Expandable thermoplastic composition, thermoplastic foam, and method for producing the same

Abstract

1. A low density thermoplastic foam comprising: (a) thermoplastic polymer cells having cell walls forming closed cells, the thermoplastic polymer comprising an ethylene furanoate portion and an optional ethylene terephthalate portion, the polymer comprising from about 1 mol % to about 100 mol % of the ethylene furanoate portion, and optionally at least about 1 mol % of the ethylene terephthalate portion; and (b) one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells.

Description

[Technical Field]

[0001] (Cross-reference of related applications) This application incorporates, by claiming and referencing, the benefit of priority with respect to U.S. Provisional Patent Application No. 63 / 312,855, filed February 23, 2022.

[0002] This application is incorporated by reference to U.S. Provisional Patent Application No. 63 / 343,990, filed on 19 May 2022.

[0003] This application is also a continuation of each of the following applications, incorporated by reference to each of the following: International Application PCT / US22 / 40504 filed August 16, 2022; PCT / US22 / 40505 filed August 16, 2022; PCT / US22 / 40506 filed August 16; and PCT / US22 / 40507 filed August 16, 2022.

[0004] (Field of invention) The present invention relates to foamable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles produced therefrom. [Background technology]

[0005] While foams are used in a wide variety of applications, it is desirable, but difficult, for many applications for foam materials to be environmentally friendly, possess excellent performance characteristics, and be cost-effective to manufacture. 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).

[0006] Certain thermoplastic foams, including polyester resins, have been studied for their potential advantages in terms of recyclability and / or sustainably availability. However, challenges have been encountered in the development of such materials. For example, the challenge has been to develop polyester resins that are truly recyclable, can be manufactured from sustainable sources, and are compatible with blowing agents that can be combined with thermoplastic materials to produce foams with good performance characteristics. In many applications, highly desirable performance characteristics 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.

[0007] Regarding the selection of thermoplastic resins, European Patent No. 3,231,836 expressed interest in thermoplastic resins, particularly polyester resins, but acknowledged that this interest faced development difficulties, such as the difficulty in identifying appropriate foaming grades for such resins. Furthermore, European Patent No. 3,231,836 mentions that certain polyethylene terephthalate (PET) resins (including recycled PET) can be melt-extruded with suitable physical and / or chemical blowing agents to obtain closed-cell foams with the potential for low density and good mechanical properties, but it does not disclose that any of these resins can be used to immediately produce foams with good environmental and performance properties, and that they can be formed from sustainable sources. Application No. 836 identifies several candidate polyester resins for use in forming open-cell foams, comprising polyethylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate, polyethylene naphthalate, polyethylene furanoate, or mixtures of two or more of these. While the use of polyester materials to produce foams that essentially lack closed cells, as required by European Patent No. 836, may be beneficial for some applications, a drawback of such structures is that open-cell foams generally exhibit relatively poor mechanical strength properties.

[0008] Chinese Patent No. 108484959 discloses that the production of foam products based on 2,5-flangemethyl copolyester is problematic because the dissolution of foaming agents into polyester is alleged to be an issue, and proposes a specific process including the use of a combination of liquid and gaseous foaming agents, and the sequential use of these different types of foaming agents.

[0009] U.S. Patent Publications 2020 / 0308363 and 2020 / 0308396 disclose the production of amorphous polyester copolymers, which include starting from recycled polyester, with PET being the only exemplified main component, and then obtaining amorphous copolymers, i.e., copolymers that do not have crystalline properties, through a series of processing steps. A wide variety of different types of blowing agents for use with such amorphous polymers are mentioned.

[0010] With respect to blowing agents, the general use of halogenated olefin blowing agents, including hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs), is also known, for example, disclosed in U.S. Patent Application Publication No. 2009 / 0305876, which has been assigned to the assignee of the present invention and is incorporated herein by reference. Application No. 876 discloses the use of HFOs and HFCOs blowing agents with various thermoplastic materials to form foams including PET, but makes no disclosure or suggestion of the use of any of such blowing agents with any other type of polyester resin.

