEF was first prepared by adding 498 grams of FDCA (2.7 mol) and 417 grams of EG (6.72 mol) to a 1000 mL cylindrical glass reactor equipped with an overhead stirrer and a distillation / condensation device, which was immersed in a 190°C salt bath. After purging with nitrogen, 0.414 grams of titanium (IV) isopropoxide catalyst was added to the flask and top 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 and N2, vacuum was started. After 40 minutes under vacuum, the temperature was raised to 240°C and continued for 2 hours, after which the reaction was stopped and PEF was produced.

[0468] PEF oligomers were prepared by adding 109 g of EG and 0.45 g of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated until boiling in a salt bath at 230°C. An aliquot (160 g) of PEF from the above step was added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The resulting mixture was a PEF oligomer.

[0469] PET oligomers were 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. 160 grams of commercially available recycled PET flakes were then added. The mixture was allowed to react under reflux for 2 hours until the reaction ceased. The result was a PET oligomer mixture.

[0470] The copolymer was prepared by rapidly adding 12.0 g of PEF oligomer and 111.7 g of PET oligomer to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus immersed in a 220° C. salt bath, followed by the addition of 0.9083 g of titanium (IV) isopropoxide. Shortly thereafter (<2 minutes), a vacuum was applied to remove the EG. After 40 minutes, the temperature was raised to 270° C. and the contents of the reactor were kept under vacuum for 40 minutes. Under an N2 atmosphere, 0.483 g of PMDA was slowly added. Mixing was allowed to proceed for another 30 minutes at this temperature before the reaction was stopped. Solid-state polymerization was performed as follows: an aliquot (30 g) of the above product was ground and then heated at 180° C. for 3 days on a rotary evaporator under vacuum to produce a PET9:PEF1 copolymer having a PET molecular weight of 117.9 kg / mol.

[0471] Synthesis Examples 3A to 3E - Preparation of Polymers with Molecular Weights of About 57 KG / MOL to 57 KG / MOL Using ADR, PMDA, Talc and PENTA 69KG / MOL PET9:PEF1 copolymer

[0472] Using the additives and polymer formation procedures generally as described in Synthesis Examples 1 to 3, three (3) block copolymers of PET9:PEF1 (9:1 molar ratio) and one (1) block copolymer of PET19:PEF1 (19:1 molar ratio) were prepared, wherein the target molecular weight of the PET portion of the copolymer was from about 10 kg / mol to about 69 kg / mol, except that PMDA+talc, chain extender ADR-4468 (hereinafter referred to as "ADR") were used. 2 and PENTA replace PMDA alone.

[0473] The PET:PEF copolymer thus produced was tested using the measurement protocol described above and found to have the characteristics reported in Table SyEx3 below:

[0474] Table SyEx3

[0475]

[0476] Synthesis Examples 4A to 3D - Preparation of Polymers with Molecular Weights in the Range of 80 KG / MOL to 96 KG / MOL and Crystalline Polymers Using PMDA PET homopolymer with a density of 32 to 43

[0477] Four (4) PET homopolymers were prepared by polycondensation to produce polymer products having molecular sizes ranging from about 80 kg / mol to about 96 kg / mol using the procedures described above in Synthesis Example 1 and variations of these procedures to achieve polymers with molecular weights as shown below as SyEx4.

[0478] The PET polymers are designated herein as PETC1, PETC2, PETC3 and PETC and were tested and found to have the characteristics reported in Table SyEx4 below:

[0479] Table SyEx4

[0480] SyEx4C1 SyEx4C2 SyEx4C3 SyEx4C4 name PETC1 PETC2 PETC3 PETC4 PET homopolymer molecular weight 95,596 80,871 80,900 83,900 Glass transition temperature, °C 74 74.9 76.1 76 Melting point, °C 219 230 225 227 Decomposition temperature, °C 382 378 386 376 Crystallinity, % 33.3 42.9 31.9 41

[0481] As shown in the table above, each of the PET homopolymers was produced utilizing the preferred high crystallinity aspects of the present invention.

[0482] Foam Formation Example

[0483] Foam Formation Example 1 - Preparation using PETC1, PETC2, PETC3 and PETC4 with 1234ZE(E) blowing agent PET foam

[0484] In a series of runs, 1 gram of each PET polymer (as shown in Table SyEx4 above) in a glass container was loaded into a 60cc volume autoclave and then dried under vacuum at an elevated temperature in the range of 130°C to 150°C for six (6) hours. The dried polymer was then cooled to room temperature. For each case, the blowing agent was 1234ze (E), which was then pumped into the autoclave containing the dried polymer, which was then heated to allow the polymer to reach a molten state, the temperature, pressure and time of which are listed in Table FFeX-Low Density Foam and Table FFeX-High Density Foam above. After the melting time shown, the temperature and pressure of the melt / blowing agent were then reduced to the pre-foaming temperature and pre-foaming pressure, as shown in the table above, within a period of about 5 minutes to 15 minutes. The autoclave was then kept at about this temperature and pressure for about 30 minutes to ensure that the amount of the blowing agent introduced into the melt under such conditions reached equilibrium. 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 acceptable foams with RFD values ​​ranging from about 0.05 to about 0.25. The temperature and pressure in the autoclave were then rapidly reduced (pressure was reduced over a period of about 10 seconds and temperature was reduced over a period of about 1 minute to 10 minutes using cold water) to ambient conditions (about 22°C and 1 atmosphere), and foaming occurred.

