Foamable thermoplastic composition, thermoplastic foam and preparation method thereof

Abstract

A method of forming an extruded thermoplastic foam comprising extruding a foamable composition comprising a thermoplastic polymer and a blowing agent wherein the thermoplastic polymer consists essentially of an ethylene furanate moiety and optionally an ethylene terephthalate moiety, and wherein the extruding step comprises forcing the foamable composition from a relatively high pressure region through a die to a relatively low pressure region.

Description

Cross-references to related applications

[0001] This application claims priority to each of US 63 / 534,340 (filed August 8, 2023) and US 63 / 533,699, each of which is incorporated herein by reference as if fully set forth below.

[0002] This application is also incorporated by reference in US 18 / 113,605, filed February 23, 2023. Technical Field

[0003] This invention relates to foamable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles prepared therefrom. Background Technology

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

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

[0006] Regarding the selection of thermoplastic resins, EP 3,231,836 acknowledges that while there is interest in thermoplastic resins, particularly polyester-based resins, this interest has encountered difficulties in development, including the difficulty in determining suitable foaming grades for such resins. Furthermore, 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 foaming agents to produce closed-cell foams with the potential for low density and good mechanical properties, it does not disclose any such resin capable of simultaneously producing foams with good environmental and performance properties, and also capable of being formed from sustainable sources. The '836 application identifies several possible polyester resins for forming open-cell foams, including polyethylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate, polyethylene naphthalate, polyvinyl furanoate, or mixtures of two or more of these. Although the use of polyester materials to prepare foams that are essentially free of closed cells, as required by EP'836, may be beneficial for some applications, the disadvantage of such structures is that, in general, open-cell foams will exhibit relatively poor mechanical strength properties.

[0007] CN 108484959 discloses that the preparation of foam products based on 2,5-furandimethyl copolyester is problematic because it asserts the issue of the blowing agent dissolving into the polyester, and proposes a combination of liquid and gaseous blowing agents and a specific method involving the sequential use of these different classes of blowing agents.

[0008] US 2020 / 0308363 and US 2020 / 0308396 each disclose the production of amorphous polyester copolymers, which involve starting with recycled polyester (PET being an example only) as the main component, followed by a series of processing steps to obtain an amorphous copolymer, i.e., a copolymer without crystallinity. Various types of blowing agents are mentioned for use in such amorphous polymers.

[0009] Regarding foaming agents, the use of halogenated olefin foaming agents (including hydrofluoroolefins (HFO) and hydrochlorofluoroolefins (HCFO)) is generally known, as disclosed, for example, in US 2009 / 0305876, which is assigned to the assignee of this invention and is incorporated herein by reference. While '876 application discloses the use of HFO and HFCO foaming agents with various thermoplastic materials (including PET) for forming foams, it does not disclose or suggest the use of any such foaming agents with any other type of polyester resin.

[0010] The applicant has realized that by using a combination of polyester resins as disclosed herein with a blowing agent comprising one or more hydrohalogenated olefins as disclosed herein, one or more unexpected advantages can be achieved in relation to the formation of thermoplastic foams, particularly extruded thermoplastic foams. Summary of the Invention

[0011] This invention includes extruded thermoplastic foams comprising the following:

[0012] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer is substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 100 mol% of the ethylene furanate portion and optionally at least about 1 mol% of the polyethylene terephthalate portion; and

[0013] (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 closed pores.

[0014] For convenience, the foam referred to in this paragraph will be called Foam 1A in this document.

[0015] This invention includes extruded thermoplastic foams comprising the following:

[0016] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has at least about 5% crystallinity and is substantially composed of an ethylene furanate moiety and optionally a polyethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 100 mol% of the ethylene furanate moiety and optionally at least about 1 mol% of the polyethylene terephthalate moiety; and

[0017] (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 closed pores.

[0018] For convenience, the foam described in this paragraph will be referred to as Foam 1B in this document.

[0019] This invention includes extruded thermoplastic foams comprising the following:

[0020] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate moiety and at least about 1 mol% of the ethylene terephthalate moiety; and

[0021] (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 closed pores.

[0022] For convenience, the foam referred to in this paragraph will be called Foam 1C.

[0023] This invention includes extruded thermoplastic foams comprising the following:

[0024] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate moiety and about 80 mol% to about 99 mol% of the ethylene terephthalate moiety; and

[0025] (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 closed pores.

[0026] For convenience, the foam described in this paragraph will be referred to as Foam 1D in this document.

[0027] This invention includes extruded thermoplastic foams comprising the following:

[0028] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 10 mol% of the ethylene furanate moiety and about 90 mol% to about 99 mol% of the ethylene terephthalate moiety; and

[0029] (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 closed cells. For convenience, the foam described in this paragraph is referred to herein as Foam 1E.

[0030] This invention includes extruded thermoplastic foams comprising the following:

[0031] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 5 mol% of the ethylene furanate moiety and about 95 mol% to about 99 mol% of the ethylene terephthalate moiety; and

[0032] (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 closed pores.

[0033] For convenience, the foam referred to in this paragraph will be called Foam 1F in this document.

[0034] This invention includes extruded thermoplastic foams comprising the following:

[0035] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% to about 2 mol% of the ethylene furanate moiety and about 98 mol% to about 99.5 mol% of the ethylene terephthalate moiety; and

[0036] (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 closed pores.

[0037] For convenience, the foam referred to in this paragraph will be called Foam 1G in this document.

[0038] This invention includes extruded thermoplastic foams comprising the following:

[0039] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% of the ethylene furanate moiety and about 99 mol% of the ethylene terephthalate moiety; and

[0040] (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 closed pores.

[0041] For convenience, the foam referred to in this paragraph will be called foam 1H.

[0042] This invention includes extruded thermoplastic foams comprising the following:

[0043] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% of the ethylene furanate moiety and about 99.5 mol% of the ethylene terephthalate moiety; and

[0044] (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 closed pores.

[0045] For convenience, the foam referred to in this paragraph will be called Foam 1I in this document.

[0046] This invention includes extruded thermoplastic foams comprising the following:

[0047] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 5 mol% of the ethylene furanate moiety and about 95 mol% of the ethylene terephthalate moiety; and

[0048] (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 closed pores. For convenience, the foam described in this paragraph is referred to herein as foam 1J.

[0049] This invention includes extruded thermoplastic foams comprising the following:

[0050] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 10 mol% of the ethylene furanate moiety and about 90 mol% of the ethylene terephthalate moiety; and

[0051] (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 closed pores.

[0052] For convenience, the foam referred to in this paragraph will be called Foam 1K in this document.

[0053] This invention includes extruded thermoplastic foams comprising the following:

[0054] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is substantially composed of an ethylene furanate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 20 mol% of the ethylene furanate moiety and about 80 mol% of the ethylene terephthalate moiety; and

[0055] (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 closed pores.

[0056] For convenience, the foam referred to in this paragraph will be called Foam 1L.

[0057] This invention includes extruded thermoplastic foams comprising the following:

[0058] (a) A thermoplastic polymer pore comprising pore walls containing polyethylene furanate, wherein at least 25% of the pores are closed pores; and

[0059] (b) 1234ze(E) contained in the closed pore.

[0060] For convenience, the foam referred to in this paragraph will be called Foam 2A in this document.

[0061] This invention includes extruded thermoplastic foams comprising the following:

[0062] (a) A thermoplastic polymer pore comprising a pore wall comprising polyethylene furanate and substantially composed of an ethylene furanate portion and a polyethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate portion and about 0.5 mol% or more of the polyethylene terephthalate portion, wherein at least 25% of the pore is closed-cell; and

[0063] (b) 1234ze(E) contained in the closed pore.

[0064] For convenience, the foam described in this paragraph will be referred to as Foam 2B in this document.

[0065] This invention includes extruded thermoplastic foams comprising the following:

[0066] (a) A thermoplastic polymer pore comprising a pore wall comprising polyethylene furanate and substantially composed of an ethylene furanate portion and a polyethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate portion and about 0.5 mol% or more of the polyethylene terephthalate portion, wherein at least 25% of the pore is closed-cell; and

[0067] (b) 1336mzz(Z) contained in the closed pore.

[0068] For convenience, the foam described in this paragraph will be referred to as Foam 2C in this document.

[0069] This invention includes extruded thermoplastic foams comprising the following:

[0070] (a) A thermoplastic polymer pore comprising a pore wall comprising polyethylene furanate and substantially composed of an ethylene furanate portion and a polyethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate portion and about 0.5 mol% or more of the polyethylene terephthalate portion, wherein at least 25% of the pore is closed-cell; and

[0071] (b) 1223zd(E) contained in the closed aperture.

[0072] For convenience, the foam described in this paragraph will be referred to as Foam 2D ​​in this document.

[0073] This invention includes extruded thermoplastic foams comprising the following:

[0074] (a) A thermoplastic polymer pore comprising a pore wall comprising polyethylene furanate and substantially composed of an ethylene furanate portion and a polyethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate portion and about 0.5 mol% or more of the polyethylene terephthalate portion, wherein at least 25% of the pore is closed-cell; and

[0075] (b) 1224yd contained in the closed pore.

[0076] For convenience, the foam described in this paragraph will be referred to as Foam 2E in this document.

[0077] This invention includes extruded thermoplastic foams comprising the following:

[0078] (a) A thermoplastic polymer pore comprising a pore wall comprising polyethylene furanate and substantially composed of an ethylene furanate portion and a polyethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanate portion and about 0.5 mol% or more of the polyethylene terephthalate portion, wherein at least 50% of the pores are closed pores; and

[0079] (b) The gas in the closed pore, wherein the gas contains about 25% to 100% by weight of 1234ze(E). For convenience, the foam according to this paragraph is referred to herein as foam 2F.

[0080] Numbered foams (e.g., foam 1) or numbered foam groups as defined herein will be mentioned in various places throughout this document, and such references refer to each of such numbering systems, including each system with in-group numbers, including any suffix numbering systems. For example, mentioning foam 1 includes individually referring to each of foams 1A, 1B, 1C, 1D, etc., and mentioning foams 1 to 2 should be understood to include individually referring to each of foams 1A, 1B, 1C, 1D, etc., and each of foams 2A, 2B, 2C, 2D, etc. Furthermore, this convention applies throughout this specification to other defined materials, including foaming agents.

[0081] This invention includes extruded thermoplastic foams comprising the following:

[0082] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer is substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein the thermoplastic polymer: (i) comprises about 10 mol% to about 100 mol% of an ethylene furanate portion and optionally at least about 1 mol% of a polyethylene terephthalate portion; and (ii) has a molecular weight of at least about 25,000; and

[0083] (b) The trans 1234ze contained in the closed pore.

[0084] For convenience, the foam described in this paragraph will be referred to as Foam 3 in this document.

[0085] This invention includes extruded thermoplastic foams comprising the following:

[0086] (a) A thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer is substantially composed of an ethylene furanate moiety and optionally a polyethylene terephthalate moiety, wherein the thermoplastic polymer: (i) comprises about 10 mol% to about 100 mol% of an ethylene furanate moiety and optionally at least about 1 mol% of a polyethylene terephthalate moiety; and (ii) has a molecular weight of about 25,000 to about 140,000; and

[0087] (b) The trans 1234ze contained in the closed pore.

[0088] For convenience, the foam described in this paragraph will be referred to as Foam 4 in this article.

[0089] This invention includes expandable thermoplastic compositions comprising:

[0090] (a) A thermoplastic material comprising substantially an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein the thermoplastic material comprises about 1 mol% to about 100 mol% of the ethylene furanate portion and optionally at least about 1 mol% of the polyethylene terephthalate portion; and

[0091] (b) A foaming agent comprising one or more HFO having three or four carbon atoms and / or one or more HFCO having three or four carbon atoms.

[0092] For convenience, the foamable composition according to this paragraph is referred to herein as foamable composition 1.

[0093] The present invention includes a method for forming a thermoplastic composition having improved crystallinity, the method comprising:

[0094] (a) A thermoplastic material comprising polymer chains containing an ethylene furanate moiety and / or an ethylene terephthalate moiety; and

[0095] (b) Dissolving at least a portion of the thermoplastic material in a solvent, wherein the thermoplastic material comprises about 1 mol% to about 100 mol% of an ethylene furanate portion and optionally at least about 1 mol% of a polyethylene terephthalate portion; and

[0096] (c) Distilling the solvent from the thermoplastic material.

[0097] For convenience, the method of forming a thermoplastic composition according to this paragraph is referred to herein as thermoplastic molding method 1.

[0098] The present invention also provides a method for forming thermoplastic foam, the method comprising foaming a foamable composition of the present invention (including foamable composition 1). For convenience, the method according to this paragraph is referred to herein as foaming method 1.

[0099] The present invention also provides a method for forming extruded thermoplastic foams, the method comprising extruding the foamable composition of the present invention, including foamable composition 1. For convenience, the method according to this paragraph is referred to herein as foaming method 2.

[0100] The present invention also provides a method for forming extruded thermoplastic foams, the method comprising extruding the foamable composition of the present invention, including foamable composition 1, the method comprising moving the foamable composition through a die in an extruder from a relatively high-pressure region to a relatively low-pressure region. For convenience, the method according to this paragraph is referred to herein as extrusion method 1. Attached Figure Description

[0101] Figure 1 This is a schematic diagram of an embodiment of the present invention and an extrusion system and method according to the embodiments herein.

[0102] Figures 2A to 2C This is a graphical representation of the results of Example C1B.

[0103] Figure 3A and Figure 3B This is a graphical representation of the results of embodiment C2B.

[0104] Figure 4 This is a graphical representation of the results of Example 1B.

[0105] Figure 5A and Figure 5B This is a graphical representation of the results of Example 2B.

[0106] Figures 6A to 6D This is a graphical representation of the results of Example 3B.

[0107] Figure 7 This is a graphical representation of the results of Example 4B.

[0108] Figure 8 This is a graphical representation of the results of Example 5B.

[0109] Figure 9 This is a graphical representation of the results of Example 6B.

[0110] Figure 10 This is a graphical representation of the results of Example 7B.

[0111] Figure 11 This is a graphical representation of the results of Example 8B.

[0112] Figure 12 This is a graphical representation of the results of Example 9B.

[0113] Figure 13 A graphical representation of the results of Example 10B

[0114] Figure 14 A graphical representation of the results of Example 11B

[0115] Figure 15 A graphical representation of the results of Example 12B

[0116] Figure 16 A graphical representation of the results of Example 12C

[0117] Figure 17 A graphical representation of the results of Example 13B1

[0118] Figure 18 A graphical representation of the results of Example 13B2

[0119] Figure 19 A graphical representation of the results of Example 13B3

[0120] Figure 20 This is a graphical representation of the results of Examples 16B1-B3.

[0121] Figure 22 This is a schematic diagram of an exemplary wind turbine.

[0122] Figure 23 is a half-schematic diagram of an exemplary wind turbine blade.

[0123] Figure 24 A is a cross-section of an exemplary wind turbine blade.

[0124] Figure 24 B is a cross-section of an exemplary wind turbine blade.

[0125] Figure 24 C is the cross-section of an exemplary wind turbine blade.

[0126] Figure 25 This is a graphical representation of the results of Example 21B.

[0127] definition

[0128] 1234ze refers to 1,1,1,3-tetrafluoropropylene, and there are no restrictions on isomers.

[0129] Trans-1234ze and 1234ze(E) refer to trans-1,3,3,3-tetrafluoropropylene.

[0130] Cis-1234ze and 1234ze(Z) respectively refer to cis-1,3,3,3-tetrafluoropropylene.

[0131] 1234yf refers to 2,3,3,3-tetrafluoropropylene.

[0132] 1233zd refers to 1-chloro-3,3,3-trifluoropropene, and there are no restrictions on its isomer forms. trans-1233zd and 1233zd(E) each refer to trans-1-chloro-3,3,3-trifluoropropene.

[0133] 1224yd refers to cis-1-chloro-2,3,3,3-tetrafluoropropane, and there are no restrictions on isomers.

[0134] 1336mzz refers to 1,1,1,4,4,4-hexafluorobutene, and there are no restrictions on its isomer forms.

[0135] Trans-1336mzz and 1336mzz(E) refer to trans-1,1,1,4,4,4-hexafluorobutene.

[0136] cis-1336mzz and 1336mzz(Z) respectively refer to cis-1,1,1,4,4,4-hexafluorobutene.

[0137] Closed-cell foam refers to foam in which a significant percentage of the volume of pores are closed, for example, about 20% or more by volume.

[0138] The ethylene furanate moiety refers to the following structure:

[0139]

[0140] FDCA refers to 2,5-furandicarboxylic acid and has the following structure:

[0141]

[0142] MEG refers to monoethylene glycol and has the following structure:

[0143]

[0144] FDME refers to dimethyl 2,5-furandicarboxylate and has the following structure:

[0145]

[0146] PEF homopolymer refers to a polymer having at least 99 mol% ethylene furanate moiety.

[0147] PEF copolymers refer to polymers having at least about 10 mol% of an ethylene furanoate portion and more than 1% of a polymer portion other than the ethylene furanoate portion.

[0148] PEF:PET copolymer refers to a polymer having at least about 10 mol% of ethylene furanate moiety and at least 1% of polyethylene terephthalate moiety.

[0149] PEF stands for poly(ethylene furanoate) and encompasses and is intended to reflect the description of PEF homopolymers and PEF copolymers.

[0150] The ethylene terephthalate moiety refers to the following structure and repeating units based on this structure as understood by those skilled in the art:

[0151]

[0152] SSP refers to solid-state polymerization.