[0011] The applicants have come to recognize that by using the polyester resins disclosed herein in combination with blowing agents comprising one or more hydrohaloolefins disclosed herein, one or more unexpected advantages can be achieved in relation to the formation of thermoplastic foams, particularly extruded thermoplastic foams. [Overview of the project]

[0012] The present invention (a) Thermoplastic polymer bubbles including cell walls that form closed cells, wherein the thermoplastic polymer essentially consists of an ethylene furanoate moiety and an optional ethylene terephthalate moiety, and the polymer comprises about 1 mol% to about 100 mol% of the ethylene furanoate moiety and optionally at least about 1 mol% of the ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1A.

[0013] The present invention (a) Thermoplastic polymer bubbles comprising cell walls forming closed cells, wherein the thermoplastic polymer has a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an optional ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 100 mol% of the ethylene furanoate moiety and optionally at least about 1 mol% of the ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1B.

[0014] The present invention (a) Thermoplastic polymer bubbles comprising cell walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate moiety and at least about 1 mol% of the ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1C.

[0015] The present invention (a) Thermoplastic polymer bubbles comprising cell walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate moiety and about 80 mol% to about 99 mol% of the ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1D.

[0016] The present invention (a) Thermoplastic polymer bubbles comprising cell walls forming closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% to about 5 mol% of the ethylene furanoate moiety and about 90 mol% to about 99 mol% of the ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1E.

[0017] The present invention (a) A thermoplastic polymer foam including bubble walls that form closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer includes from about 1 mol% to about 5 mol% of an ethylene furanoate moiety and from about 95 mol% to about 99 mol% of an ethylene terephthalate moiety, the thermoplastic polymer foam; (b) A low-density thermoplastic foam including one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells. For convenience, in this specification, the foam according to this paragraph is referred to as Foam 1F.

[0018] The present invention relates to (a) A thermoplastic polymer foam including bubble walls that form closed cells, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a crystallinity of at least about 5%, and consists essentially of an ethylene furanoate moiety and an ethylene terephthalate moiety, and the polymer includes from about 0.5 mol% to about 2 mol% of an ethylene furanoate moiety and from about 98 mol% to about 99.5 mol% of an ethylene terephthalate moiety, the thermoplastic polymer foam; (b) A low-density thermoplastic foam including one or more HFOs having 3 or 4 carbon atoms and / or one or more HFCOs having 3 or 4 carbon atoms contained within the closed cells. For convenience, in this specification, the foam according to this paragraph is referred to as Foam 1G.

[0019] The present invention relates to (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 1 mol% of an ethylene furanoate moiety and about 99 mol% of an ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1H.

[0020] The present invention (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, 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 essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 0.5 mol% of an ethylene furanoate moiety and about 99.5 mol% of an ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1I.

[0021] The present invention (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 5 mol% of an ethylene furanoate moiety and about 95 mol% of an ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1J.

[0022] The present invention (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 10 mol% of an ethylene furanoate moiety and about 90 mol% of an ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 1K.

[0023] The present invention (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, wherein the polymer comprises about 20 mol% of an ethylene furanoate moiety and about 80 mol% of an ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms contained within closed cells. For convenience, the foam prepared in this paragraph will be referred to as 1 liter of foam in this specification.

[0024] The present invention (a) Thermoplastic polymer bubbles comprising a cell wall containing polyethylene furanoate, wherein at least 25% of the bubbles are closed cells, (b) A low-density thermoplastic foam containing 1234ze(E) contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 2A.

[0025] The present invention (a) Thermoplastic polymer bubbles containing polyethylene furanoate and comprising a cell wall essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate portion and about 0.5 mol% or more of the ethylene terephthalate portion, and at least 25% of the bubbles are closed cells, (b) A low-density thermoplastic foam containing 1234ze(E) contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 2B.

[0026] The present invention (a) Thermoplastic polymer bubbles containing polyethylene furanoate and comprising a cell wall essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate portion and about 0.5 mol% or more of the ethylene terephthalate portion, and at least 25% of the bubbles are closed cells, (b) A low-density thermoplastic foam containing 1336 mzz(Z) contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 2C.