[0485] The PET foams thus produced have the properties indicated in Table FFeX - Low Density Foam and Table FFeX - High Density Foam above.

[0486] Foam Formation Example 2 - Using PEF1A1 and PEF1A2 with trans-1234ZE blowing agent and 60 minutes melt time Preparation of PEF foam

[0487] As described herein, using a foaming process designed according to the same criteria as described in SyExC1 above, one foam was made using PEF1 and four foams were made using PEF2, the PEF1 and the PEF2 being identified in the above Table FFeX-Low Density Foam and Table FFeX-High Density Foam. The foams thus produced were tested and found to have the properties reported in the above Table FFeX-Low Density Foam and Table FFeX-High Density Foam and as shown in the following Table FFEx2.

[0488] Table FFEx2

[0489]

[0490]

[0491] Foam Formation Example 3 - Using PET9PEF1-EX3A with trans-1234ZE blowing agent and 60 minutes melt time Preparation of PEF foam

[0492] Six (6) foams were prepared from PET9PEF1-EX3A using a foaming process designed according to the same criteria as described in Comparative Example 1. The foams thus produced were tested and found to have the properties reported in Table E3B below:

[0493] Table E3B

[0494]

[0495]

[0496] Foam Formation Example 4 - Foam Formation Using PET9:PEF1 and Trans-1234ZE, Trans-1233ZD and Cis-1336 Preparation of PET9:PEF1 foam with foaming agent and 60 min melting time

[0497] A series of foams were prepared using PET9:PEF1 using a foaming process designed according to the same criteria as described in Foam Synthesis Examples 1 to 3. The foams thus produced were tested and found to have the properties reported in Table FFEx 4 below:

[0498] Table FFEx4

[0499]

[0500] As disclosed by the data in Table FFEx4 above and other examples presented herein, Applicants have surprisingly found that when the blowing agent comprises 1234ze(E) or consists essentially of 1234ze(E) or consists of 1234ze(E), the PEF:PET foam according to the present invention generally has superior strength characteristics compared to other blowing agents including 1233zd and 1336, as disclosed by the data in the above table. However, when the blowing agent comprises 1233zd(E) or 1336mzz(Z), or consists essentially of or consists of them, acceptable foams are prepared and have comparable utility, as disclosed by the above data.

[0501] Foam Formation Example 5 - Using PET9PEF1-EX3A with trans-1234ZE blowing agent and PENTA, ADR and Preparation of PEF foam with PMDA+talc additive

[0502] In Synthesis Example 4 above, foam was made from PET9PEF1 as described above using a foaming process designed according to the same criteria as described in Foam Formation Examples 1 to 3. The foam thus produced was tested and found to have the properties reported in Table FFEx5 below:

[0503] Table FFEx5

[0504]

[0505] As revealed by the data in Table FFEx4 above, Applicants have surprisingly discovered that when the preferred blowing agent comprises 1234ze(E) or consists essentially of 1234ze(E) or consists of 1234ze(E) together with various polymeric additives, the PET:PEF foam according to the present invention generally has excellent strength characteristics.

Claims

1. A wind turbine blade, comprising: a. Blade shell; and b. The foam in the blade shell, the foam comprising a thermoplastic foam, the thermoplastic foam comprising: (1) thermoplastic polymer pores comprising pore walls forming closed cells, wherein the thermoplastic polymer comprises ethylene furanoate moieties and optionally ethylene terephthalate moieties; and (b) A foaming agent contained in the closed cells.

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

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

4. The wind turbine blade of claim 1, wherein the thermoplastic polymer (i) comprises from about 0.5 mol% to about 99.5 mol% of ethylene furanoate moieties and from 0.5 mol% to about 99.5 mol% of ethylene terephthalate moieties; 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 pores are closed pores. 6 . The wind turbine blade of claim 1 , wherein the foam has a foam density of about 0.05 g / cc to about 0.25 g / cc.

7. A faced foam, comprising: a. a thermoplastic foam core comprising polymer cells, the polymer cells comprising cell walls forming closed cells, wherein the thermoplastic polymer comprises ethylene furanoate moieties and a blowing agent contained in the closed cells; and b. A facing attached to and / or integral with at least a portion of the first foam.

8. An article comprising the faced foam according to claim 9.

9. An energy generating device comprising the faced foam according to claim 9.

10. An energy generating device according to claim 13, comprising a blade, foil or rotor in a wind turbine generator.

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