[0153] PMDA refers to pyromellitic dianhydride with the following structure:

[0154] Detailed Implementation

[0155] Poly(ethylene furanate)

[0156] The present invention relates to foams and foam articles comprising pore walls comprising poly(ethylene furanate) (“PEF”).

[0157] The PEF forming the pore walls of the foams and foam articles of the present invention can be a PEF homopolymer or a PEF copolymer, and in particular a PEF:PET copolymer.

[0158] PEF homopolymer is a known material that is known to be formed by: (a) esterification and polycondensation of FDCA with MEG; or (b) transesterification and polycondensation of FDME with MEG, as shown below, for example:

[0159]

[0160] A detailed description of such known esterification and condensation polymerization methods is provided in GB Patent 621971 (Drewitt, JGN and Lincoln, J., entitled "Improvements in Polymers"), which is incorporated herein by reference. Detailed descriptions of these known transesterification reactions and condensation polymerization methods are provided in: Gandini, A., Silvestre, AJD, Neto, CP, Sousa, AF and Gomes, M. (2009), "The furan counterpart of poly(ethylene terephthalate): an alternative material based on renewable resources," J. Polym. Sci. Polym. Chem. 47, 295–298. doi: 10.1002 / pola.23130, which is incorporated herein by reference.

[0161] Foam

[0162] The foams of the present invention (including each of foams 1 to 4) are formed from PEF homopolymers, PEF copolymers, or combinations / mixtures thereof.

[0163] In a preferred embodiment, the foam 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% by weight or at least 99.9% by weight of an ethylene furanate portion.

[0164] In a preferred embodiment, the foams of the present invention (including each of foams 1 to 4) are expected to be formed from PEF copolymers, wherein the polymer (including the PEF copolymers) has about 60% to about 99% by weight of ethylene furanoate portion, or about 70% to about 99% by weight of ethylene furanoate portion, or about 80% to about 99% by weight of ethylene furanoate portion, or about 90% to about 99% by weight of ethylene furanoate portion, or about 95% to about 99.5% by weight of ethylene furanoate portion.

[0165] It is anticipated that the foams of the present invention (including each of foams 1 to 4) may be formed from PEF copolymers in a preferred embodiment, wherein the polymer (including the PEF copolymer) has about 40% to about 1% ethylene furanoate portion, or about 30% to about 1% ethylene furanoate portion, or about 20% to about 1% ethylene furanoate portion, or about 10% to about 1% ethylene furanoate portion, or about 5% to about 1% ethylene furanoate portion, or about 5% to about 0.5% ethylene furanoate portion.

[0166] In a preferred embodiment, the foams of the present invention (including each of foams 1 to 4) are expected to be formed from PEF copolymers, wherein the polymer (including the PEF copolymer) has about 40 mol% to about 1 mol% of ethylene furanoate portion and about 60 mol% to about 99 mol% of polyethylene terephthalate portion, or about 30 mol% to about 1 mol% of ethylene furanoate portion and about 70 mol% to about 99 mol% of polyethylene terephthalate portion, or about 20 mol% to about 1 mol% of ethylene furanoate portion. And about 80 mol% to about 99 mol% of ethylene terephthalate, or about 10 mol% to about 1 mol% of ethylene furanoate and about 90 mol% to about 99 mol% of ethylene terephthalate, or about 5 mol% to about 1 mol% of ethylene furanoate and about 95 mol% to about 99 mol% of ethylene terephthalate, or about 5 mol% to about 0.5 mol% of ethylene furanoate and about 95 mol% to about 99.5 mol% of ethylene terephthalate.

[0167] For those embodiments of the invention involving PEF copolymers, in light of the teachings contained herein, it is expected that those skilled in the art will be able to select the type and amount of copolymer material to be used within each of the ranges described herein to achieve the desired reinforcement / modification of the polymer without excessive experimentation.

[0168] For embodiments of the invention involving the use of PEF homopolymers or PEF copolymers, it is contemplated that such materials having a variety of molecular weights and physical properties within the scope of the invention can be formed. In a preferred embodiment, the foam (including each of foams 1 to 4) is formed from PEF having the characteristic ranges defined in Table 1 below, which are measured as described in the embodiments herein:

[0169] Table 1

[0170]

[0171] In general, given the teachings contained herein, those skilled in the art will be able to formulate PEF polymers within the aforementioned property range without excessive experimentation. However, in preferred embodiments, PEFs (including PEF homopolymers and PEF copolymers) possessing these properties are achieved using one or more of the above-described synthetic methods in combination with various known supplementary processing techniques, including treatment with chain extenders such as PMDA (and alternatives and supplements to PMDA, such as ADR, PENTA, and talc as described in this embodiment), chain branching agents such as trimethylolpropane triacrylate (TMPTA), PMDA (which provides both chain extension and branching), poly(glycolic acid) (which provides both chain extension and branching), triglycidyl isocyanurate (which provides both chain extension and branching), bisphenol A diglycidyl ether (which provides both chain extension and branching), and / or SSP processing (including treatment in an extruder). It is believed that, given the disclosure contained herein, including the polymer synthesis described in the examples below, those skilled in the art will be able to prepare PEF polymers within the characteristic range described in the table above and elsewhere herein, including using methods that enhance polymer crystallization. Such processing conditions include the methods for increasing crystallization described herein, including the thermoplastic molding method 1 of the present invention and such methods disclosed in the embodiments herein.

[0172] An example of a chain extension method for polyester is provided in the article “Recycled poly(ethylene terephthalate) chain extension by areactive extrusion process”, Firas Awaja, Fugen Daver, Edward Kosior, August 16, 2004, available at [date / date]. https: / / doi.org / 10.1002 / pen.20155As explained in US 1009 / 0264545, which is incorporated herein by reference, chain extenders are generally compounds that are at least bifunctional relative to a reactive group, which can react with end groups or functional groups in a polyester to extend the length of the polymer chain. In some cases, as disclosed herein, such treatment can advantageously increase the average molecular weight of the polyester to improve its melt strength and / or other important properties. The degree of chain extension achieved is at least in part related to the structure and functionality of the compound used. A variety of compounds can be used as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing polyfunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposites such as finely dispersed nanoclays can optionally be used to control viscosity. Commercially available chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema. The amount of chain extender 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, is 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. Patent No. 4,219,527, which is incorporated herein by reference.

[0173] An example of the SSP processing method for poly(ethylene furanoate) is provided in the article “Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase”, Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which are incorporated herein by reference.

[0174] PEF thermoplastic polymers that are particularly advantageous for preparing the foamable compositions and foams of the present invention are listed in the following table of thermoplastic polymers (Table 2A), wherein all values ​​in the table are understood to be preceded by the word "about".

[0175] Table 2A - Thermoplastic Polymers

[0176]

[0177] The PEF thermoplastic polymers particularly advantageous for preparing the foamable compositions and foams of the present invention also include those materials identified in the following table of thermoplastic polymers (Table 2B), wherein all values ​​in the table are understood to be preceded by the word "about".

[0178] Table 2B - Thermoplastic Polymers

[0179]

[0180] The PEF thermoplastic polymers particularly advantageous for preparing the foamable compositions and foams of the present invention also include those materials identified in the following table of thermoplastic polymers (Table 2C), wherein all values ​​in the table are understood to be preceded by the word "about".

[0181] Table 2C - Thermoplastic Polymers

[0182]

[0183]

[0184] For the purpose of defining the terminology used herein, it should be noted that throughout this document, references will be made to the thermoplastic polymers shown in the first column of each row in the TPP table above, and references to each of these numbers will be references to the thermoplastic polymer as defined in the corresponding column of that row. Referring to a group of TPPs defined in the table above by referring to a TPP number means referring to each TPP with such a number individually and independently, including each TPP with the number shown, including any such number with a suffix. Thus, for example, referring to TPP1 is referring to TPP1A, TPP1B, TPP1C, TPP1D, and TPP1E individually and independently. Referring to TPP1-TPP2 is referring to TPP1A, TPP1B, TPP1C, TPP1D, TPP1E, TPP2A, TPP2B, TPP2C, TPP2D, and TPP1E individually and independently. This convention of use also applies to the foamable compositions table and the foam table below.

[0185] foaming agent

[0186] As explained in detail herein, the present invention includes, but is not limited to, the applicant’s discovery that a selected set of foaming agents can provide foamable PEF foam compositions and PEF foams with an unattainable and surprising combination of physical properties, including low density and good mechanical strength properties.

[0187] The blowing agent used according to the invention preferably comprises one or more hydrogen halide olefins having three or four carbon atoms. For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1.

[0188] The foaming agent used according to the present invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as foaming agent 2 for convenience); or comprises one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 3 for convenience); or comprises one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 4 for convenience); or comprises trans 1234z One or more of e and trans-1336mzz (hereinafter referred to as foaming agent 5 for convenience); or containing trans-1234ze (hereinafter referred to as foaming agent 6 for convenience); or containing trans-1336mzz (hereinafter referred to as foaming agent 7 for convenience); or containing cis-1336mzz (hereinafter referred to as foaming agent 8 for convenience); or containing 1234yf (hereinafter referred to as foaming agent 9 for convenience); or containing 1224yd (hereinafter referred to as foaming agent 10 for convenience); or containing trans-1233zd (hereinafter referred to as foaming agent 11 for convenience).

[0189] Therefore, it is contemplated that the foaming agents of the present invention (including each of foaming agents 1 to 11) may also include, in addition to each of the aforementioned foaming agents, a co-foaming agent comprising one or more optional potential co-foaming agents as described below. In a preferred embodiment, the foamable compositions, foams, and foaming methods of the present invention include foaming agents as described herein, wherein the foaming agents (including compounds or groups of compounds specifically identified in each of foaming agents 1 to 11) are present in an amount of at least about 50% by weight, or preferably at least about 60% by weight, preferably at least about 70% by weight, or preferably at least about 80% by weight, or preferably at least about 90% by weight, or preferably at least about 95% by weight, or preferably at least about 99% by weight, based on the total weight of all foaming agent components.

[0190] The foaming agent used according to the present invention is preferably composed substantially of one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as foaming agent 12 for convenience); or substantially composed of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 13 for convenience); or substantially composed of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 14 for convenience); or substantially composed of trans 1234ze and trans 13 It consists of one or more of the following 36mzz (hereinafter referred to as foaming agent 15 for convenience); or is essentially composed of trans 1234ze (hereinafter referred to as foaming agent 16 for convenience); or is essentially composed of trans 1336mzz (hereinafter referred to as foaming agent 17 for convenience); or is essentially composed of cis 1336mzz (hereinafter referred to as foaming agent 18 for convenience); or is essentially composed of 1234yf (hereinafter referred to as foaming agent 19 for convenience); or is essentially composed of 1224yd (hereinafter referred to as foaming agent 20 for convenience); or is essentially composed of trans 1233zd (hereinafter referred to as foaming agent 21 for convenience).

[0191] It is anticipated and understood that the foaming agents of the present invention (including each of foaming agents 1 to 21) may include one or more co-foaming agents not included in the illustrated selection, provided that the amount of such co-foaming agents used does not interfere with or eliminate the ability to obtain relatively low-density foams (including each of foams 1 to 4) as described herein, and preferably does not interfere with or eliminate the ability to obtain foams with mechanical strength properties as described herein. Therefore, in consideration of the teachings contained herein, it is anticipated that those skilled in the art will be able to select one or more of the following potential co-foaming agents for a particular application without excessive experimentation: one or more saturated hydrocarbons or hydrofluorocarbons (HFCs) known in the art, particularly C4-C6 hydrocarbons or C1-C4 HFCs. Examples of such HFC co-foaming agents include, but are not limited to, difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and one or a combination of all isomers of all such HFCs. Regarding hydrocarbons, in some preferred embodiments, the foaming agent composition of the present invention may further include, for example, isopentane, n-pentane and / or cyclopentane, and butane and / or isobutane. Other materials may also be included, such as water, CO2, CFCs (such as trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, such as dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (such as ethanol and / or propanol and / or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (such as dimethyl ether and diethyl ether), diethers (such as dimethoxymethane and diethoxymethane)) and methyl formate, organic acids (such as, but not limited to, formic acid), including any combination of these, but such components are not necessarily preferred in many embodiments due to their negative environmental impact.

[0192] The foaming 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 foaming agent 22 for convenience); or composed of one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 23 for convenience); or composed of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 24 for convenience); or composed of trans 1234ze and trans It may consist of one or more of 1336mzz (hereinafter referred to as foaming agent 25 for convenience); or consist of trans 1234ze (hereinafter referred to as foaming agent 26 for convenience); or consist of trans 1336mzz (hereinafter referred to as foaming agent 27 for convenience); or consist of cis 1336mzz (hereinafter referred to as foaming agent 28 for convenience); or consist of 1234yf (hereinafter referred to as foaming agent 29 for convenience); or consist of 1224yd (hereinafter referred to as foaming agent 30 for convenience); or consist of trans 1233zd (hereinafter referred to as foaming agent 31 for convenience).

[0193] Foam and foaming methods

[0194] The foams of the present invention (including each of foams 1 to 4) or foams made from the PEF polymers of the present invention (including thermoplastic polymers TPP1A to TPP22E, or any foam described in Examples 1 to 22) can generally be formed from the foamable compositions of the present invention. Generally, the foamable compositions of the present invention can be formed by combining the PEF polymers of the present invention (including each of thermoplastic polymers TPP1A to TPP22E) with the blowing agents of the present invention (including each of blowing agents 1 to 31).

[0195] The following tables of expandable compositions (Tables 3A and 3B) describe expandable compositions that are included in the present invention and provide specific advantages in relation to the formation of the foams of the present invention, wherein all numerical values ​​in the tables are understood to be preceded by the word "about", and wherein the following terms used in the tables have the following meanings:

[0196] CBAG1 refers to a foaming agent selected from the group consisting of: 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf, and combinations of two or more of these.

[0197] CBAG2 refers to a foaming agent selected from the group consisting of: water, CO2, C1-C6 hydrocarbons (HC), HCFC, C1-C5 HFC, C2-C4 hydrohalogenated olefins, C1-C5 alcohols, C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers, C1-C4 esters, organic acids, and combinations of two or more of these.

[0198] CCBAG3 refers to a foaming agent selected from the group consisting of: water, CO2, isobutane, n-butane, isopentane, cyclopentane, cyclohexane, trans-dichloroethylene, ethanol, propanol, butanol, acetone, dimethyl ether, diethyl ether, dimethoxymethane, diethoxymethane, methyl formate, difluoromethane (HFC-32), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), trifluoroethane (HFC-143), 1112-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and combinations of any two or more of these.

[0199] NR means not required.

[0200] Table 3A - List of Foamable Compositions

[0201]

[0202]

[0203]

[0204]

[0205]

[0206]

[0207] Table 3BA - Foamable Compositions

[0208]

[0209]

[0210] Foam Formation Methods

[0211] In light of the disclosure contained herein, it is contemplated that the foams of the present invention can be formed using any one or more of a variety of known techniques for forming thermoplastic foams, including each of foams 1 to 4 and foamable compositions 1 to 11, as well as all such techniques and all foams formed therefrom or within the broad scope of the present invention. For clarity, it should be noted that the definitions of foams in the table below all begin with the letter F, in contrast to the foams defined in the paragraphs of the above description of the invention, which begin with the capitalized word "Foamable Composition".

[0212] Typically, the formation step involves first introducing the inventive foaming agent, comprising each of the foaming agents 1 to 31, into the inventive PEF polymer comprising each of TPP1 to TPP22 to form a foamable PEF composition comprising PEF and a foaming agent. An example of a preferred method for forming the foamable PEF composition of the present invention is plasticizing the PEF, preferably comprising heating the PEF to its melting temperature, preferably above its melting temperature, and then exposing the PEF melt to the foaming agent under conditions that effectively incorporate the desired amount of foaming agent (preferably by dissolution) into the polymer melt.

[0213] In a preferred embodiment, the foaming method of the present invention includes providing a foamable composition of the present invention comprising each of FC1 to FC11, and foaming the provided foamable composition. In a preferred embodiment, the foaming method of the present invention includes providing a foamable composition of the present invention comprising each of FC1 to FC11, and extruding the provided foamable composition to form a foam of the present invention comprising each of foams 1 to 4 and each of foams F1 to F8. The foaming method of the present invention may include intermittent, semi-intermittent, continuous methods, and combinations of two or more of these methods. Intermittent methods generally involve preparing at least a portion of a foamable polymer composition in a storable state, comprising each of FC1 to FC11, and then using that portion of the foamable polymer composition to prepare foam at a future point in time. Semi-intermittent methods involve preparing at least a portion of a foamable polymer composition comprising each of FC1 to FC11, and intermittently expanding the foamable polymer composition into a foam comprising each of foams 1 to 4 and each of foams F1 to F11, all in a single method. For example, U.S. Patent No. 4,323,528, which is incorporated herein by reference, discloses a method for preparing thermoplastic foam by cumulative extrusion. Therefore, the present invention includes a method comprising: 1) mixing a homopolymer PEF thermoplastic polymer and / or copolymer PEF foam (preferably with a PET copolymer) (including each of TPP1-TPP22), a blowing agent composition of the present invention (including each of blowing agents 1-31), and preferably one or more blowing additives under conditions for forming a foamable PEF composition, wherein at least a majority, and preferably substantially all, of the blowing agent composition is dissolved in the polymer component of the foamable composition; 2) extruding the foamable PEF composition by maintaining the foamable PEF composition (including each of FC1 to FC11) in a holding region, the holding region being maintained in a state where foaming is not permitted. At the temperature and pressure at which the composition foams, the end of the holding zone preferably includes: a die head defining an orifice leading to a zone of lower pressure and temperature where the foamable polymer composition (including each of FC1 to FC11) foams; and an openable door that closes the die head orifice; 3) periodically opening the door while applying mechanical pressure substantially simultaneously to the foamable polymer composition (including each of FC1 to FC11) by a movable pressure head to discharge it from the holding zone through the die head orifice into the zone of lower pressure and temperature; and 4) causing the discharged foamable polymer composition to expand under the action of a foaming agent to form foam, including each of foams 1 to 4 and each of foams F1 to F8.