[0027] The present invention (a) Thermoplastic polymer bubbles containing polyethylene furanoate and comprising a cell wall essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate portion and about 0.5 mol% or more of the ethylene terephthalate portion, and at least 25% of the bubbles are closed cells, (b) A low-density thermoplastic foam containing 1223zd(E) contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 2D.

[0028] The present invention (a) Thermoplastic polymer bubbles containing polyethylene furanoate and comprising a cell wall essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate portion and about 0.5 mol% or more of the ethylene terephthalate portion, and at least 25% of the bubbles are closed cells, (b) A low-density thermoplastic foam comprising 1224 yd contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 2E.

[0029] The present invention (a) Thermoplastic polymer bubbles containing polyethylene furanoate and comprising a cell wall essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, wherein the polymer comprises about 1 mol% to about 20 mol% of the ethylene furanoate portion and about 0.5 mol% or more of the ethylene terephthalate portion, and at least 50% of the bubbles are closed cells, (b) A low-density thermoplastic foam comprising a gas within the closed cells, wherein the gas contains approximately 25% to 100% by weight of 1234ze(E). For convenience, the foam according to this paragraph will be referred to as foam 2F in this specification.

[0030] Throughout this specification, references are made to the numbered foams (e.g., foam 1) or groups of numbered foams as defined herein, and such references mean each of such numbered systems, for example, each system having a number within the group, including systems with any subscript number. For example, a reference to foam 1 is understood to include separate references to each of foams 1A, 1B, 1C, 1D, etc., and a reference to foams 1-2 is understood to include separate references to each of foams 1A, 1B, 1C, 1D, etc., and each of foams 2A, 2B, 2C, 2D, etc. Furthermore, this convention is used throughout this specification for other defined materials, including blowing agents.

[0031] The present invention (a) Thermoplastic polymer bubbles comprising cell walls forming closed cells, wherein the thermoplastic polymer essentially consists of an ethylene furanoate moiety and an optional ethylene terephthalate moiety, and the thermoplastic polymer comprises (i) about 10 mol% to about 100 mol% of an ethylene furanoate moiety and optionally at least about 1 mol% of an ethylene terephthalate moiety, and (ii) having a molecular weight of at least about 25,000, (b) A low-density thermoplastic foam comprising trans 1234ze contained within closed cells. For convenience, the foam described in this paragraph will be referred to as foam 3.

[0032] The present invention (a) Thermoplastic polymer bubbles comprising cell walls forming closed cells, wherein the thermoplastic polymer essentially consists of an ethylene furanoate moiety and an optional ethylene terephthalate moiety, and the thermoplastic polymer comprises (i) about 10 mol% to about 100 mol% of an ethylene furanoate moiety and optionally at least about 1 mol% of an ethylene terephthalate moiety, and (ii) having a molecular weight of at least about 25,000 to about 140,000, (b) A low-density thermoplastic foam comprising trans 1234ze contained within closed cells. For convenience, the foam according to this paragraph will be referred to as foam 4 in this specification.

[0033] The present invention (a) A thermoplastic material comprising essentially an ethylene furanoate moiety and an optional ethylene terephthalate moiety, wherein the thermoplastic material includes about 1 mol% to about 100 mol% of the ethylene furanoate moiety and at least about 1 mol% of the optional ethylene terephthalate moiety. (b) A foaming agent comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms, comprising a foaming thermoplastic composition. For convenience, the foaming composition described in this paragraph will be referred to as foaming composition 1 in this specification.

[0034] The present invention relates to a method for forming a thermoplastic composition having improved crystallinity, (a) Forming a thermoplastic material comprising a polymer chain containing an ethylene furanoate moiety and / or an ethylene terephthalate moiety, (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 furanoate portion and optionally at least about 1 mol% of an ethylene terephthalate portion. (c) A method comprising distilling the solvent from the thermoplastic material. For convenience, the method for forming a thermoplastic composition according to this paragraph will be referred to as Thermoplastic Forming Method 1 in this specification.

[0035] The present invention also provides a method for forming a thermoplastic foam, comprising foaming the foaming composition of the present invention, which includes foaming composition 1. For convenience, the method according to this paragraph will be referred to as foaming method 1.

[0036] The present invention also provides a method for forming an extruded thermoplastic foam, comprising extruding the foaming composition of the present invention, which includes foaming composition 1. For convenience, the method according to this paragraph will be referred to as foaming method 2.

[0037] The present invention also provides a method for forming an extruded thermoplastic foam, comprising extruding the foamed composition of the present invention, which includes foamed composition 1. For convenience, the method according to this paragraph will be referred to as extrusion method 1. [Brief explanation of the drawing]

[0038] [Figure 1] This is a schematic diagram of an embodiment of the present invention and an extrusion system and process according to the embodiments herein. [Figure 2A] This is a graph showing the results for Example C1B. [Figure 2B] This is a graph showing the results for Example C1B. [Figure 2C] This is a graph showing the results for Example C1B. [Figure 3A] This is a graph showing the results for Example C2B. [Figure 3B] This is a graph showing the results for Example C2B. [Figure 4] This is a graph showing the results of Example 1B. [Figure 5A] This is a graph showing the results of Example 2B. [Figure 5B] This is a graph showing the results of Example 2B. [Figure 6A] This is a graph showing the results of Example 3B. [Figure 6B] This is a graph showing the results of Example 3B. [Figure 6C] This is a graph showing the results of Example 3B. [Figure 6D] This is a graph showing the results of Example 3B. [Figure 7] This is a graph showing the results of Example 4B. [Figure 8] This is a graph showing the results of Example 5B. [Figure 9] This is a graph showing the results of Example 6B. [Figure 10] This is a graph showing the results of Example 7B. [Figure 11] This is a graph showing the results of Example 8B. [Figure 12] This is a graph showing the results of Example 9B. [Figure 13] This is a graph showing the results of Example 10B. [Figure 14] This is a graph showing the results of Example 11B. [Figure 15] This is a graph showing the results of Example 12B. [Figure 16] This is a graph showing the results of Example 12C. [Figure 17] This is a graph showing the results of Example 13B1. [Figure 18] This is a graph showing the results of Example 13B2. [Figure 19] This is a graph showing the results of Example 13B3. [Figure 20] This is a graph showing the results of Example 18. [Figure 21] This is a schematic diagram of an example wind turbine. [Figure 22] This is a semi-circular diagram of an exemplary wind turbine blade. [Figure 23A] This is an illustrative cross-sectional view of a wind turbine blade. [Figure 23B] This is an illustrative cross-sectional view of a wind turbine blade. [Figure 23C] This is an illustrative cross-sectional view of a wind turbine blade. [Figure 24] This is a cross-sectional view of an exemplary coated foam of the present invention in a specific form of sandwich structure. [Figure 25] This is a graph showing the results of Example 20. [Figure 26] This is a graph showing the results of Example 21.

[0039] definition 1234ze means 1,1,1,3-tetrafluoropropene and is not limited to isomer morphology.

[0040] Trans-1234ze and 1234ze(E) refer to trans-1,3,3,3-tetrafluoropropene, respectively.

[0041] cis1234ze and 1234ze(Z) each refer to cis-1,3,3,3-tetrafluoropropene.

[0042] 1234yf stands for 2,3,3,3-tetrafluoropropene.

[0043] 1233zd means 1-chloro-3,3,3-trifluoropropene and is not limited to isomer morphology.

[0044] Trans-1233zd and 1233zd(E) refer to trans-1-chloro-3,3,3-trifluoropropene, respectively.

[0045] 1224yd means cis-1-chloro-2,3,3,3-tetrafluoropropane and is not limited to isomer morphology.

[0046] 1336mzz refers to 1,1,1,4,4,4-hexafluorobutene and is not limited to isomer morphology.

[0047] Trans-1336mzz and 1336mzz(E) refer to trans-1,1,1,4,4,4-hexafluorobutene, respectively.