[0214] The present invention can also use a continuous method to form foam. For example, such a continuous method involves forming an expandable PEF composition, comprising each of FC1 to FC11, and then expanding the expandable PEF composition substantially without interruption. For example, a foamable PEF composition (including each of FC1 to FC11) can be prepared in an extruder as follows: heating a selected PEF homopolymer and / or copolymer resin (including each of TPP1 to TPP22) to form a PEF melt, incorporating the foaming agent composition of the present invention (including each of foaming agents 1 to 31) and optionally, but preferably, one or more foaming additives into the PEF melt, preferably by dissolving the foaming agent composition and additives (if present) into the PEF melt under initial pressure to form a foamable PEF composition comprising a substantially homogeneous combination of PEF and foaming agents (including each of FC1 to FC11), and then extruding the foamable PEF composition through a die into a zone under a selected foaming pressure, allowing the foamable PEF composition to expand into foam under the influence of the foaming agents, including each of foams 1 to 4 and each of foams F1 to F8 described below. Optionally, a foamable PEF composition comprising PEF homopolymers and / or copolymers (including each of FC1 to FC11) and incorporated blowing agents (including each of blowing agents 1 to 31) and blowing additives (when present) may be partially cooled before the composition is extruded through a die to enhance certain desired properties of the resulting foam (including each of foams 1 to 6 and each of foams F1 to F8).

[0215] This method can be used, for example, by using Figure 1The extrusion is performed using general-type extrusion equipment disclosed herein. Specifically, the extrusion apparatus may include a raw material feed hopper 10 for receiving the PEF polymer 15 of the present invention (including each of TPP1 to TPP22) and one or more optional components (which may be added together with the PEF in the hopper or optionally added elsewhere in the process, depending on the specific needs of the user). The feed 15 (which may include a portion of foaming agent and / or foaming additives) may be loaded into the hopper 10 and delivered to the screw extruder 20. The extruder 20 typically has a cooling section 50 located upstream of the die 60, in which cooling of the foamable composition may occur, and a mixing section 30 upstream of the cooling section, into which foaming agent (including each of foaming agents 1 to 31) and optional foaming additives may be added. The extruder preferably includes thermocouples (not shown) located at three points along its length and a pressure sensor (not shown), preferably between the discharge end of the extruder mixing section 30. Preferably, one or more metering pumps 40A and 40B are provided for introducing one or more of the foaming agent components and preferably one or more foam additives into the PEF melt in the mixer section 30. Sensors (not shown) may be included for monitoring the temperature and pressure of the mixer section 30. The mixer section 30 may then discharge the foamable composition melt of the present invention (including each of FC1 to FC11) into one or more melt coolers 50 preferably oriented in series, wherein temperature sensors (not shown) are located in each cooler to monitor the melt temperature. The melt is then extruded through a die 60, which also has temperature sensors and pressure sensors (not shown) for monitoring the temperature and pressure at the die. The die pressure and temperature may be varied according to the needs of each specific extrusion application that produces the foam 70 of the present invention (including each of foams 1 to 4 and each of foams F1 to F8 as described below). Preferably, a melt pump is provided before the die to help maintain the desired pressure. The foam can then be transported from the extrusion equipment by a conveyor belt 80.

[0216] The foamable polymer compositions of the present invention (including each of FC1-FC11) may optionally contain additional additives, including but not limited to chain extenders (including preferred chain extenders as described below and in the examples), chain branching agents (including preferred chain branching agents as described below and in the examples), nucleating agents, cell control agents, glass and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR attenuators, and thermal insulating additives. Nucleating agents particularly include materials such as talc, calcium carbonate, sodium benzoate, and chemical foaming agents such as azodicarbonamide or sodium bicarbonate and citric acid. IR attenuators and thermal insulating additives may include carbon black, graphite, silica, metal flakes or powders, etc. Flame retardants particularly include brominated materials such as hexabromocyclodecane and polybrominated diphenyl ethers. According to known techniques, each of the above-mentioned additional optional additives may be introduced into the foam at different times and locations in the process, and all such additives and methods of addition are within the broad scope of the present invention.

[0217] Foam

[0218] 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 embodiments herein:

[0219] Table 4

[0220]

[0221] Foams included within this invention and providing certain advantages are described in Table 5 below, wherein all values ​​in the table are understood to be preceded by the word "about", and wherein the name NR means "not required".

[0222] Table 5 - Foam Table

[0223]

[0224]

[0225]

[0226]

[0227]

[0228]

[0229]

[0230]

[0231]

[0232]

[0233]

[0234]

[0235]

[0236]

[0237]

[0238]

[0239]

[0240]

[0241]

[0242]

[0243]

[0244]

[0245]

[0246]

[0247]

[0248] The foams of this invention have a wide range of applications. The foams of this invention (including each of foams 1 to 4 and foams F1 to F11) have unexpected advantages in applications requiring low density and / or good compressive and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recycled materials and recyclable. In particular, the foams of this invention (including each of foams 1 to 6 and each of foams F1 to F8) have unexpected advantages in the following applications: wind energy applications (wind turbine blades (shear webs, shells, cores, and roots)); marine applications (hulls, decks, superstructures, bulkheads, chords, and interior trim); industrial low-weight applications; and automotive and transportation applications (internal and external parts of cars, trucks, trains, airplanes, and spacecraft).

[0249] PEF:PET copolymers can be formed in any manner known to those skilled in the art, including but not limited to the procedures described in the embodiments herein.

[0250] The foams of the present invention (including each of foams 1 to 4) are made of PEF homopolymer, PEF copolymer, PEF:PET copolymer or a combination / mixture thereof.

[0251] 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% by weight, or at least 99.9% by weight, an ethylene furanate portion.

[0252] The foams of the present invention (including each of foams 1 to 3) are intended to be formed from PEF copolymers in a preferred embodiment, wherein the polymer (including the PEF copolymer) has about 10% by weight to about 99% by weight of ethylene furanate portion. The present invention includes foams (including each of foams 1 to 3) wherein the thermoplastic polymer is substantially composed of the components described in the following table:

[0253]

[0254]

[0255] The foams of the present invention (including each of foams 1 to 3) may include closed-cell walls, which include each of the thermoplastic polymers of the present invention, including each of TMP1 to TMP12 as described in the table above.

[0256] For those embodiments of the invention involving PEF copolymers, in light of the teachings included herein, it is expected that those skilled in the art will be able to select the type of amount of copolymer material to be used within each of the ranges described herein to achieve the desired reinforcement / modification of the polymer without excessive experimentation.

[0257] It is anticipated that the TMP of the present invention can form polymers with a variety of physical properties, including the following polymer characteristic ranges, which are measured as described in the examples herein:

[0258]

[0259] In general, given the teachings contained herein, those skilled in the art will be able to formulate PEF polymers within the aforementioned property range without excessive experimentation. However, in preferred embodiments, PEF polymers (including the PEF:PET copolymers of the present invention) having these properties are achieved using one or more of the above-described synthetic methods, combined with various known supplementary processing techniques (including treatment with chain extenders such as PMDA, and / or SSP).

[0260] Foam and foaming methods

[0261] The foam of the present invention is a thermoplastic foam, and in view of the disclosure included herein, it is generally contemplated that any one or more of the various known techniques for forming thermoplastic foams may be used, and all such techniques and all foams formed therefrom are within the broad scope of the present invention.

[0262] Generally, the forming steps involve introducing a foaming agent into the PEF according to the invention to form a foamable PEF composition comprising PEF and a foaming agent. An example of a preferred method for forming such a foamable composition is plasticizing PEF, which preferably involves heating the PEF to its melting temperature, preferably above its melting temperature, and then exposing the PEF melt to the foaming agent under conditions that effectively incorporate the desired amount of foaming agent (preferably by dissolution) into the polymer melt.

[0263] The foaming methods of the present invention may include intermittent, semi-intermittent, continuous methods, and combinations of two or more of these methods. Intermittent methods typically involve preparing at least a portion of a foamable polymer composition in a storable state, and then using that portion of the foamable polymer composition to prepare foam at a future point in time. Semi-intermittent methods include preparing at least a portion of a foamable polymer composition and intermittently expanding the foamable polymer composition into foam in a single process. For example, U.S. Patent No. 4,323,528, incorporated herein by reference, discloses a method for preparing thermoplastic foam by a cumulative extrusion method. Therefore, the present invention includes the following method, comprising: 1) mixing a PEF thermoplastic polymer and the foaming agent of the present invention under conditions for forming a foamable PEF composition; 2) extruding the foamable PEF composition into a holding zone maintained at a temperature and pressure at which foaming of the foamable composition is not permitted, wherein the holding zone preferably includes a die defining an orifice leading to a low-pressure zone under which the foamable polymer composition foams, and the holding zone further includes an openable door that closes the die orifice; 3) periodically opening the door while applying mechanical pressure to the foamable polymer composition substantially simultaneously by a movable pressure head to discharge it from the holding zone through the die orifice into the low-pressure zone; and 4) causing the discharged foamable polymer composition to expand under the action of the foaming agent to form foam.

[0264] The present invention can also use continuous methods to form foam. For example, such continuous methods involve forming a foamable PEF composition and then allowing the foamable PEF composition to expand substantially uninterruptedly. For example, the foamable PEF composition can be prepared in an extruder as follows: heating a selected PEF polymer resin to form a PEF melt, incorporating the foaming agent of the present invention into the PEF melt, preferably by dissolving the foaming agent into the PEF melt at an initial pressure to form a foamable PEF composition comprising a substantially homogeneous combination of PEF and the foaming agent, and then extruding the foamable PEF composition through a die into a region at a selected foaming pressure and allowing the foamable PEF composition to expand into foam under the influence of the foaming agent. Optionally, the foamable PEF composition comprising the PEF polymer and the incorporated foaming agent can be cooled before extruding the composition through a die to enhance certain desired properties of the resulting foam.

[0265] The foamable compositions according to a preferred aspect of the invention may optionally contain additional additives, including but not limited to chain extenders (including preferred chain extenders described below and in the examples), chain branching agents (including preferred chain branching agents described below and in the examples), such as nucleating agents, cell control agents, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR attenuators, and thermal insulating additives.

[0266] Nucleating agents include, in particular, materials such as talc, calcium carbonate, and sodium benzoate, as well as chemical foaming agents such as azodicarbonamide or sodium bicarbonate and citric acid. IR attenuators and thermal insulation additives may include carbon black, graphite, silica, metal flakes or powders, etc. Flame retardants may include, in particular, brominated materials such as hexabromocyclodecane and polybrominated diphenyl ethers. According to known techniques, each of the above-mentioned optional additives may be introduced into the foam at different times and locations in the process, and all such additives and methods of addition are within the broad scope of this invention.

[0267] In a preferred embodiment, the foam of the present invention is formed in a commercial extrusion apparatus and has the characteristics shown in the table below, wherein the values ​​are measured as shown in the table and, as supplemented in the embodiments herein, should be understood to be modified by “about”:

[0268]

[0269] The foams of this invention have a wide range of applications. The foams of this invention (including each of foams 1 to 3) offer unexpected advantages in applications requiring low density and / or good compressive and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from and recyclable materials. In particular, the foams of this invention (including each of foams 1 to 3) offer unexpected advantages in: wind energy applications (wind turbine blades (shear webs, shells, cores, and nacelles); marine applications (hulls, decks, superstructures, bulkheads, chords, and interior trim); industrial low-weight applications; and automotive and transportation applications (internal and external components of cars, trucks, trains, airplanes, and spacecraft).

[0270] Example

[0271] Without limiting the full scope of the invention, the applicant conducted a series of experiments to demonstrate the practicality of the PEF homopolymers and PEF-based copolymers of the invention, and to compare the performance of foams prepared according to the invention with that of foams prepared from PET. These tests involved the synthesis of a range of PET polymers covering a range of physical properties, including molecular weight, crystallinity, and melting point. The applicant also prepared a range of PEF polymers (including homopolymers and copolymers) with similar ranges of physical properties. A series of foams were prepared using the highly preferred 1234ze(E) as a blowing agent. Foams prepared using other halogenated C3 and C4 olefin blowing agents according to the invention were also tested. For a given range of comparable polymer properties, a consistent set of extrusion processing conditions was used. Details of each of these extrusion result sets are explained in detail in the following examples. By summary, the following table provides an indication of some important polymer properties and the advantages of the foams of the invention relative to comparable foams prepared from PET homopolymers.

[0272]

[0273]

[0274] As shown in the table above, a unique set of extrusion conditions was determined for each polymer for the extrusion experiments. Apart from the amount of foaming agent, the extrusion conditions were kept substantially constant to produce strength data as a function of polymer expansion or foam relative density (RFD) in these foaming experiments. The extrusion conditions were selected to ensure appropriate expansion and foam formation.

[0275] The foam density was determined using a method typically corresponding to ASTM D71, used throughout the examples in this application, to test the resulting foams, except that hexane was used instead of water for displacement. For ease of comparison of the foam densities produced in these examples, the applicant has reported foam densities as relative foam density (RFD), which is the foam density measured as described above divided by the density of the starting polymer. In this document, all foam densities, whether derived from PEF or PET homopolymers or from PEF-PET copolymers, are normalized to the density of the PEF polymer at 1.43 g / cc, which is approximately 7% lower than that of PET. Thus, when comparing the strength of the various polymer foams under the same RFD, they are also compared at the same total density.

[0276] In addition, each of the foams produced in these embodiments was tested to determine tensile and compressive strength. Tensile and compressive strength measurements were based on guidelines provided in ASTM C297 and ISO 844, respectively, and in each case, measurements were taken in the extrusion direction but on samples without seams or weld lines.

[0277] Following these measurements, the applicant found that the foam produced in Example C3B4-1 had tensile and compressive strength values ​​equal to (i.e., within approximately 10%) the expected values ​​of a commercially available PET foam sample (110 kg / m³) tested under the applicant's experimental conditions. Therefore, for ease of comparison of the test results provided herein, the tensile and compressive strength values ​​of the foam produced in Example C2B4-1 are each set as a baseline value of 1, and all other foam strength results reported in these examples are reported as relative tensile strength (“RTS”) and relative compressive strength (“RCS”) relative to the foam of C2B4-1. For example, a foam with a measured tensile strength twice that of Example C2B4-1 is reported as having an RTS of 2.

[0278] Comparative Example C1A - Preparation of a PET homopolymer with a molecular weight of 105.3 kg / mol using PMDA and SSP 1

[0279] PET homopolymers with a molecular weight of about 105 kg / mol were prepared using the additives and polymer formation procedures described in Example C1A below.

[0280] The resulting homopolymer (referred to as PETC1) was tested and found to have the characteristics reported in Table C1 below:

[0281] Table C1

[0282]

[0283] 1The designation of embodiments as “comparisons” herein should not be construed as representing any item of the prior art, but is presented merely for comparison with preferred aspects of the invention presented in other embodiments.

[0284] 2 In all these embodiments, the molecular weights determined and mentioned herein refer to those determined by diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY NMR) according to the description contained in “Application of 1H DOSY NMR in Measurement of Polystyrene Molecular Weights”, *VNU Journal of Science: Natural Sciences and Technology*, Vol. 36, No. 2 (2020) 16-21, June 2020, Nam et al., except for the solvent used. The aforementioned references used 3 mg of polystyrene and 0.5 ml of deuterated chloroform. For these embodiments, NMR measurements were performed using a dissolved portion of 2 mg to 3 mg of the polymer in 0.6 ml of a mixture of 50 vol% deuterated chloroform and 50 vol% trifluoroacetic acid.

[0285] Comparative Example C1B - Preparation of PET Foam Using PET1A and 1234ze(E) Blowing Agent

[0286] In a series of tests, polymers as shown in Table CIA above were extruded in commercial extrusion equipment. The extrusion conditions used, including the amount of foaming agent, as well as the melt temperature and pressure, were determined after several tests based on the ability to form acceptable foams with RFD values ​​within the desired range.

[0287] The extruded foam produced in Comparative Example 1B was tested and found to have the characteristics reported in Table C1B below.

[0288] Table C1B

[0289]

[0290] The relative tensile strength, relative compressive strength, and combined relative tensile and compressive strength results of the foam reported in Table C1B above (hereinafter referred to as "RTS+RCS") are plotted as a function of relative foam density (RFD) on [the graph / table]. Figures 2A to 2C In the diagram, the dashed line is used to show a linear representation of the tensile strength data as a function of the relative foam density.

[0291] The chart shows that as the foam density increases within this density range, the tensile strength and compressive strength of PET foam are generally expected to increase (the dashed lines represent the linear trend of the data).

[0292] Comparative Example 2A - Preparations were made using PMDA and SSP with molecular weights in the range of 80 kg / mol to 96 kg / mol and a crystallinity of 32-. 43% PET homopolymer

[0293] Using the procedures described in Synthesis Examples C2A1, C2A2, C2A3 and variations thereof, four (4) PET homopolymers were prepared by polycondensation to produce polymer products having a molecular size range from about 80 kg / mol to about 96 kg / mol, to achieve a polymer with a molecular weight of 83,900, hereinafter referred to as PETC2A4.