[0048] cis1336mzz and 1336mzz(Z) refer to cis1,1,1,4,4,4-hexafluorobutene, respectively.

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

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

[0051] [ka]

[0052] FDCA stands for 2,5-franzicarboxylic acid and has the following structure.

[0053] [ka]

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

[0055] [ka]

[0056] FDME stands for dimethyl 2,5-franzicarboxylate and has the following structure.

[0057] [ka]

[0058] PEF homopolymer refers to a polymer having at least 99 mol% ethylene furanoate moiety.

[0059] PEF copolymer refers to a polymer having at least about 10 mol% of ethylene furanoate and more than 1% of polymer parts other than ethylene furanoate.

[0060] PEF:PET copolymer means a polymer having at least about 10 mol% of ethylene furanoate moiety and at least 1% of ethylene terephthalate moiety.

[0061] PEF stands for poly(ethylene furanoate) and is intended to encompass and reflect the descriptions of PEF homopolymer and PEF copolymer.

[0062] The ethylene terephthalate portion has the following structure:

[0063] [ka]

[0064] SSP stands for solid-phase polymerization.

[0065] PMDA refers to pyromellitic dianhydride having the following structure.

[0066] [ka] [Modes for carrying out the invention]

[0067] Poly(ethylene furanoate) The present invention relates to a foam and a foam article, which include a bubble wall containing a PEF portion.

[0068] The PEF that forms the bubble walls of the foam and foam article of the present invention may be a PEF homopolymer or a PEF copolymer, particularly a PEF:PET copolymer.

[0069] PEF homopolymers are known materials that can be formed by either (a) esterification and polycondensation of FDCA and MEG, or (b) transesterification and polycondensation of FDME and MEG, for example, as shown below.

[0070] [ka]

[0071] A detailed description of such known esterification and polycondensation synthesis methods is provided in British Patent No. 621971 (Drewitt, JGN and Lincoln, J., titled "Improvements in Polymers"), which is incorporated herein by reference. A detailed description of such known transesterification and polycondensation synthesis methods is provided in Gandini, A., Silvestre, 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.

[0072] foam The foam of the present invention, comprising each of foams 1 to 4, is formed from either a PEF homopolymer, a PEF copolymer, or a combination / mixture thereof.

[0073] In preferred embodiments, the foams of the present invention, each comprising foams 1 to 4, may be formed from a PEF homopolymer having at least 99.5% by weight or at least 99.9% by weight of an ethylene furanoate moiety.

[0074] In preferred embodiments, the foams of the present invention, each of foams 1 to 4, are intended to be formed from a PEF copolymer having a polymer comprising about 60% to about 99% by weight of ethylene furanoate, or about 70% to about 99% by weight of ethylene furanoate, or about 80% to about 99% by weight of ethylene furanoate, or about 90% to about 99% by weight of ethylene furanoate, or about 95% to about 99.5% by weight of ethylene furanoate.

[0075] In preferred embodiments, the foams of the present invention, each of foams 1 to 4, are intended to be formed from a PEF copolymer having a polymer comprising about 40% to about 1% by weight of ethylene furanoate, or about 30% to about 1% by weight of ethylene furanoate, or about 20% to about 1% by weight of ethylene furanoate, or about 10% to about 1% by weight of ethylene furanoate, or about 5% to about 1% by weight of ethylene furanoate, or about 5% to about 0.5% by weight of ethylene furanoate.

[0076] In preferred embodiments, the foams of the present invention, each of foams 1 to 4, are intended to be formed from a PEF copolymer having a polymer comprising about 40 mol% to about 1 mol% of ethylene furanoate moiety, or about 30 mol% to about 1 mol% of ethylene furanoate moiety, or about 20 mol% to about 1 mol% of ethylene furanoate moiety, or about 10 mol% to about 1 mol% of ethylene furanoate moiety, or about 5 mol% to about 1 mol% of ethylene furanoate moiety, or about 5 mol% to about 0.5 mol% of ethylene furanoate moiety.