[0294] The PET polymers are designated as PETC2A1, PETC2A2, PETC2A3, and PETC2A4 in this document, and have been tested and found to have the characteristics reported in Table C2A as follows:

[0295] Table C2A

[0296]

[0297] As shown in the table above, each of the PET homopolymers was prepared using the preferred high crystallinity aspect of the present invention. Therefore, the PET foam prepared using the blowing agent of the present invention has unexpectedly high strength compared to PET foam prepared from PET polymers that do not use this aspect of the present invention, as illustrated by comparison with the results of Comparative Example 1A.

[0298] Comparative Example 2B: Preparation of PET using PETC2A1, PETC2A2, PETC2A3 and PETC2A4 with 1234ze(E) foaming agent Foam

[0299] In a series of tests, the polymers shown in Table C2A above were extruded to form foams. After several tests, the conditions used, including the amount of blowing agent, as well as the melt temperature and pressure, were determined based on the ability to form acceptable foams with RFD values ​​in the range of about 0.05 to about 0.2.

[0300] The PET foam thus prepared in this embodiment C2B was tested and found to have the properties reported in Table C2B below.

[0301] Table C2B

[0302]

[0303] The unexpected ability to obtain high-strength PET foam with relatively low density and relatively high molecular weight and improved crystallinity by forming extruded foam using the preferred foaming agents of the present invention (including HFO-1234ze foaming agent used in this embodiment) is evident in... Figure 3A and Figure 3B As shown in the figures, these figures compare the TS and RTS+RCS results of the C2B1, C2B2, and C2B3 data of this comparative example with those of comparative example 1B.

[0304] The data provided in this embodiment demonstrate the unexpected advantages of aspects of the applicant's invention involving the formation of high-strength, low-density extruded thermoplastic foams (including PET foams and PEF foams (including PEF copolymers)) with relatively high crystallinity. In particular, by using PET polymers with a crystallinity greater than about 20%, and even more preferably greater than about 30%, as in the case of Example C2B, the tensile strength and RTS+RCS of the extruded foam are unexpectedly improved by about 2 times compared to polymers with higher molecular weight but lower (i.e., 13.9%) crystallinity.

[0305] Example 1A - Preparation of molecules with molecular weights from approximately 41 kg / mol to 75 kg / mol and crystallinity of 36% to 41 kg / mol using PMDA and SSP. 42% PEF homopolymer

[0306] Two homopolymers of PEF were prepared using the additives and polymer formation procedures described in Synthesis Examples 1A1 and 1A2, resulting in polymer products with a molecular size range of about 41 kg / mol to about 75 kg / mol.

[0307] The PEF polymers are designated as PEF1A1 and PEF1A2 in this document and were tested using the measurement scheme described above in Comparative Example 1A, and were found to have the characteristics reported in Table E1A below:

[0308] Table E1A

[0309]

[0310] The PEF polymers produced in these examples are referred to as PEF1A1 and PEF1A2 in Table E1 above and below.

[0311] Example 1B - Using PEF1A1 and PEF1A2 with trans 1234 ze Preparation of extruded PEF foam with foaming agent

[0312] One extruded foam was prepared using PEF1A1 and four foams were prepared using PEF1A2, and the foam extrusion method with the same standard design as described in Comparative Example 1B was used as described herein. The resulting foams were tested and found to have the properties reported in Table E1B below.

[0313] Table E1B

[0314]

[0315] As revealed by the data in Table E1B above, the applicant has surprisingly discovered that the extruded PEF foam according to the invention exhibits unexpectedly high tensile and compressive strength values ​​compared to PET foam at approximately equal crystallinity (based on the trend line), even compared to extruded PET foam according to the invention which uses higher crystallinity values ​​and has a substantially higher molecular weight than the extruded PEF foam. This is in Figure 4 As shown, for example, by comparing the trend line of the foam formed from PET of Comparative Example 1A in the range of relative foam density of 0.04-0.13, especially considering that the molecular weight of the extruded PEF foam of this embodiment is significantly lower than that of the extruded PET foam.

[0316] As revealed in the above charts and all the examples given herein, the extruded PEF foam of the present invention exhibits significantly superior strength properties compared to extruded PET foam. Referring particularly to the above charts, although foam strength typically increases with increasing molecular weight, the extruded PEF foam of the present invention is significantly stronger than extruded PET foam (within the same crystallinity range), even though the molecular weight of the extruded PEF foam is significantly lower than that of the extruded PET foam. Thus, for example, in this chart, at an RFD of approximately 0.08, the trend line for PEF has an RTS+RCS that is 1.3 times greater than that of the PET trend line, which is based on extruded PET foam formed at a much higher molecular weight. This result is highly advantageous and unexpected.

[0317] Example 2A - Preparation of PEF homopolymers with molecular weights ranging from approximately 90 kg / mol to 96 kg / mol using PMDA and SSP

[0318] Two PEF homopolymers were prepared using the additives and polymer formation methods described in Synthesis Examples 2A1 and 2A2, yielding polymer products with molecular sizes of about 90 kg / mol and about 96 kg / mol.

[0319] The resulting PEF polymer was tested using the measurement protocol described above in Comparative Example 1A and was found to have the characteristics reported in Table E2A below:

[0320] Table E2A

[0321]

[0322] The PEF polymers produced in these examples are referred to as PEF2A1 and PEF2A2 in Table E2A above and below.

[0323] Example 2B - Using PEF1A1 and PEF1A2 with trans 1234 ze Preparation of extruded PEF foam with foaming agent

[0324] Three types of foam were prepared using PEF2A1 and one type of foam was prepared using PEF2A2, as described herein, using the same standard design as described in Comparative Example 1B. The resulting foams were tested and found to have the properties reported in Table E2B below.

[0325] Table E2B

[0326]

[0327] As revealed by the data in Table E1B above, the applicant has surprisingly discovered that the extruded PEF foam according to the invention possesses unexpectedly high tensile strength and RTS+RCS values. This is illustrated, for example, by reference to the foam formed from extruded PET of Comparative Example 2A, as... Figure 5A and Figure 5B As shown, it includes extruded PET data from Table C2B for comparison purposes and trend lines for all extruded PET data from Table C2B.

[0328] As can be seen from the results of this embodiment, the extruded PEF homopolymer foam of the present invention exhibits unexpectedly superior strength compared to extruded PET homopolymer foam (including the preferred HFO-1234ze blowing agent of the present invention) prepared using the same foam forming technology of the present invention.

[0329] An unexpected advantage of the invention illustrated by this embodiment is the significantly higher relative tensile strength and the RTS+RCS of the foam, as summarized in Table E2C below:

[0330] Table E2C

[0331]

[0332] The results summarized in Table EIC above are particularly unexpected because the extruded PET foam of this embodiment is not disclosed in the prior art; that is, the extruded PET results combine the preferred aspects of the invention involving the formation of foam from polymers with relatively high crystallinity and high molecular weight using the preferred blowing agent of the invention (i.e., HFO-1234ze(E)). Furthermore, when foamed with other halogenated olefin blowing agents as shown in Example 14 herein, the PEF-based extruded foam foamed with HFO-1234ze(E) of the invention also unexpectedly outperforms the PEF-based extruded foam of the invention.

[0333] Example 3A - Preparation of PET9:PEF1 copolymer with a molecular weight of approximately 117.9 kg / mol using PMDA

[0334] Using the additives and polymer formation procedure described in Synthesis Example 3A, a block copolymer of PET9:PEF1 (mol ratio of 9:1) was prepared, wherein the target molecular weight of the PET portion of the copolymer was approximately 117,900 g / mol.

[0335] The resulting PET9:PEF1 copolymer was tested using the measurement scheme described above in Comparative Example 1A and was found to have the characteristics reported in Table E3A below:

[0336] Table E3A

[0337]

[0338] The resulting PET9:PEF1 copolymer is referred to as PET9PEF1-EX3A in these examples.

[0339] Example 3B - Using PET9PEF1-EX3A and trans 1234 ze Preparation of PEF foam with foaming agent

[0340] Six (6) foams were prepared from PET9PEF1-EX3A using an extrusion foaming method designed with the same standard as described in Comparative Example 1. The resulting foams were tested and found to have the properties reported in Table E3B below:

[0341] Table E3B

[0342]

[0343] As revealed by the data in Table E3B above, the applicant has surprisingly discovered that the extruded foam prepared using PET9:PEF1-EX3B according to the present invention has unexpectedly high strength properties.

[0344] Figures 6A to 6D The average tensile strength values ​​of extruded foam in three density regions are shown, i.e. in the following ranges at RFD: (i) 0.056-0.062; (ii) 0.077-0.079; and 0.171-0.177, as shown in Table E3B above, and average data from the same regions of PET data from Table C2B are included for comparison purposes.

[0345] As can be seen from the results of this embodiment, the extruded PET9:PEF1 copolymer foam of the present invention exhibits unexpectedly superior strength over a wide range of relative densities, as demonstrated by this embodiment in terms of significantly higher relative tensile strength and significantly higher compressive strength of the extruded foam. In particular, the extent of this unexpected advantage of the embodiment is summarized in Table E3C below:

[0346] Table E3C

[0347]

[0348] The context of these results includes the fact that the comparative examples combine preferred aspects of the invention involving the formation of extruded foams from polymers with relatively high crystallinity and high molecular weight and the preferred blowing agent of the invention (i.e., HFO-1234ze(E)).

[0349] Comparative Example 3B: Using PETC2A1 and PETC2A2 with 1234 ze (E) Preparation of PET foam with foaming agent

[0350] Seven types of foam (three from PETC2A1 and four from PETC2A2) were prepared using an extrusion foaming method designed with the same standard as described in Comparative Example 1. The resulting foams were tested and found to have the properties reported in Table C3B below.

[0351] Table C3B

[0352]

[0353] Example 4B - Using PEF2A2 and trans 1234 ze Preparation of PEF foam with foaming agent

[0354] Six (6) types of foam were prepared using PEF2A2, as described in Table E2A and using the same standard extrusion foaming method as described in Comparative Example 1B. The resulting foams were tested and found to have the properties reported in Table E4B below.

[0355] Table E4B

[0356]

[0357] As revealed by the data in Table E4B above, the applicant has surprisingly discovered that the extruded PEF foam according to the invention possesses unexpectedly high tensile and compressive strength values. This is illustrated, for example, by reference to the extruded foam formed from PET of Comparative Example C3B2, as... Figure 7 As shown in the charts, in particular, the comparative examples combine preferred aspects of the invention involving the formation of extruded foams from polymers with relatively high crystallinity and high molecular weight and the preferred blowing agent of the invention (i.e., HFO-1234ze(E)). Figure 7 Data results for foam are shown in the RFD region of approximately 0.116.

[0358] As can be seen from the results of this embodiment, the PEF homopolymer foam of the present invention exhibits unexpectedly superior strength compared to PET homopolymer foam (including the preferred HFO-1234ze blowing agent of the present invention) prepared using the same foam forming technology of the present invention. For example, as shown in this embodiment, the relative tensile strength and RTS+RCS of the extruded foam are significantly higher. In particular, the extent of this unexpected advantage is summarized in Table E4C below:

[0359] Table E4C

[0360]

[0361] Example 5A - Preparation of PET9:PEF1 with a molecular weight of approximately 45 kg / mol and a crystallinity of 28.6 CR% using PMDA polymer

[0362] Using the additive polymer formation steps described in Synthesis Example 5Ae, a block copolymer of PET9:PEF1 (mol ratio 9:1) was prepared, with a target molecular weight of approximately 45,000 g / mol for the PET portion of the copolymer.

[0363] The resulting PET9:PEF1 copolymer was tested using the measurement protocol described above in Comparative Example 1A and was found to have the characteristics reported in Table E5A below:

[0364] Table E5A

[0365]

[0366] The resulting PET9:PEF1 copolymer is referred to as PET9PEF1-EX5A in these examples.

[0367] Example 5B - Using PET9PEF1-EX5A and trans 1234 ze Preparation of PEF foam with foaming agent

[0368] Two (2) extruded foams were prepared from PET9PEF1-EX5A using the same standard foam extrusion method as described in Comparative Example 1. The resulting foams were tested and found to have the properties reported in Table E5B below:

[0369] Table E5B

[0370]

[0371] As revealed by the data in Table E5B above, the applicant has surprisingly discovered that the extruded foam prepared using PET9:PEF1-EX5B according to the present invention has unexpectedly high strength properties.

[0372] Figure 8The diagram shows a comparison of foam strength values ​​with the average values ​​of PETC3B2 foam (as reported in Table C3B above) in the same density ranges covering Table E5B above, namely approximately 0.05–0.06 and approximately 0.13–0.15.

[0373] As can be seen from the results of this embodiment, the extruded PET9:PEF1 copolymer foam of the present invention exhibits unexpectedly excellent strength, as shown in this embodiment, with significantly higher RCS in the range of RFD of about 0.06 and about 0.14. In particular, the extent of this unexpected advantage of the embodiment is summarized in Table E5C below:

[0374] Table E5C

[0375]

[0376] Examples 6A1 and 6A2 - Preparation of PET with a molecular weight of approximately 92 kg / mol to 97 kg / mol and high crystallinity using PMDA and SSP PET99:PEF1 copolymer with a Cr content of 28.8% to 33.5%

[0377] Two random copolymers of PET99: PEF1 (99:1 mol ratio) was prepared using the additives and polymer formation method or a variation thereof as described in the following synthesis example 6A1, with PET portions having target molecular weights of about 92 kg / mol and 97 kg / mol, and PET portions of copolymers having target molecular weights of about 45,000 g / mol, to obtain polymers with target molecular weights of 92,160.

[0378] The PET99:PEF1 copolymer was tested and found to have the characteristics listed in Table E6A:

[0379] Table E6A

[0380]

[0381] The resulting PET99:PEF1 copolymers are referred to as PET99PEF1-EX6A1 and PET99PEF1-EX6A2 in these examples.

[0382] Example 6B - Using PET99PEF1-EX6A1 and A2 with trans 1234 ze Foaming agent for foam preparation

[0383] Six (6) types of foam were prepared from PET99PEF1-EX6B using an extrusion method designed with the same standard as described in Comparative Example 1. The resulting foams were tested and found to have the properties reported in Table EB as follows:

[0384] Table E6B

[0385]

[0386] As revealed by the data in Table E6B above, the applicant has surprisingly discovered that the extruded foam prepared using PET99:PEF1-EX6A1 and EX6A2 according to the present invention has unexpectedly high strength properties.

[0387] Figure 9 The table above shows the tensile strength, compressive strength, and combined tensile and compressive strength values ​​of the foams. For ease of comparison, data from PET in Table C1B are also included.

[0388] As can be seen from the results of this embodiment, the extruded PET99:PEF1 copolymer foam of the present invention exhibits unexpectedly superior strength, as illustrated, for example, by comparison with the extruded PET homopolymer foam prepared from Comparative Example 1 using the preferred HFO-1234ze blowing agent of the present invention. As can be seen from the results of this embodiment, the PET homopolymer foam of the present invention exhibits unexpectedly superior strength compared to PET99:PEF1 copolymer foam (including the preferred HFO-1234ze blowing agent of the present invention) prepared using the same foam forming technology of the present invention. In particular, the extent of this unexpected advantage is summarized in Table E6C below:

[0389] Table E6C

[0390]

[0391] Example 7A1 - Preparation of PET19 with a molecular weight of approximately 46 kg / mol and a crystallinity of 30.2 Cr% using PMDA: PEF1 copolymer

[0392] Using the same additives and basic polymer formation steps as described in Synthesis Example 8A, a random copolymer of PET19:PEF1 (mol ratio of 19:1) was prepared from a PET portion with a target molecular weight of about 46 kg / mol, except that a PET with a target molecular weight of about 46 kg / mol was obtained.

[0393] The PET19:PEF1 copolymer was tested and found to have the characteristics listed in Table E7A:

[0394] Table E7A

[0395]

[0396] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX7A1 in this embodiment.

[0397] Example 7B - Preparation of foam using PET19PEF1-EX7A1 and trans-1234ze blowing agent

[0398] Foam was prepared from PET19PEF1-EX7A using an extrusion method designed with the same standard as described in Comparative Example 1. The resulting extruded foam was tested and found to have the properties reported in Table E7B below:

[0399] Table E7B

[0400]

[0401] As revealed by the data in Table E7B above, the applicant has found that extruded foams prepared using PET19:PEF1-EX7A1 according to the present invention exhibit extremely high strength properties. For example, foams produced using the relatively low-density copolymers of the present invention have strength values ​​that are advantageous compared to the average results of extruded PET homopolymer foams, which are identified in Table C3B above as C3B2-14 (RFD 0.063) and C3B2-2 (RFD 0.088), and whose molecular weights are almost twice that of the PET19:PEF1 copolymer of the present invention. Figure 10 The unexpected result is shown in the comparison with RTS+RCS.

[0402] Assuming that the molecular weight of the PET homopolymer is more than twice that of the PET19:PEF1 of this invention, it is unexpected that the strength values ​​of the extruded PET19:PEF1 foam are comparable.

[0403] Examples 8A1 and 8A2 - Preparation of PET with a molecular weight of approximately 72 kg / mol to 79 kg / mol and high crystallinity using PMDA and SSP The content of PET19:PEF1 copolymer ranges from 27.62% to 32%.

[0404] Using the additives and polymer formation methods described in Synthesis Examples 8A1 and 8A2, two random copolymers PET19:PEF1 (mol ratio 19:1) were prepared with PET portions having target molecular weights of about 72 kg / mol and about 79 kg / mol.

[0405] The PET19:PEF1 copolymer was tested and found to have the characteristics listed in Table E8A:

[0406] Table E8A

[0407]

[0408] The resulting PET19:PEF1 copolymers are referred to as PET19PEF1-EX8A1 and PET19PEF1-EX8A2 in this embodiment.

[0409] Example 8B - Using PET19PEF1-EX8A1 and EX8A2 with trans 1234 ze Foaming agent for foam preparation

[0410] Foam was prepared from each of PET19PEF1-EX8A1 and EX8A2 using an extrusion method with the same standard design as described in Comparative Example 1.

[0411] Tests were conducted on the resulting extruded foam and it was found to have the following properties:

[0412] The following features are reported in Table E8B:

[0413] Table E8B

[0414]

[0415] As revealed by the data in Table E8B above, the applicant has found that extruded foams prepared using PET19:PEF1-EX8A1 and EX8A2 according to the present invention exhibit extremely high strength properties. For example, the extruded foam of the present invention, with an average RFD of 0.091, exhibits advantageous strength values ​​compared to the extruded PET homopolymer foams identified as C3B1-2 and C3B2-2 in Table C3B above, which have the same average density as the PET19:PEF1 copolymer of this embodiment with an RFD. This unexpected result in Figure 11 As shown in the image.

[0416] Assuming the crystallinity of the extruded PET homopolymer foam is 1.3 times that of the extruded PET19:PEF1 copolymer foam, and the molecular weight (MW) of the extruded PET homopolymer is 1.2 times that of the extruded PET19:PEF1 foam in this embodiment, surprisingly, the strength value of the extruded PET19:PEF1 foam will be comparable to that of the extruded PET19:PEF1 foam.

[0417] The extruded foam formed from PET homopolymer is comparable, and quite unexpectedly, the relative compressive strength of the present invention will be greater than those values ​​of PET homopolymer, resulting in a combined RTS+CTS value that is also higher than that of foam formed from PET homopolymer.

[0418] Example 9A1 - Preparation of PET with a molecular weight of approximately 62 kg / mol and a crystallinity of 26.1 Cr% using PMDA and SSP PET19:PEF1 copolymer

[0419] Using the same additives and basic polymer formation steps as described in Synthesis Example 8A, a random copolymer of PET19:PEF1 (mol ratio of 19:1) was prepared from a PET portion with a target molecular weight of about 62 kg / mol, except that a PET with a target molecular weight of about 62 kg / mol was obtained.

[0420] The PET19:PEF1 copolymer was tested and found to have the characteristics listed in Table E9A:

[0421] Table E9A

[0422]

[0423] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX9A1 in this embodiment.

[0424] Example 9B - Using PET19PEF1-EX9A1 and trans 1234 ze Foaming agent for foam preparation

[0425] Foam was prepared from PET19PEF1-EX9A using a foam extrusion method designed according to the same standard as described in Comparative Example 1. The resulting extruded foam was tested and found to have the properties reported in Table E9B below:

[0426] Table E9B

[0427]

[0428] As revealed by the data in Table E9B above, the applicant has found that extruded foams prepared using PET19:PEF1-EX9A1 according to the present invention exhibit extremely high strength properties. For example, the strength values ​​of extruded foams produced using the relatively low-density copolymer of the present invention are advantageous compared to extruded PET homopolymer foams identified as C3B1-3 in Table C3B above (whose density is 0.104, and therefore very close to the density of extruded foams formed from the PET19:PEF1 copolymer of the present invention). This unexpected result in Figure 12 As shown in the image.

[0429] Assuming that the molecular weight of the extruded foam made from PET homopolymer is more than 1.5 times that of the foam formed from PET19:PEF1 of the present invention, it is entirely unexpected that each reported strength value of the PET19:PEF1 extruded foam will be substantially equivalent to the strength value of the PET homopolymer extruded foam.

[0430] Example 10A - Preparation of PET with a molecular weight of approximately 79 kg / mol and a crystallinity of 32.4 Cr% using PMDA and SSP PET19:PEF1 copolymer

[0431] Using the additives and basic polymer formation steps described in Synthesis Example 8A, PET19:PEF1 (mol ratio 19:1) was prepared from a PET fraction with a target molecular weight of approximately 79 kg / mol.

[0432] The random copolymers, unlike the others, yielded PET with a target molecular weight of approximately 79 kg / mol.

[0433] The PET19:PEF1 copolymer was tested and found to have the characteristics listed in Table E10A:

[0434] Table E10A

[0435]

[0436] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX10A in this embodiment.

[0437] Example 10B - Using PET19PEF1-EX10A and trans 1234 ze Foaming agent for foam preparation

[0438] Extruded foams were prepared from PET19PEF1-EX10A using an extrusion method designed according to the same standard as described in Comparative Example 1. The resulting extruded foams were tested and found to possess the properties reported in Table E10B below:

[0439] Table E10B

[0440]

[0441] As revealed by the data in Table E10B above, the applicant has found that the extruded foam prepared using PET19:PEF1-EX1OA according to the present invention exhibits extremely high strength properties. For example, the extruded foam of this embodiment has a density of 0.13, but exhibits a strength value that is considerably better than that of extruded foam made from PET homopolymers having substantially the same density but a much higher molecular weight. In particular, the extruded PET homopolymer foam identified as C3B1-4 in Table C3B above has a density of 0.129, and its molecular weight is 20% higher than that of the PET19:PEF1 copolymer used to prepare the foam of the present invention. However, the strength values ​​of the two foams are unexpectedly comparable, as... Figure 13 As shown.

[0442] Assuming that the molecular weight of the PET homopolymer is about 20% higher than that of PET19:PEF1 in this embodiment, it is completely unexpected that the reported extruded foam strength value of each PET19:PEF1 will be approximately the same as that of the PET homopolymer.

[0443] Example 11A - Preparation of PET with a molecular weight of approximately 83 kg / mol and a crystallinity of 20.7 Cr% using PMDA and SSP PET19:PEF1 copolymer

[0444] As described in the following synthesis example 11A, a block copolymer PET19:PEF1 (19:1 mol ratio) was prepared using a PET fraction with a target molecular weight of about 83 kg / mol.

[0445] The PET19:PEF1 copolymer was tested and found to have the characteristics shown in Table E11A:

[0446] Table E11A

[0447]

[0448] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX11A in this embodiment.

[0449] Example 11B - Using PET19PEF1-EX10A and trans 1234 ze Foaming agent for foam preparation

[0450] Foam was prepared from PET19PEF1-EX11A using a foam extrusion method designed with the same standard as described in Comparative Example 1. The resulting extruded foam was tested and found to have the properties reported in Table E11B below:

[0451] Table E11B

[0452]

[0453] As revealed by the data in Table E11B above, the applicant has found that the extruded foam prepared using PET19:PEF1-EX11A according to the present invention exhibits extremely high strength properties. For example, the extruded foam of this embodiment is made from a copolymer having a PET portion with a molecular weight of about 83 kg / mol and a crystallinity of about 21%, but still exhibits a strength value that is good or even exceeds that of a PET homopolymer foam made from a polymer with substantially the same density but a molecular weight 1.2 times higher and a crystallinity 1.6 times higher. In particular, the extruded PET homopolymer foam identified as C3B1-4 in Table C3B above has a density of 0.129 and a relative compressive strength, for example, a relatively low density compressive strength that is substantially lower than that of the PET19:PEF1 data of this embodiment. Figure 14 As shown.

[0454] Assuming that the molecular weight of the PET homopolymer is about 20% higher than that of PET19:PEF1 in this embodiment, and that the crystallinity is about 60% higher, it is completely unexpected that each reported strength value of the PET19:PEF1 extruded foam will be approximately the same as or slightly higher than that of the extruded foam made from the PET homopolymer.

[0455] Examples 12A1 and 12A2 – Preparations of molecular weights from approximately 57 kg / mol to 69 kg / mol using ADR and PMDA, talc and SSP. PET9:PEF1 copolymer with a crystallinity of 28 Cr% to 34 Cr% mol

[0456] Using the additives and polymer formation procedures described in Synthesis Examples 12A1 and 12A2, two (2) block copolymers of PET9:PEF1 (mol ratio of 9:1) with a target molecular weight of about 57 kg / mol to about 69 kg / mol were prepared for the PET portion of the copolymer.

[0457] The resulting PET9:PEF1 copolymer was tested using the measurement protocol described above in Comparative Example 1A and was found to have the characteristics reported in Table E12A below:

[0458] Table E12A

[0459]

[0460] The resulting PET9:PEF1 copolymers are referred to as PET9PEF1-EX12A1, PET9PEF1-EX12A2, and PET9PEF1-EX12A3 in these examples.

[0461] Example 12B - Using PET9PEF1-EX12A1 and trans 1234 ze Preparation of PEF foam with foaming agent

[0462] Three (3) types of foam were prepared from PET9PEF1-EX12A1 using a foam extrusion method designed with the same standard as described in Example 5A. The resulting extruded foams were tested and found to have the properties reported in Table E12B1 below:

[0463] Table E12B1

[0464]

[0465] As revealed by the data in Table E12B above, the applicant has surprisingly discovered that the extruded foam prepared using PET9:PEF1-EX12A1 according to the present invention has unexpectedly high strength properties.

[0466] Figure 15 The strength values ​​of the extruded foam compared to the PET9:PEF1 foam prepared using PMDA in Example 5 are shown in the same density regions covered in Table E5B above, namely approximately 0.05-0.06 and approximately 0.13-0.15.

[0467] The results of this embodiment show that PET9:PEF1-EX12 can be made into an acceptable extruded foam with good expansion.

[0468] Example 12C - Using PET9PEF1-EX12A2 and trans 1234 ze Preparation of PEF foam with foaming agent

[0469] Extruded foam was prepared from PET9PEF1-EX12A2 using the same standard extrusion foaming method as described in Example 5A. The resulting extruded foam was tested and found to have the properties reported in Table E12B2 below:

[0470] Table E12B2

[0471]

[0472] As revealed by the data in Table E12B2 above, the applicant has surprisingly discovered that the extruded foam prepared using PET9:PEF1-EX12A2 according to the present invention has unexpectedly high strength properties.

[0473] Figure 16 The strength values ​​of the extruded foam compared to the PET9:PEF1 foam prepared using PMDA in Example 5 are shown in the density region shown in Table E5B above, i.e., between about 0.055 and about 0.144.

[0474] The results of this embodiment show that PET9:PEF1-EX12 can be made into an acceptable extruded foam with good expansion.

[0475] Examples 13A1 and 13A2 - using PEN TA PET9 with molecular weights of approximately 47 kg / mol and 12 kg / mol was prepared using SSP. PEF1 and PET19:PEF1 copolymer

[0476] Using the PENTA additive, a first block copolymer of PET9:PEF1 (mol ratio of 9:1) with a target PET molecular weight of about 47 kg / mol and PET and PEF oligomer blocks of 1-5 (monomers) and 1-5 (monomers) was prepared using the polymer formation procedure described in Synthesis Example 13A to achieve a target molecular weight of 47,030, or variations were made to Synthesis Example 13A to achieve a target molecular weight of about 45,000 kg / mol or about 12,000 kg / mol.

[0477] The resulting PET:PEF copolymer was tested using the measurement scheme described above in Comparative Example 1A and was found to have the characteristics reported in Table E13A below:

[0478] Table E13A

[0479]

[0480] The resulting PET9:PEF1 copolymers are referred to as PET9PEF1-EX13A1, PET9PEF1-EX13A2 and PET9PEF1-EX13A3 in these examples, as shown in Table E13A above.

[0481] Example 13B1 - Using PET9PEF1-EX13A1 and trans 1234 ze Preparation of PEF foam with foaming agent

[0482] Foam was prepared from PET9PEF1-EX13A1 using the same standard extrusion foaming method as described in Comparative Example 5, except that PENTA was used instead of PMDA. The resulting extruded foam was tested and found to have the properties reported in Table E13B below:

[0483] Table E13B1

[0484]

[0485] As revealed by the data in Table E13B1 above, the applicant has surprisingly discovered that the extruded foam prepared using PET9:PEF1-EX13A1 according to the present invention has unexpectedly high strength properties.

[0486] Figure 17 The strength values ​​of the extruded foam are shown in the density region of the foam shown in Table E5B above, with a value of about 0.055, compared to the PET9:PEF1 foam prepared using PMDA in Example 5.

[0487] The results of this embodiment show that PET9:PEF1-EX12 can be made into an acceptable extruded foam with good expansion.

[0488] Example 13B2 - Preparation of PET19:PEF1 copolymer with a molecular weight of approximately 45 kg / mol using PENTA

[0489] Foam was prepared from PET19PEF1-EX13A2 using the same standard extrusion foaming method as described in Example 7, except that PENTA was used instead of PMDA. The resulting foam was tested and found to have the properties reported in Table E13B2 below:

[0490] Table E13B2

[0491]

[0492] As revealed by the data in Table E13B2 above, the applicant has surprisingly discovered that the extruded foam prepared using PET9:PEF1-EX13A2 according to the present invention has unexpectedly high strength properties.

[0493] Figure 18 The strength values ​​of the extruded foam are shown in the density region of the foam shown in Table E7B above, with a value of about 0.08, compared to the extruded PET9:PEF1 foam prepared using PMDA in Example 7.

[0494] The results of this embodiment show that PET9:PEF1-EX12 can be made into an acceptable extruded foam with good expansion.

[0495] Example 13B3 - Preparation of PET19:PEF1 copolymer with a molecular weight of approximately 11.69 kg / mol using PENTA and SSP

[0496] Foam was prepared from PET19PEF1-EX13A3 using the same standard extrusion method as described in Example 9B, except that PENTA was used instead of PMDA. The resulting foam was tested and found to have the properties reported in Table E13B3 as follows:

[0497] Table E13B3

[0498]

[0499] As revealed by the data in Table E13B3 above, the applicant has been surprised to find that the foam prepared using PET9:PEF1-EX13A3 according to the present invention has unexpectedly high strength properties.

[0500] Figure 19 The strength values ​​of the foam shown in Table E97B above, in the density region of the foam having a value of about 0.107, are compared with the PET9:PEF1 foam prepared using PMDA in Example 9.

[0501] The results of this embodiment show that PET9:PEF1-EX12 can be made into an acceptable foam with good expansion.

[0502] Example 14B - Using PET9:PEFl_Ex3A and trans-123zd, trans-1233zd and cis-1336 foaming agents Prepare PET9:PEF1 foam

[0503] A series of foams were prepared using PET9:PEFl_Ex3A using an extrusion foaming method designed with the same standard as described in Comparative Example 1B.

[0504] The resulting foam was tested and found to have the properties reported in Table E14B below.

[0505] Table E14B

[0506]

[0507] As revealed by the data in Table E1B above, the applicant has surprisingly found that, when the blowing agent contains or is substantially composed of 1234ze(E), the extruded PET:PEF foam according to the present invention generally exhibits superior strength characteristics compared to other blowing agents including 1233zd and 1336, as revealed by the data in the table above. However, when the blowing agent contains or is substantially composed of 1233zd(E) or 1336mzz(Z), acceptable extruded foams with considerable practicality are prepared, as revealed by the data above.

[0508] Comparative Example 4A - Preparation of a PET homopolymer with a molecular weight of 46.4 kg / mol using PMDA and SSP

[0509] PET homopolymers were prepared using the same design conditions as described in Comparative Example 1, but with process conditions aimed at preparing polymers in the molecular weight range of 40,000 g / mol to 50,000 g / mol. As in Comparative Example 1, the polymer was treated with 0.7 wt% of the chain extender PMDA according to known techniques, and then solid-state polymerization was carried out as described in Comparative Example 1 to prepare the PET homopolymers. The PET homopolymers were tested and found to have the characteristics reported in Table C4A below:

[0510] Table C4A

[0511]

[0512] The resulting PET polymer is referred to as PETC4A in these examples.

[0513] Comparative Example 4B: Preparation of PET Foam Using PETC4A and 1234ze(E) Blowing Agent

[0514] Two (2) types of foam were prepared using an extrusion foaming method designed according to the same standards as described in Comparative Example 1B. The extruded foam produced in Comparative Example 4 was tested and found to have the characteristics reported in Table C4B below:

[0515] Table C4

[0516]

[0517] Example 15A - Preparation of PEF homopolymer with a molecular weight of approximately 49 kg / mol using PMDA and SSP

[0518] PEF homopolymers were prepared using the same additives and basic polymer-forming procedures as those used to form the PET homopolymer of Comparative Example 3 to obtain a polymer molecular weight of approximately 49,000 g / mol. Specifically, the 49 kg / mol PEF homopolymer was formed by esterification and polycondensation of 75 g of 2,5-furandicarboxylic acid (FDCA) with 59.8 g of monoethylene glycol (EG). The reactants were added to a 500 mL cylindrical steel reactor equipped with a top stirrer and a distillation / condensation device. After evacuation and refilling with nitrogen, 0.067 g of titanium isopropoxide (IV) catalyst was added to the flask. The flask was then lowered into a 180 °C salt bath, and top mixing was initiated at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under nitrogen, evacuation was initiated. After 40 minutes under vacuum, the temperature was raised to 230 °C and maintained for 1 hour. Under a nitrogen stream, 0.58 g (0.7 wt%) of PMDA was slowly added over approximately 5 minutes. For SSP (Sequencing Sample Spray), aliquots (30 g) of the product were ground and heated in a rotary evaporator at 180 °C under vacuum for 3 days to produce the PEF homopolymer described below. The PEF homopolymer was tested using the same measurement techniques as described in Comparative Example 1 and was found to have the characteristics reported in Table E15 below:

[0519] Table E15

[0520]

[0521] The resulting PEF polymer is referred to as PEF15A in Table E3 and the examples below.