[0077] In a preferred embodiment, the foam of the present invention, comprising each of foams 1 to 4, contains a polymer comprising about 40 mol% to about 1 mol% ethylene furanoate and about 60 mol% to about 99 mol% ethylene terephthalate, or about 30 mol% to about 1 mol% ethylene furanoate and about 70 mol% to about 99 mol% ethylene terephthalate, or about 20 mol% to about 1 mol% ethylene furanoate and about 80 mol% to about 99 mol% ethylene terephthalate. It is intended to be formed from a PEF copolymer having a phthalate portion, or an ethylene furanoate portion of about 10 mol% to about 1 mol% and an ethylene terephthalate portion of about 90 mol% to about 99 mol%, or an ethylene furanoate portion of about 5 mol% to about 1 mol% and an ethylene terephthalate portion of about 95 mol% to about 99 mol%, or an ethylene furanoate portion of about 5 mol% to about 0.5 mol% and an ethylene terephthalate portion of about 95 mol% to about 99.5 mol%.

[0078] With respect to these embodiments of the present invention, including PEF copolymers, those skilled in the art will find that, taking into account the teachings contained herein, they can select the type and amount of copolymer material to be used within each of the ranges described herein in order to achieve the desired enhancement / modification of the polymer without excessive experimentation.

[0079] With respect to these embodiments of the present invention involving the use of PEF homopolymers or PEF copolymers, it is intended that such materials having a wide variety of molecular weights and physical properties within the scope of the present invention can be formed. In preferred embodiments, foams comprising each of foams 1 to 4 are formed from PEF having the range of properties specified in Table 1 below, as measured as described in the examples herein.

[0080] [Table 1]

[0081] Generally, it is intended that those skilled in the art can formulate PEF polymers within the range of the above properties without excessive experimentation, taking into account the teachings contained herein. However, in preferred embodiments, PEF (including PEF homopolymers and PEF copolymers) having these properties is achieved by using one or more of the above synthesis methods in combination with various known supplemental processing techniques, including treatment with chain extenders such as PMDA (and PMDA substitutes and supplements such as ADR, PENTA, and talc, as described in the Examples of the Invention and elsewhere) and / or SSP treatment. Taking into account the disclosures contained herein, including the polymer synthesis described in the following Examples and the use of methods to enhance polymer crystallization, it is considered that those skilled in the art can produce PEF polymers within the range of properties described in the above Table and elsewhere in this Spec. Such processing conditions include methods to increase crystallization described herein, including thermoplastic formation method 1 of the Invention, such methods are those disclosed in the Examples of this Spec.

[0082] An example of a process for chain extension treatment of polyester is provided in the document “Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process,” Firas Awaja, Fugen Daver, Edward Kosior, 16 August 2004, https: / / doi.org / 10.1002 / pen.20155, which is incorporated herein by reference. As described in U.S. Patent Application Publication No. 1009 / 0264545, incorporated herein by reference, chain extenders are generally compounds that are at least bifunctional with respect to reactive groups that can react with terminal groups or functional groups in polyester to extend the length of polymer chains. In particular cases, as disclosed herein, such treatments can favorably increase the average molecular weight of the polyester and improve its melt strength and / or other important properties. The degree of chain extension achieved is at least in part related to the structure and functionality of the compound used. A variety of compounds are useful as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing polyfunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposite materials, such as finely dispersed nanoclay, may optionally be used to control viscosity. Commercially available chain extenders include Clariant's CESA-Extend, BASF's Joncryl, or Arkema's Lotader. The amount of chain extender may vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to process the polymer can vary widely, in preferred embodiments ranging from about 0.1 to about 5% by weight, or preferably from about 0.1 to about 1.5% by weight. Examples of chain extenders are also described in U.S. Patent No. 4,219,527, which is incorporated herein by reference.

[0083] An example of a process for SSP treatment of poly(ethylene furanoate) is provided in the paper "Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase," Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which is incorporated herein by reference.