[0522] Example 15B: Preparation of PEF foam using PEF3 and trans-1234ze as blowing agents

[0523] Three types of foam were prepared from PEF2 using an extrusion foaming method with the same standard design as described in Comparative Example 1, as described herein. The resulting extruded foams were tested and found to have the properties reported in Table 15A below:

[0524] Table E15A

[0525]

[0526] Surprisingly, the extruded foam prepared with lower molecular weight PEF in this embodiment did not exhibit a significant decrease in tensile strength compared to PET foam prepared with higher molecular weight PET. This result was unexpected. Therefore, the tensile strength of the extruded foam made from a PEF homopolymer with a molecular weight of 49K and a blowing agent of 1234ze(E) was significantly better than that of the extruded foam made from a PET homopolymer with a molecular weight of 46.5K and a blowing agent of 1234ze(E). This unexpected result can be demonstrated, for example, by observing that the average RFD of three PEF data points according to the invention resulted in an average density of 0.079 and an average relative tensile strength of 1.34. Compared to extruded PET foam with a density more than 200% greater than the average density of extruded PEF foam, the PEF foam of the present invention still produces an average tensile strength four times that of high-density PET foam (0.35). This is a very important and unexpected result.

[0527] Example 16 - Preparation of PET9:PEF1 copolymer with a molecular weight of approximately 133.8 kg / mol using PMDA and SSP

[0528] A random copolymer of PET9:PEF1 (mol ratio 9:1) was prepared by adding 8.7 g (0.0472 mol) methyl furanate (FDME), 106.8 g (0.42 mol) bis(2-hydroxyethyl) terephthalate (BHET), and 6.2 g (0.1 mol) EG to a 500 mL cylindrical steel reactor equipped with a top stirrer and distillation / condensation device. After evacuation and backfilling with N2, 0.046 g of titanium isopropoxide (IV) catalyst was added. The reactor was then placed in a 180 °C salt bath, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes under N2, vacuum was introduced. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 40 minutes. 0.59 g of PMDA (0.0027 mol) was slowly added under N2 atmosphere. Before stopping the reaction, allow mixing at this temperature for an additional 30 minutes. Solid-state polymerization was then carried out by grinding equal portions (30 g) of the above product and then heating under vacuum at 180°C for 3 days on a rotary evaporator. Testing of the PEF polymer revealed that it possessed the characteristics shown in Table E7.

[0529] Table E16

[0530]

[0531] The resulting PET9:PEF1 random copolymer is referred to as PET9PEF1-EX16 in these examples.

[0532] Example 16B1-16B3 - Preparation of PETPEF co-foaming agents using PET9PEF1-EX16B and trans-1234ze as blowing agents Polymer foam

[0533] Three (3) extruded foams were prepared from PET9PEF1-EX16B using the same standard extrusion foaming method as described in Comparative Example 1. The resulting extruded foams were tested and found to have the properties reported in Table E16B as follows:

[0534] Table E16B

[0535]

[0536] As revealed by the data in Table E16B above, the applicant has surprisingly discovered that extruded foams prepared from PEF9:PET1-EX16B according to the present invention exhibit unexpectedly superior tensile strength compared to extruded foams formed from PET homopolymers. Figure 20 As shown, it includes PET tensile strength data from comparative examples for comparison.

[0537] like Figure 20 As shown, compared with extruded foam made from PET9PEF1-EX16B copolymer containing a relatively low percentage of PEF portion (about 10 mol%) and using 1234ze(E) as a blowing agent, extruded foam exhibits superior relative tensile strength.

[0538] For example, one aspect of this unexpected result can be shown by noting that the two extruded foams prepared from the PET9PEF1-EX16B copolymer have an average relative tensile strength of 0.89 at an RFD of approximately 0.062. Conversely, at the same RFD of approximately 0.062, based on the trend line of PET data, the extruded PET homopolymer has a relative tensile strength of approximately 0.52, as shown by the dashed line in the graph above. This indicates that the relative tensile strength of the PET9PEF1 foam of the applicant's embodiment is approximately 1.7 times that of the extruded foam made from the PET homopolymer. Similarly, at an RFD of approximately 0.088, the PET9PEF1 extruded foam has a relative tensile strength of 1.41. Conversely, at the same RFD of approximately 0.088, based on the PET trend line, the extruded PET homopolymer foam has a relative tensile strength of approximately 0.75. This indicates that the relative tensile strength is approximately 1.9 times that of the applicant's PET9PEF1 foam. These are important and unexpected results.

[0539] Comparative Example C5: Preparation of PET homopolymer with a molecular weight of approximately 38 kg / mol using PMDA and SSP

[0540] PET homopolymers were prepared by adding approximately 93 g (0.3659 mol) of bis(2-hydroxyethyl) terephthalate (BHET) to a 500 mL round-bottom flask. After evacuation and backfilling with N2, the flask was lowered to a 180 °C salt bath, and top mixing was initiated at 100 rpm under a flow of N2. 0.13 g (0.00045 mol) of titanium isopropoxide catalyst was added to the flask. After 1 hour, the bath temperature was raised to 230 °C. At this temperature, after 30 minutes under N2, a vacuum was initiated and maintained for 1 hour, then the temperature was further raised to 285 °C. After two hours at 285 °C, pyromellitic dianhydride PMDA (0.49 g; 0.0022 mol) was slowly added over approximately 10 minutes. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out by grinding an aliquot (30 g) of the above product and then heating it under vacuum at 180 °C for 3 days on a rotary evaporator. Testing of the PET homopolymer prepared in this manner revealed that it possessed the characteristics reported in Table C5 below:

[0541] Table C5

[0542]

[0543] The resulting PET polymer is referred to as PETC3 in these examples.

[0544] Comparative Example 6: Preparation of PET foam using PETC3 with 1234ze(E) blowing agent

[0545] In Comparative Example 6, extruded foam was generated and tested, and it was found to have the characteristics reported in Table C6 below:

[0546] Table C6

[0547]

[0548] Example 17A - Preparation of PEF homopolymer with a molecular weight of 33 kg / mol using PMDA and SSP

[0549] PEF homopolymers were prepared using the same additives and basic polymer-forming procedures as those used to form the PEF homopolymer of Comparative Example 3 to obtain a polymer molecular weight of approximately 30,000 kg / mol. Specifically, PEF homopolymers were formed by esterification and condensation polymerization of 2,5-furandicarboxylic acid with monoethylene glycol according to methods consistent with those described herein, and then treated with 0.7 wt% PMDA according to known techniques. The polymer was then subjected to solid-state polymerization consistent with the previous examples to produce PEF homopolymers. The PEF polymers were tested using the same measurement techniques described in Comparative Example 1 and were found to have the characteristics reported in Table E17A below:

[0550] Table E17A

[0551]

[0552] The PEF polymer produced in this embodiment is referred to as PEF-Exl7A in Table E17A above and below.

[0553] Examples 17B-1 and 17B: Preparation of PEF foam using PEF-Exl7A and trans-1234ze as blowing agents

[0554] Two extruded foams were prepared from PEF-EX17A using an extrusion foaming method with the same standard design as described in these embodiments. The resulting extruded foams were tested and found to possess the properties reported in Table E17A below:

[0555] Table E17A

[0556]

[0557] Surprisingly, the tensile strength of extruded foam made from PEF homopolymer and 1234ze(E) blowing agent is significantly better than that of extruded foam made from PET homopolymer and 1234ze(E) blowing agent. It is important to note in this respect that the molecular weight of the PET used to prepare the extruded PET foam (37.6K) is reasonably close to the molecular weight of the extruded PEF foam (33K), making the data comparable from a molecular weight perspective. This unexpected result can be shown, for example, by first averaging two PEF data points according to the invention with an RFD less than 0.1, and then noting that the average density of these two points is 0.0805 and the average relative tensile strength is 1.34. The PEF foam of the present invention still produces an average tensile strength equal to that of PET foam, compared to PET foam with a density greater than 2.4 times that of foam made from the PEF of the present invention. This is a very important and unexpected result.

[0558] Surprisingly, the extruded foam made from PEF homopolymer and 1234ze(E) blowing agent exhibits significantly better compressive strength than foam made from PET homopolymer and 1234ze(E) blowing agent. This unexpected result can be observed, for example, by first averaging two PEF data points according to the invention with an RFD less than 0.1, and noting that the average density of these two points is 0.0805 and the average relative compressive strength is 0.84. Compared to PET foam, which has a density more than twice the average PEF foam density, the PEF foam of the present invention still produces an average tensile strength equal to that of PET foam. This is a very important and unexpected advantage of PEF foam compared to PET foam.

[0559] Example 18A - Preparation of PET9:PEF1 copolymer with a molecular weight of approximately 133.8 kg / mol using PMDA and SSP

[0560] A random copolymer of PET9:PEF1 (mol ratio 9:1) was prepared by adding 8.7 g (0.0472 mol) methyl furanate (FDME), 106.8 g (0.42 mol) bis(2-hydroxyethyl) terephthalate (BHET), and 6.2 g (0.1 mol) EG to a 500 mL cylindrical steel reactor equipped with a top stirrer and distillation / condensation device. After evacuation and backfilling with N2, 0.046 g of titanium isopropoxide (IV) catalyst was added. The reactor was then placed in a 180 °C salt bath, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes under N2, vacuum was introduced. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 40 minutes. 0.59 g of PMDA (0.0027 mol) was slowly added under N2 atmosphere. Before stopping the reaction, allow mixing at this temperature for an additional 30 minutes. Solid-state polymerization was then carried out by grinding equal portions (30 g) of the above product and then heating under vacuum at 180°C for 3 days in a rotary evaporator. Testing of the PEF polymer revealed that it possessed the characteristics shown in Table E18A:

[0561] Table E18A

[0562]

[0563] The resulting PET9:PEF1 random copolymer is referred to as PET9PEF1-EX18A in these examples.

[0564] Examples 18B1, 18B2, and 18C3 – Preparation of extrusions using PET9PEF1-EX18A and trans-1234ze as foaming agents Molded PETPEF copolymer foam

[0565] Three (3) extruded foams were prepared from PET9PEF1-EX18A using the same standard extrusion foaming method as described in Comparative Example 1. The resulting extruded foams were tested and found to have the properties reported in Table E18B as follows:

[0566] Table E18B

[0567]

[0568] As revealed by the data in Table E18B above, the applicant has surprisingly discovered that the extruded foam prepared from PEF9:PET1-EX18A according to the present invention has unexpectedly superior tensile strength to the extruded foam formed from PET homopolymer, including PET tensile strength data from comparative examples for comparison.

[0569] Extruded foams made from PET9PEF1-EX18A copolymer (which contains a relatively low percentage of PEF portion (about 10 mol%) and uses 1234ze(E) as a blowing agent) exhibit superior relative tensile strength compared to foams made from comparative PET homopolymer foams, even though they are formed using the preferred 1234ze(E) blowing agent of the present invention.

[0570] For example, one aspect of this unexpected result can be shown by noting that the two extruded foams prepared from the PET9PEF1-EX7 copolymer have an average relative tensile strength of 0.89 at an RFD of approximately 0.062. Conversely, at the same RFD of approximately 0.062, based on the trend line of PET data, the PET homopolymer has a relative tensile strength of approximately 0.52, as shown by the dashed line in the graph above. This indicates that the relative tensile strength of the PET9PEF1 foam of the applicant's embodiment is approximately 1.7 times that of the foam made from the PET homopolymer. Similarly, at an RFD of approximately 0.088, the PET9PEF1 foam has a relative tensile strength of 1.41. Conversely, at the same RFD of approximately 0.088, according to the PET trend line, the PET homopolymer foam has a relative tensile strength of approximately 0.75. This indicates that the relative tensile strength is approximately 1.9 times that of the applicant's PET9PEF1 foam. These are important and unexpected results.

[0571] Example 19A - Preparation of PET1:PEF9 copolymer with a molecular weight of approximately 85 kg / mol using PMDA and SSP

[0572] A random copolymer of PET1:PEF9 (mol ratio 1:9) with a target molecular weight of approximately 85,000 g / mol was prepared. Specifically, 90.7 g of FDME (0.49 mol), 13.9 g of BHET (0.055 mol), and 64.1 g of EG (1.03 mol) were added to a 500 mL round steel reactor with a top stirrer and distillation / condensation apparatus. After evacuation and backfilling with N2, 0.074 g of titanium isopropoxide (IV) catalyst was added. The flask was then lowered to a 180 °C salt bath, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under N2, evacuation was initiated. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 2 hours. Under N2 atmosphere, 0.68 g of PMDA was slowly added. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Equal portions (30g) of the above product were ground and then subjected to solid-state polymerization under vacuum at 180°C for 3 days in a rotary evaporator. The resulting copolymer was a random copolymer with a PET:PEF ratio of 1:9 and a PET:PEF ratio of 1:1. Testing of the PEF polymer revealed a molecular weight of approximately 85-100.

[0573] The resulting PET1:PEF9 copolymer is referred to as PET1PEF9-EX19A in these examples.

[0574] Example 19B - Preparation of PET1PEF9 copolymer foam using PET1PEF9EX11 and trans-1234ze as blowing agents foam

[0575] An extruded foam was prepared from PET1PEF9-EX19A using an extrusion foaming method designed with the same standard as described in the comparative examples. The resulting extruded foam was tested and found to have the properties reported in Table E19B below:

[0576] Table El9B

[0577]

[0578] As revealed by the data in Table E19B above, the applicant has surprisingly discovered that the tensile strength of extruded foam prepared using the PET1:PEF9-EX19A copolymer of the present invention is unexpectedly superior to that of extruded foam formed from PET homopolymer. The tensile strength of the extruded foam made from the PET1PEF9-EX19A copolymer (which contains approximately 10% PET and uses 1234ze(E) as a blowing agent) is significantly superior to that of the comparative PET homopolymer made using 1234ze(E) as a blowing agent. In this respect, it is important to note that the molecular weights of the PET homopolymers used to prepare the extruded PET foam (83.9 kg / mol and 105.3 kg / mol) are sufficiently close to the molecular weight of the foam prepared using the PET1PEF9-EX19A copolymer (85.1 K) to make the data comparable to those of the PET homopolymer from a molecular weight perspective.

[0579] One aspect of this unexpected result can be shown, for example, by noting that the foam made from the PET1PEF9 copolymer exhibits a tensile strength of 1.2 at an RFD of approximately 0.063. Conversely, at the same RFD of approximately 0.063, the PET homopolymer has a tensile strength of approximately 0.6, based on the trend line. This indicates that the tensile strength of the PET1PEF9 foam of this embodiment is approximately twice that of the foam made from the PET homopolymer. This is an important and unexpected result.

[0580] Example 20 - Preparation of PET9:PEF1 copolymer with a molecular weight of approximately 65.7 kg / mol using PMDA chain extender and SSP

[0581] A block copolymer of PET9:PEF1 (mol ratio 9:1) with a target molecular weight of approximately 65,000 g / mol was prepared, with PET and PEF blocks in a 1-5, 1-3 configuration. Specifically, PEF was first prepared by adding 498 g of FDCA (2.7 mol) and 417 g of EG (6.72 mol) to a 1000 mL cylindrical glass reactor equipped with a top stirrer and a distillation / condensation apparatus immersed in a 190 °C salt bath. After purging with nitrogen, 0.414 g of titanium isopropoxide (IV) catalyst was added to the flask, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under N2, vacuum was applied. After 40 minutes under vacuum, the temperature was raised to 240 °C and maintained for 2 hours, after which the reaction was stopped, and PEF was produced.

[0582] 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 a top stirrer. The mixture was heated to boiling (196 °C), and then an aliquot (160 g) of PEF from the previous step was added. The mixture was allowed to react under reflux for 2 hours until the reaction was stopped. The resulting mixture was the PEF oligomer.

[0583] PET oligomers were prepared by adding EG (28 g) and sodium carbonate (0.46 g) to a 500 mL cylindrical reactor equipped with a condenser and a top stirrer. The mixture was heated until boiling (196 °C). Then 170 g of commercially available PET was added. The mixture was allowed to react under reflux for 2 hours until the reaction stopped. The result was a mixture of PET oligomers.

[0584] The copolymer was prepared by rapidly adding 7.14 g of PEF oligomer and 67.9 g of PET oligomer to a 500 mL cylindrical steel reactor equipped with a top stirrer and a distillation / condensation device immersed in a 220 °C salt bath. Shortly thereafter (<2 minutes), a vacuum was applied to remove EG. After 40 minutes, the temperature was raised to 270 °C, and the contents of the reactor were held under vacuum for 40 minutes. Under a nitrogen atmosphere, 0.46 g of PMDA was slowly added at approximately 5-minute intervals. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was then carried out by grinding an aliquot (30 g) of the product and heating it under vacuum at 180 °C for 3 days on a rotary evaporator.

[0585] The PET9:PEF1 copolymer was tested and found to have the characteristics listed in Table E20A:

[0586] Form E20A

[0587]

[0588] The resulting PET:PEF block copolymer is referred to as PET9PEF1-EX20A in these examples.