[0084] PEF thermoplastic polymers particularly advantageous for producing the foaming compositions and foams of the present invention are identified in the following thermoplastic polymer table (Table 2A), and all values ​​in the table are understood to be preceded by the word "approximately".

[0085] [Table 2]

[0086] The PEF thermoplastic polymers particularly advantageous for producing the foaming compositions and foams of the present invention also include the materials specified in the following thermoplastic polymer table (Table 2B), and all numerical values ​​in the table are understood to be preceded by the word "approximately".

[0087] [Table 3]

[0088] The PEF thermoplastic polymers particularly advantageous for producing the foamed compositions and foams of the present invention also include the materials specified in the following thermoplastic polymer table (Table 2C), and all numerical values ​​in the table are understood to be preceded by the word "approximately".

[0089] [Table 4-1]

[0090] [Table 4-2]

[0091] For the purposes of defining terms used herein, note that in various parts of this specification, thermoplastic polymers identified in the first column of each row in the TPP table above are referenced, and each reference to one of these numbers is a reference to the thermoplastic polymer defined in the corresponding column of that row. References to the group of TPPs defined in the table above by reference to the TPP number mean each such numbered TPP, including any such number with a subscript, and each TPP having the indicated number, separately and individually. Thus, for example, a reference to TPP1 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1D, and TPP1E. References to TPP1-TPP2 are separate and independent references to TPP1A, TPP1B, TPP1C, TPP1D, TPP1E, TPP2A, TPP2B, TPP2C, TPP2D, and TPP1E. This convention of use is also applied to the following tables of foamed compositions and foams.

[0092] foaming agent As described in detail herein, the present invention includes, but is not limited to, the applicant's discovery that a selected group of blowing agents can provide foamable PEF foam compositions and PEF foams having a difficult-to-achieve and remarkable combination of physical properties, including low density and good mechanical strength properties.

[0093] The blowing agent used in accordance with the present invention preferably comprises one or more hydrohaloolefins having three or four carbon atoms. For convenience, the blowing agent according to this paragraph may be referred to as blowing agent 1 in this specification.

[0094] The foaming agent used in accordance with the present invention preferably contains one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as foaming agent 2 for convenience), or contains one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 3 for convenience), or contains one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as foaming agent 4 for convenience), or trans 123 It contains one or more of 4ze and transform 1336mzz (hereinafter referred to as blowing agent 5 for convenience), or transform 1234ze (hereinafter referred to as blowing agent 6 for convenience), or transform 1336mzz (hereinafter referred to as blowing agent 7 for convenience), or cis 1336mzz (hereinafter referred to as blowing agent 8 for convenience), or 1234yf (hereinafter referred to as blowing agent 9 for convenience), or 1224yd (hereinafter referred to as blowing agent 10 for convenience), or transform 1233zd (hereinafter referred to as blowing agent 11 for convenience).

[0095] Accordingly, the blowing agents of the present invention, each comprising blowing agents 1 to 11, are intended to include co-blowing agents comprising, in addition to each of the blowing agents specified above, one or more of the optional co-blowing agents described below. In preferred embodiments, the blowing compositions, foams, and blowing methods of the present invention comprise the blowing agents described herein, wherein the indicated blowing agents (including the compounds or groups of compounds specifically identified in each of blowing agents 1 to 11) are present in an amount of at least about 50% by weight, preferably at least about 60% by weight, preferably at least about 70% by weight, preferably at least about 80% by weight, preferably at least about 90% by weight, preferably at least about 95% by weight, or preferably at least about 99% by weight, based on the total weight of all blowing agents present and based on the sum of all blowing agent components.

[0096] The blowing agent used in accordance with the present invention is also preferably essentially composed of one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as blowing agent 12 for convenience), or essentially composed of one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as blowing agent 13 for convenience), or essentially composed of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as blowing agent 14 for convenience), or trans 1234ze and trans Essentially composed of one or more of 1336mzz (hereinafter referred to as blowing agent 15 for convenience), or essentially composed of transformer 1234ze (hereinafter referred to as blowing agent 16 for convenience), or essentially composed of transformer 1336mzz (hereinafter referred to as blowing agent 17 for convenience), or essentially composed of cis 1336mzz (hereinafter referred to as blowing agent 18 for convenience), or essentially composed of 1234yf (hereinafter referred to as blowing agent 19 for convenience), or essentially composed of 1224yd (hereinafter referred to as blowing agent 20 for convenience), or essentially composed of transformer 1233zd (hereinafter referred to as blowing agent 21 for convenience).