[0589] Examples 20B1, 20B2 and 20B3 - prepared using PET9PEF1-EX20A and trans-1234ze as foaming agents PETPEF copolymer foam

[0590] Three (3) extruded foams were prepared from PET9PEF1-EX20A using an extrusion foaming method designed with the same standard as described in the examples above. The resulting extruded foams were tested and found to have the properties reported in Table E20B as follows:

[0591] Table E20B

[0592]

[0593] As the data in Table E20B above reveals, applicants have been surprised to find that... Figure 20A As shown, the extruded PET9:PEF1-EX2OB copolymer foam according to the present invention unexpectedly exhibits superior tensile strength compared to extruded foams formed from comparable PET homopolymers, and for comparative purposes, it includes PET tensile strength data from comparative examples. Figure 20B As shown, the compressive strength of the foam prepared using the PET9PEF1 copolymer and 1234ze(E) of this invention is as good as that of the foam with an RFD greater than 0.07, and is substantially and unexpectedly better than the compressive strength exhibited by the foam prepared from PET homopolymer. Referring to the above RFD data of 0.07, the extruded foam made from the PET9PEF1 copolymer exhibits an average relative compressive strength of 1.065, while based on the trend line, the PET foam at this RFD has a compressive strength of about 0.7. Therefore, at densities above 0.07, based on the PET data trend line, the extruded foam made from the PET9PEF1 copolymer and 1234ze(E) produces 1.5 times the compressive strength of the foam made from the PET homopolymer. This is an important and unexpected result.

[0594] Example 21 - Preparation of PET1:PEF9 copolymer with a molecular weight of approximately 25 kg / mol using PMDA and SSP

[0595] A random copolymer of PET1:PEF9 (mol ratio 1:9) was prepared, with a target molecular weight of approximately 25,000 g / mol and a 1:1 ratio of PET and PEF blocks. Specifically, 40 g of FDME (0.26 mol), 7.24 g of BHET (0.0285 mol), and 31.8 g of EG (0.5123 mol) were added to a 250 mL round-bottom flask equipped with a stir bar. After evacuation and backfilling with N2, the flask was lowered to a 180 °C salt bath, and top mixing was initiated at 100 rpm under a flow of N2. Then, 0.04 g of isopropanol Ti(IV) catalyst was added. After 2.5 hours, the bath temperature was raised to 230 °C. After 30 minutes at this temperature under N2, evacuation was initiated and maintained for 2 hours. Under N2 atmosphere, 0.313 g of PMDA was slowly added at approximately 10-minute intervals. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out by grinding equal portions (20g) of the above product and then heating them at 180°C under vacuum for 3 days in a rotary evaporator. The PET1:PEF9 copolymer was tested and found to possess the characteristics listed in Table E21A.

[0596] Table E21A

[0597]

[0598] The resulting PET1:PEF9 random copolymer is referred to as PET1PEF9-EX21A in these examples.

[0599] Examples 21B1 and 21B2 - Preparation of PETPEF co-foaming agents using PET1PEF9-EX21A and trans-1234ze as blowing agents Polymer foam

[0600] Extruded foam was prepared from PET1PEF9-EX21A using the same standard extrusion foaming method as described in the examples above. The resulting extruded foam was tested and found to have the properties reported in Table E21B below:

[0601] Table E2IB

[0602]

[0603] As revealed by the data in Table E21B above, the applicant has surprisingly discovered that the extruded PEF foam of the PET1PEF9-EX21B copolymer according to the present invention has unexpectedly superior tensile strength compared to extruded foam formed from PET. Figure 25 As shown, it includes PET tensile strength data from comparative examples for comparison.

[0604] Synthesis Examples

[0605] Synthesis Example 1A1

[0606] A PEF homopolymer with a molecular weight of 41.2 kg / mol was formed by esterification and polycondensation of 75 g of 2,5-furandicarboxylic acid (FDCA) and 55 g of monoethylene glycol (EG). The reactants were added to a 500 mL cylindrical steel reactor equipped with a top stirrer and a distillation / condenser. After evacuation and repurging with nitrogen, 0.228 g of titanium isopropoxide (IV) catalyst was added to the flask. The flask was then lowered to a 180 °C salt bath, and top mixing was initiated at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under nitrogen, evacuation was initiated. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 1 hour. PMDA (0.5732 g) was slowly added over approximately 5 minutes under a nitrogen flow. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. To perform SSP, aliquots of the product were ground and heated in a rotary evaporator at 180°C under vacuum for 3 days to produce a PEF homopolymer with a molecular weight of 41 kg / mol as reported in Example 1A.

[0607] Synthesis Example 1A2-75000

[0608] Specifically, a 75 kg / mol PEF homopolymer was formed by esterification and polycondensation of 350 g of 2,5-furandicarboxylic acid (FDCA) and 279 g of monoethylene glycol (EG). The reactants were added to a 1-liter cylindrical steel reactor equipped with a top stirrer and a distillation / condenser. After evacuation and refilling with nitrogen, 0.228 g of titanium isopropoxide (IV) catalyst was added to the flask. The flask was then lowered to a 180°C salt bath, and top mixing was initiated at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. After 30 minutes at this temperature and under nitrogen, evacuation was initiated. After 40 minutes under vacuum, the temperature was raised to 230°C and maintained for 1 hour. PMDA (2.73 g - 0.7 wt%) was slowly added over approximately 5 minutes under a nitrogen flow. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. To perform SSP, aliquots (30 g) of the product were ground and heated in a rotary evaporator at 180 °C under vacuum for 3 days to produce a PEF homopolymer with a molecular weight of 75 kg / mol as reported in Example 1A.

[0609] Synthesis Example 2A1 - Preparation of PEF homopolymers with a molecular weight range of approximately 90 kg / mol using PMDA and SSP

[0610] For a polymer with a molecular weight of 90.8 kg / mol, FDCA (75 g) and EG (54.6 g) were added to a 500 mL cylindrical steel reactor equipped with a top stirrer and a distillation / condenser. After evacuation and refilling with nitrogen, 0.100 g of titanium isopropoxide (IV) catalyst was added to the flask. The flask was then lowered to a 180 °C salt bath, and top mixing was initiated at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under nitrogen, evacuation was initiated. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 2 hours. PMDA (0.587 g) was slowly added over a time span of approximately 5 minutes under a nitrogen flow. The reaction was stopped after mixing at this temperature for another 30 minutes. The product was removed from the container. γ-valerol 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-valerol was distilled from the polymer under vacuum to obtain a solid. For SSP, aliquots (30 g) of the product were ground and heated under vacuum at 180 °C for 3 days on a rotary evaporator to produce a PEF homopolymer with a molecular weight of 90.8 kg / mol as reported in Example 2A.

[0611] Synthesis Example 2A2 - Preparation of PEF homopolymers with a molecular weight range of approximately 96 kg / mol using PMDA and SSP

[0612] For a polymer concentration of 96,078 g / mol MW, 75 g of 2,5-furandicarboxylic acid (FDCA) and 55 g of monoethylene glycol (EG) were used. The reactants were added to a 500 mL cylindrical steel reactor equipped with a top stirrer and a distillation / condenser. After evacuation and refilling with nitrogen, 0.228 g of titanium isopropoxide (IV) catalyst was added to the flask. The flask was then placed in a 180 °C salt bath, and top mixing was initiated at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under nitrogen, evacuation was initiated. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 1 hour. PMDA (0.5732 g) was slowly added over approximately 5 minutes under a nitrogen flow. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. To perform SSP, aliquots of the product were ground and heated in a rotary evaporator at 180°C and under vacuum for 3 days to produce a PEF homopolymer as described below. The product was removed from the container. γ-valerol 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-valerol was distilled off from the polymer under vacuum to obtain a solid. To perform SSP, aliquots of the product were ground and heated in a rotary evaporator at 180°C and under vacuum for 3 days to produce a PEF homopolymer with a molecular weight of 96,078 as reported in Example 2A.

[0613] Synthesis Example 3A - Preparation of PET9:PEF1 copolymer with a molecular weight of approximately 117.9:90.4 kg / mol using PMDA and SSP thing

[0614] A block copolymer of PET9:PEF1 (mol ratio 9:1) with a target molecular weight of approximately 117,900 g / mol was prepared, with 4 PET blocks and 4 PEF blocks. Specifically, PEF was first prepared by adding 498 g of FDCA (2.7 mol) and 417 g of EG (6.72 mol) to a 1000 mL cylindrical glass reactor equipped with a top stirrer and a distillation / condenser, which was immersed in a 190 °C salt bath. After purging with nitrogen, 0.414 g of titanium isopropoxide (IV) catalyst was added to the flask, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under N2, vacuum was applied. After 40 minutes under vacuum, the temperature was raised to 240 °C and maintained for 2 hours, after which the reaction was stopped, and PEF was produced.

[0615] 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 a top stirrer. The mixture was heated until it boiled in a salt bath at 230 °C. An aliquot (160 g) of PEF from the previous step was added. The mixture was allowed to react under reflux for 2 hours until the reaction was stopped. The resulting mixture was the PEF oligomer.

[0616] PET oligomers were prepared by adding 103 g of EG and 0.45 g of sodium carbonate to a 500 mL cylindrical reactor equipped with a condenser and a top stirrer. The mixture was heated in a salt bath at 230 °C. Then, 160 g of commercially available recycled PET flakes was added. The mixture was allowed to react under reflux for 2 hours until the reaction stopped. The result was a mixture of PET oligomers.

[0617] 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 a top stirrer and a distillation / condensation device immersed in a 220 °C salt bath. Shortly thereafter (<2 minutes), a vacuum was applied to remove EG. After 40 minutes, the temperature was raised to 270 °C, and the contents of the reactor were held under vacuum for 40 minutes. Under a nitrogen atmosphere, 0.483 g of PMDA was slowly added. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out as follows: aliquots (30 g) of the above product were ground and then heated in a rotary evaporator under vacuum at 180 °C for 3 days to produce a PET9:PEF1 copolymer with a PET molecular weight of 117.9 kg / mol as reported in Example 3A.

[0618] Synthesis Example 5A - Preparation of PET9:PEF1 block copolymer with a molecular weight of approximately 44.9 kg / mol using PMDA and SSP

[0619] A block copolymer of PET9:PEF1 (mol ratio of 9:1) with a target molecular weight of approximately 44,900 g / mol was prepared, with 6 PET blocks and 7 PEF blocks.

[0620] PEF oligomers were prepared by adding 40.5 g of EG and 0.174 g of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and a top stirrer. The mixture was heated to 230 °C until the catalyst was completely dissolved. 59.5 g of commercially available PEF was added, and the mixture was refluxed under N2 for 2 hours. The resulting mixture was the PEF oligomer.

[0621] PET oligomers were prepared by adding 235 g of EG and 1.0 g of sodium carbonate to a 1000 mL cylindrical reactor equipped with a condenser and a top stirrer. The mixture was heated to 230 °C until the catalyst was completely dissolved. Commercially available PET (364 g) was added, and the mixture was refluxed under N2 for 2 hours. The result was a mixture of PET oligomers.

[0622] The copolymer was prepared by rapidly adding 12 g of PEF oligomer and 111.7 g of PET oligomer (both melted at 160 °C) to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation device immersed in a 220 °C salt bath. Shortly thereafter (<2 min), a vacuum was slowly applied to remove EG. After 40 min, the temperature was raised to 270 °C, and the contents of the reactor were held under vacuum for 40 min. Under a N2 atmosphere, 0.483 g of PMDA was slowly added. Mixing was allowed for an additional 30 min at this temperature before stopping the reaction, yielding a polymer with a molecular weight of approximately 34,900 g / mol. Aliquots of this sample were set to 60 M and crystallized at 165 °C under N2 for 4 h. The crystallized product was then subjected to solid-state polymerization in a rotary evaporator under vacuum at 180°C for 1 day to produce a PET9:PEF1 copolymer with a molecular weight of 117.9 kg / mol as reported in Example 5A.

[0623] Synthesis Example 6A1 - Preparation of PET99:PEF1 random copolymer with a molecular weight of approximately 97.2 kg / mol using PMDA and SSP thing

[0624] A random copolymer of PET99:PEF1 (99:1 mol ratio) was prepared by adding 0.68 g (0.0037 mol) methyl furanate (FDME), 93.0 g (0.366 mol) bis(2-hydroxyethyl) terephthalate (BHET), and 0.46 g (0.0074 mol) EG to a 500 mL round-bottom flask equipped with a top stirrer and distillation / condenser. After evacuation and backfilling with N2, 0.138 g of titanium isopropoxide (IV) catalyst was added. The reactor was then placed in a 180 °C salt bath, and top mixing was initiated at 100 rpm under N2 atmosphere. After 1 hour, the bath temperature was raised to 230 °C. After 30 minutes, the temperature was raised to 270 °C. After 2.5 hours at this temperature under N2, vacuum was initiated and maintained for 3 hours. 0.50 g of PMDA (0.0023 mol) was slowly added under N2 atmosphere. Mixing at this temperature was allowed for an additional 25 minutes before clamping the mixer to produce a polymer with a molecular weight of approximately 58,000 g / mol. Solid-state polymerization was carried out as follows: equal portions of the above product were ground and then heated in a rotary evaporator under vacuum at 180°C for 1 day to produce a PET99:PEF1 copolymer with a molecular weight of 97,190 g / mol as reported in Example 6A.

[0625] A variation of this technique was used to produce a PET99:PEF1 copolymer with a molecular weight of 92,190 g / mol, as reported in Example 6A.

[0626] Synthesis Examples 8A1 and 8A2 - Preparation of molecules with molecular weights of approximately 72 kg / mol and 79 kg / mol using PMDA and SSP PET19:PEF1 random copolymer

[0627] A random copolymer of PET95:PEF5 (95:5 mol ratio) was prepared by adding 3.54 g (0.0192 mol) methyl furanate (FDME), 93.0 g (0.366 mol) bis(2-hydroxyethyl) terephthalate (BHET), and 2.39 g (0.0385 mol) EG to a 500 mL round-bottom flask equipped with a top stirrer and distillation / condenser. After evacuation and backfilling with N2, 0.144 g of titanium isopropoxide (IV) catalyst was added. The reactor was then placed in a 180 °C salt bath, and top mixing was initiated at 100 rpm under N2 atmosphere. After 1 hour, the bath temperature was raised to 230 °C. After 30 minutes, the temperature was raised to 270 °C. After 1 hour at this temperature under N2, vacuum was initiated and maintained for 2 hours. 0.515 g of PMDA (0.0024 mol) was slowly added under N2 atmosphere. The mixture was further mixed at this temperature for 30 minutes to obtain a polymer with a molecular weight of approximately 40,000 g / mol. Solid-state polymerization was carried out as follows: equal portions of the above product were ground and then heated in a rotary evaporator under vacuum at 180°C for 1 day to produce a PET19:PEF1 copolymer with a molecular weight of 72.6 kg / mol as reported in Example 7A1.

[0628] A variation of this technique was used to produce a PET19:PEF1 copolymer with a molecular weight of 79 kg / mol, as reported in Example 7A2. Specifically, a random copolymer of PET95:PEF5 (mol ratio 95:5) was prepared by adding 3.54 g (0.0192 mol) methyl furanate (FDME), 93.0 g (0.366 mol) bis(2-hydroxyethyl) terephthalate (BHET), and 2.39 g (0.0385 mol) EG to a 500 mL round-bottom flask equipped with a top stirrer and a distillation / condenser. After evacuation and backfilling with N2, 0.144 g of titanium isopropoxide (IV) catalyst was added. The reactor was then placed in a 180°C salt bath, and top mixing was initiated at 100 rpm under a N2 atmosphere. After 1 hour, the bath temperature was increased to 230°C. After 30 minutes, the temperature was increased to 270°C. After 1 hour at this temperature under N2 atmosphere, a vacuum was initiated and maintained for 2 hours. 0.515 g of PMDA (0.0024 mol) was slowly added under N2 atmosphere. The mixture was then stirred for another 30 minutes at this temperature to obtain a polymer with a molecular weight of approximately 40,000 g / mol. Equal portions of the above product were ground and then subjected to solid-state polymerization under vacuum at 180°C for 1 day in a rotary evaporator to produce a PET19:PEF1 copolymer with a molecular weight of 79 kg / mol, as reported in Example 7A2.

[0629] Synthesis Example 11A - Preparation of PET95:PEF5 block copolymer with a molecular weight of approximately 83 kg / mol using PMDA

[0630] A block copolymer of PET95:PEF5 (mol ratio of 95:5) with a target molecular weight of approximately 83,000 g / mol was prepared, with 7 PET blocks and 7 PEF blocks.

[0631] PEF oligomers were prepared by adding 40.5 g of EG and 0.174 g of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and a top stirrer. The mixture was heated to 230 °C until the catalyst was completely dissolved. 59.5 g of commercially available PEF was added, and the mixture was refluxed under N2 for 2 hours. The resulting mixture was the PEF oligomer.

[0632] PET oligomers were prepared by adding 235 g of EG and 1.0 g of sodium carbonate to a 1000 mL cylindrical reactor equipped with a condenser and a top stirrer. The mixture was heated to 220 °C until the catalyst was completely dissolved. Commercially available PET (364 g) was added, and the mixture was refluxed under N2 for 2 hours. The result was a mixture of PET oligomers.

[0633] The copolymer was prepared by rapidly adding 6 g of PEF oligomer and 117.9 g of PET oligomer (both melted at 160 °C) to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation device immersed in a 220 °C salt bath. Shortly thereafter (<2 min), a vacuum was slowly applied to remove EG. After 40 min, the temperature was raised to 270 °C, and the contents of the reactor were held under vacuum for 40 min. Under a nitrogen atmosphere, 0.483 g of PMDA was slowly added. The mixture was then stirred at this temperature for another 30 min before stopping the reaction to prepare a PET19:PEF1 copolymer with a PET molecular weight of 83.033 g / mol as reported in Example 11A.

[0634] Synthesis Example 12A1 - Preparation of PET9:PEF1 copolymer with a molecular weight of approximately 56 kg / mol using ADR

[0635] A random copolymer of PET9:PEF1 (mol ratio 9:1) was prepared by adding 8.7 g (0.0472 mol) methyl furanate (FDME), 107.6 g (0.42 mol) bis(2-hydroxyethyl) terephthalate (BHET), and 6.22 g (0.1 mol) EG to a 500 mL cylindrical steel reactor equipped with a top stirrer and distillation / condensation device. After evacuation and backfilling with N2, 0.0503 g of titanium isopropoxide (IV) catalyst was added. The reactor was then placed in a 180 °C salt bath, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes under N2, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 250 °C and maintained for 2 hours. 1.1507 g of ADR-4468 was slowly added under N2 atmosphere. Before stopping the reaction, mixing was allowed at this temperature for an additional 30 minutes. Solid-state polymerization was carried out as follows: equal portions (30 g) of the above product were ground and then heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PET9:PEF1 copolymer with a PET molecular weight of 56,794 g / mol as reported in Example 12A1.

[0636] Synthesis Example 12A2 - Preparation of PEF homopolymer with a molecular weight of approximately 70 kg / mol using PMDA, talc, and SSP.

[0637] A block copolymer of PET9:PEF1 (mol ratio 9:1) with a target molecular weight of approximately 117,900 g / mol was prepared, with 5 PET blocks and 4 PEF blocks. Specifically, PEF was first prepared by adding 498 g of FDCA (2.7 mol) and 417 g of EG (6.72 mol) to a 1000 mL cylindrical glass reactor equipped with a top stirrer and a distillation / condenser, which was immersed in a 190 °C salt bath. After purging with nitrogen, 0.414 g of titanium isopropoxide (IV) catalyst was added to the flask, and top mixing was initiated at 200 rpm under N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220 °C. After 30 minutes at this temperature and under N2, vacuum was applied. After 40 minutes under vacuum, the temperature was raised to 240 °C and maintained for 2 hours, after which the reaction was stopped, and PEF was produced.

[0638] 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 a top stirrer. The mixture was heated until it boiled in a salt bath at 230 °C. An aliquot (160 g) of PEF from the previous step was added. The mixture was allowed to react under reflux for 2 hours until the reaction was stopped. The resulting mixture was the PEF oligomer.

[0639] PET oligomers were prepared by adding 136 g of EG and 0.68 g of sodium carbonate to a 500 mL cylindrical reactor equipped with a condenser and a top stirrer. The mixture was heated in a salt bath at 230 °C. Then, 210 g of commercially available recycled PET flakes were added. The mixture was allowed to react under reflux for 2 hours until the reaction stopped. The result was a mixture of PET oligomers.

[0640] The copolymer was prepared by rapidly adding 10.15 g of PEF oligomer and 97.64 g of PET oligomer to a 500 mL cylindrical steel reactor equipped with a top stirrer and a distillation / condensation device immersed in a 220 °C salt bath. Shortly thereafter (<2 minutes), a vacuum was applied to remove EG. After 40 minutes, the temperature was raised to 270 °C, and the contents of the reactor were held under vacuum for 40 minutes. Under a nitrogen atmosphere, a mixture of 0.4615 g of PMDA and 0.3317 g of talc was slowly added. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out as follows: aliquots of the above product were ground and then heated under vacuum at 180 °C for 3 days on a rotary evaporator to produce a PET9:PEF1 copolymer with a PET molecular weight of 69,900 g / mol as reported in Example 12A2.

[0641] Synthesis Example 13A - Preparation of PET9:PEF1 block copolymer with a molecular weight of about 47 kg / mol using pentaerythritol

[0642] A block copolymer of PET9:PEF1 (mol ratio of 9:1) with a target molecular weight of approximately 47,000 g / mol was prepared, with 6 PET blocks and 7 PEF blocks.

[0643] PEF oligomers were prepared by adding 40.5 g of EG and 0.174 g of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and a top stirrer. The mixture was heated to 230 °C until the catalyst was completely dissolved. 59.5 g of commercially available PEF was added, and the mixture was refluxed under N2 for 2 hours. The resulting mixture was the PEF oligomer.

[0644] PET oligomers were prepared by adding 235 g of EG and 1.0 g of sodium carbonate to a 1000 mL cylindrical reactor equipped with a condenser and a top stirrer. The mixture was heated to 230 °C until the catalyst was completely dissolved. Commercially available PET (364 g) was added, and the mixture was refluxed under N2 for 2 hours. The result was a mixture of PET oligomers.

[0645] The copolymer was prepared by rapidly adding 12 g of PEF oligomer and 111.7 g of PET oligomer (both melted at 160 °C) to a 500 mL cylindrical steel reactor, followed by the addition of 0.332 g of pentaerythritol and 0.9 g of titanium isopropoxide (IV). The cylindrical steel reactor was equipped with a top-mounted stirrer and a distillation / condensation device immersed in a 220 °C salt bath. Shortly thereafter (<2 minutes), a vacuum was slowly applied to remove EG. After 40 minutes, the temperature was raised to 270 °C, and the contents of the reactor were held under vacuum for 40 minutes.

[0646] Synthesis Example C1A - Preparation of PEF homopolymer with a molecular weight of approximately 105 kg / mol using PMDA and SSP

[0647] Approximately 163 g of bis(2-hydroxyethyl) terephthalate (BHET) and 0.114 g of titanium isopropoxide (IV) were added to a 500 mL cylindrical reactor. The reactor was then lowered to a 180 °C salt bath, and top mixing was initiated at 200 rpm under a N2 atmosphere. After 1.5 hours, the bath temperature was raised to 250 °C. After 30 minutes at this temperature and under N2, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 280 °C and maintained for 1 hour. Under N2 atmosphere, 0.66 g of PMDA was slowly added at approximately 5-minute intervals. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out by grinding an aliquot (30 g) of the above product and then heating it under vacuum at 180 °C for 3 days on a rotary evaporator.

[0648] Synthesis Example C2A1 - Preparation of a PET homopolymer with a molecular weight of 95.6 kg / mol using PMDA and SSP

[0649] PET homopolymer was prepared by polycondensation to obtain a product with a molecular size of 48.3 kg / mol. Approximately 93 g (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET) was added to a 500 mL round-bottom flask. After evacuation and backfilling with N2, the flask was lowered to a 180 °C salt bath, and top mixing was initiated at 100 rpm under a flow of N2. 0.12 g (0.0005 mol) of titanium isopropoxide catalyst was added to the flask. After 50 minutes, the bath temperature was raised to 285 °C. After 2 hours at this temperature under N2, evacuation was initiated and maintained for 2 hours. Pyromellitic dianhydride PMDA (0.49 g; 0.0022 mol) was slowly added over approximately 10 minutes under a flow of N2. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out as follows: equal portions (30g) of the above product were ground and then heated at 180°C under vacuum for 3 days in a rotary evaporator to obtain a polymer with a molecular weight of 95.6kg / mol.

[0650] Synthesis Example C2A2 - Preparation of a PET homopolymer with a molecular weight of 80.87 kg / mol using PMDA and SSP

[0651] PET homopolymer was prepared by polycondensation to obtain a product with a molecular size of 80,871 g / mol. Approximately 93 g (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET) was added to a 500 mL round-bottom flask. After evacuation and backfilling with N2, the flask was lowered to a 180 °C salt bath, and top mixing was initiated at 100 rpm under a flow of N2. 0.123 g (0.0004 mol) of titanium isopropoxide catalyst was added to the flask. After 3 hours, the bath temperature was raised to 285 °C. After 1 hour at this temperature under N2, evacuation was initiated and maintained for 1 hour. Pyromellitic dianhydride PMDA (0.49 g; 0.0022 mol) was slowly added over approximately 10 minutes under a flow of N2. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out as follows: equal portions of the above product were ground and then heated at 180°C under vacuum for 3 days in a rotary evaporator to obtain a polymer with a molecular weight of 80.9 kg / mol.

[0652] Synthesis Example C2A3 - Preparation of a PET homopolymer with a molecular weight of 80.9 kg / mol using PMDA and SSP

[0653] PET homopolymer was prepared by polycondensation to obtain a product with a molecular size of 61.1 kg / mol. Approximately 93 g (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET) was added to a 500 mL round-bottom flask. After evacuation and backfilling with N2, the flask was lowered to a 180 °C salt bath, and top mixing was initiated at 100 rpm under a flow of N2. After heating under N2 for 3 hours, 0.123 g (0.0004 mol) of titanium isopropoxide catalyst was added to the flask. After 50 minutes, the bath temperature was raised to 285 °C. After 1.5 hours at this temperature under N2, a vacuum was initiated and maintained for 2 hours. Pyromellitic dianhydride PMDA (0.49 g; 0.0022 mol) was slowly added over approximately 10 minutes under a flow of N2. Mixing was allowed at this temperature for another 30 minutes before stopping the reaction. Solid-state polymerization was carried out as follows: equal portions (30g) of the above product were ground and then heated at 180°C under vacuum for 3 days in a rotary evaporator to obtain a polymer with a molecular weight of 81kg / mol.

[0654] Example of use

[0655] Comparative Example 7: Wind turbine generator made of PET foam

[0656] This article has Figures 21 to 24 The wind turbine generator of the general type configuration shown is constructed on land with a nacelle approximately 150 meters above the ground (refer to the nacelle centerline). Each blade has a blade span of approximately 100 meters from the hub axis to the blade tip, and the rotor diameter is approximately 200 meters. The generator produces approximately 13 MW of electrical power under peak design conditions. For the blade design where PET is the only core material used, each of the three blades will have a 26.4 m³ veneered commercial PET foam / blade shell, totaling 79.2 m³ for all three blades. Since PET has a density of approximately 100 kg / m³, the total weight of the PET foam used in the wind turbine is 7,900 kg. Based on technical data sheets provided by suppliers of commercial PET foam (i.e., Gurit, AArmacel), the PET foam provides a core compressive strength of 1.5 MPa and a core tensile strength of 2.5 MPa.

[0657] Example 22A: Wind turbine generator made from the PEF homopolymer foam of the present invention

[0658] A wind turbine generator with the configuration described in Comparative Example 7 is constructed, except that the foamed core material is the extruded foam of the present invention (including each of foams 1 to 4) or an extruded foam made of the PEF polymer of the present invention, including thermoplastic polymers TPP1A-TPP22E, or any extruded foam described in Examples 1-22. The preferred extruded PEF foam of the present invention has a higher relative tensile strength compared to extruded PET foam, such that the density of the PEF foam of the present invention is about 5 / 7 to about 5 / 6 of the density of commercially available PET foam, while matching the tensile strength of higher-density PET foam. Considering these strength advantages, the PEF-based wind turbine blade of this embodiment has 10 / 13 the foam portion of the PET-based blade of Comparative Example 4, while achieving the same energy production. Based on Sandia Report SAND2011-3779, 2011. (https: / / energy.sandia.gov / wp-content / gallery / upload / 113779.pdf) The blades of the 13MW wind turbine (100m blades) are made of 20% by weight foam core material. Reducing the foam weight to 10 / 13 results in a 5% reduction in blade weight. To balance torque, the reduction in turbine blade weight produces an additional reduction in nacelle weight, the final value depending on the distance of the nacelle's center of mass relative to the tower. Such overall weight savings in wind turbine generators are a highly advantageous and unexpected result due to the use of the foams of the present invention (including each of foams 1 to 4) or foams made from the PEF polymers of the present invention, including thermoplastic polymers TPP1A-TPP22E, or any of the foams described in Examples 1-22.

[0659] Example 23: Wind turbine made with the extruded PET:PEF copolymer foam of the present invention in the blade shell motor

[0660] A wind turbine generator having the configuration described in Comparative Example 4 is manufactured, except that the foamed core material is the extruded foam of the present invention (including each of foams 1 to 4) or a foam made of the PEF polymer of the present invention, including thermoplastic polymers TPP1A-TPP22E, or any foam described in Examples 1-22. The preferred copolymer foam exhibits approximately twice the tensile and compressive strength when its density is comparable to that of the PET foam of the comparative example. Based on information disclosed from suppliers of commercial PET foams used as the baseline for comparison, the preferred PET-PEF copolymer foam of the present invention is considered to have a shear strength advantage, which is approximately twice the average of the tensile and compressive strength advantages of the PET foam. This two-fold advantage in shear strength is an unexpected and highly advantageous result, at least in part, because it allows for a reduction in core foam thickness of up to half, as is expected, provided the flexural stiffness of the foamed core material remains acceptable. This is demonstrated by calculations described in the following: Introduction to Sandwich Structures, Chapter 3, Student Edition, 1995, Dan Zenkert.

[0661] τ c = T x / d

[0662] in:

[0663] Tx is a direct load in Newtons (per beam width, 1 cm in this case) that causes the beam (in this case, the blade) to bend.

[0664] D is the thickness of the core foam plus the outer skin, which is approximately equal to the thickness of the core foam (in cm).

[0665] τc is the shear stress experienced by the core foam due to the direct load. Since the load here is in Newtons per centimeter, the stress becomes Newtons per centimeter square (N / cm²), which has the unit of pressure. High shear strength means high shear stress (τc), making it possible to reduce the core foam thickness while still handling the same direct load on the beam.

[0666] Based on publicly available data from commercially available PET foam suppliers, the density of PET foam was increased from 80 kg / m³. 3 Increased to 135 kg / m 3 The compressive and tensile strengths of PET foam were increased by 2.5 times and 1.5 times, respectively. Within this range, the shear strength increased to approximately 2 times, which is roughly the average of the tensile and compressive strength advantages. The advantages identified in this embodiment are based on information and data contained in the following disclosures, each of which is incorporated herein by reference:

[0667] (https: / / www.gurit.com / - / media / Guirt / Datasheets / Kerdyn-Green.pdf);

[0668] (https: / / local,armacell.com / fileadmin / cms / pet-Teams / ArmaPET.Website / Product Flyer / ArmaPET struct GR)

[0669] Example 24: Wind turbine made with the extruded PET:PEF copolymer foam of the present invention in the blade shell motor

[0670] A wind turbine generator having the configuration described in Comparative Example 7 is manufactured, except that the foamed core material is an extruded foam of the present invention (including each of foams 1 to 4) or an extruded foam made of the PEF polymers of the present invention, including thermoplastic polymers TPP1A-TPP22E, or any extruded foam described in Examples 1-22. The copolymer foam of the present invention has a relative tensile strength at a comparable density that is about 1.7 times that of the PET foam of the comparative example. The copolymer foam of the present invention also has a relative compressive strength at a comparable density that is about 1.5 times that of the PET foam of the comparative example. These results indicate that the shear strength of the copolymer foam of the present invention is about 1.6 times that of the comparable PET foam, which allows for a reduction in the thickness of the foamed core material by up to 3 / 8, provided that the flexural stiffness of the foamed core material remains sufficient, as is expected. Reducing the thickness of the foamed core material results in a significant weight reduction, which is a highly advantageous but unexpected result.

Claims

1. An extruded thermoplastic foam, said extruded thermoplastic foam comprising: (a) A thermoplastic polymer pore, the thermoplastic polymer pore comprising pore walls forming closed pores, wherein the thermoplastic polymer is substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, wherein the polymer comprises about 10 mol% to about 100 mol% of the ethylene furanate portion and optionally at least about 1 mol% of the polyethylene terephthalate portion; and (b) The trans 1234ze contained in the closed pore.

2. The extruded foam according to claim 1, wherein the thermoplastic polymer: (i) comprises about 10 mol% to about 100 mol% of an ethylene furanoate portion and about 10 mol% to about 90 mol% of an ethylene terephthalate portion; and (ii) has a molecular weight of at least about 25,000.

3. The extruded foam according to claim 1, wherein the thermoplastic polymer: (i) comprises about 10 mol% to about 100 mol% of an ethylene furanoate portion and about 10 mol% to about 90 mol% of an ethylene terephthalate portion; and (ii) has a molecular weight of about 25,000 to about 140,000.

4. The extruded foam of claim 1, wherein the thermoplastic polymer has been formed by a method including treatment with a chain extender.

5. The extruded foam according to claim 1, wherein: (a) at least about 75% of the pores are closed pores; (b) the foam has a foam density of less than 0.1 g / cc; and (c) the pore walls are substantially composed of a thermoplastic with a molecular weight of about 30,000 to about 130,000.

6. A wind turbine blade and / or nacelle, the wind turbine blade and / or nacelle comprising the foam according to claim 1.

7. A wind turbine blade and / or nacelle, the wind turbine blade and / or nacelle comprising the foam according to claim 2.

8. A wind turbine blade and / or nacelle, the wind turbine blade and / or nacelle comprising the foam according to claim 5.

9. A method for forming an extruded thermoplastic foam, the method comprising extruding a foamable composition comprising a thermoplastic polymer and a foaming agent, wherein the thermoplastic polymer is substantially composed of an ethylene furanate portion and optionally a polyethylene terephthalate portion, and wherein the extrusion step comprises forcing the foamable composition from a relatively high-pressure region through a die to a relatively low-pressure region.

10. The method of claim 9, wherein the thermoplastic polymer: (i) comprises about 10 mol% to about 100 mol% of an ethylene furanoate portion and about 10 mol% to about 90 mol% of an ethylene terephthalate portion; and (ii) has a molecular weight of about 25,000 to about 140,000, and wherein the thermoplastic foam comprises a closed-cell thermoplastic foam, wherein at least about 75% of the pores in the extruded foam are closed-cell.

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