[0097] The blowing agents of the present invention, each comprising blowing agents 1 to 21, may include one or more co-blowing agents not included in the indicated selection, however, it is intended and understood that the amount of such co-blowing agent used will not interfere with or impair the ability to achieve relatively low-density foams as described herein, each comprising foams 1 to 4, and preferably further, not interfere with or impair the ability to achieve foams having mechanical strength properties as described herein. Accordingly, in consideration of the teachings contained herein, it is conceivable that, for example, without excessive experimentation, one or more saturated hydrocarbons or hydrofluorocarbons (HFCs), in particular one or more possible co-blowing agents known in the art, such as C4-C6 hydrocarbons or C1-C4 HFCs, can be selected for use in a particular application. Examples of such HFC co-blown agents include, but are not limited to, difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and one or a combination of all isomers of all such HFCs. With respect to hydrocarbons, the blowing agent compositions of the present invention may also, in certain preferred embodiments, include, for example, iso, n, and / or cyclopentane and butane and / or isobutane.Other materials may include, for example, water, CO2, CFCs (e.g., trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, for example, dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (e.g., ethanol and / or propanol and / or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (e.g., dimethyl ether and diethyl ether), diethers (e.g., dimethoxymethane and diethoxymethane)), and methyl formate, organic acids (e.g., formic acid, but not limited to these) (including any combination thereof), but such components are not necessarily preferred in many embodiments due to their adverse environmental impact.

[0098] The blowing agent used in accordance with the present invention is also preferably composed of one or more of 1234ze, 1234yf, 1336mzz, 1233zd, and 1224ydf (hereinafter referred to as blowing agent 22 for convenience), or composed of one or more of trans 1234ze, 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as blowing agent 23 for convenience), or composed of one or more of trans 1234ze, trans 1336mzz, trans 1233zd, and cis 1224yd (hereinafter referred to as blowing agent 24 for convenience), or trans 1234 It consists of one or more of ze and transformer 1336mzz (hereinafter referred to as blowing agent 25 for convenience), or transformer 1234ze (hereinafter referred to as blowing agent 26 for convenience), or transformer 1336mzz (hereinafter referred to as blowing agent 27 for convenience), or cis 1336mzz (hereinafter referred to as blowing agent 28 for convenience), or 1234yf (hereinafter referred to as blowing agent 29 for convenience), or 1224yd (hereinafter referred to as blowing agent 30 for convenience), or transformer 1233zd (hereinafter referred to as blowing agent 31 for convenience).

[0099] Foams and foaming processes Any of the foams of the present invention, comprising each of foams 1 to 4, or foams made from the PEF polymers of the present invention comprising thermoplastic polymers TPP1A to TPP22E, or foams described in Examples 1 to 22, can generally be formed from the foaming compositions of the present invention. Generally, the foaming compositions of the present invention can be formed by combining the PEF polymers of the present invention, comprising each of the thermoplastic polymers TPP1A to TPP22E, with the foaming agents of the present invention, comprising each of the foaming agents 1 to 31.

[0100] Foaming compositions that fall within the scope of the present invention and offer particular advantages in relation to the formation of foams of the present invention are listed in the following tables of foaming compositions (Tables 3A and 3B), all of which are understood to be preceded by the word "approximately", and the following terms used in the tables have the following meanings.

[0101] CBAG1 refers to a co-foaming agent selected from the group consisting of 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), 1234yf, and two or more combinations thereof.

[0102] CBAG2 refers to a co-foaming agent selected from the group consisting of water, CO2, C1-C6 hydrocarbons (HC), HCFCs, C1-C5 HFCs, C2-C4 hydrohaloolefins, C1-C5 alcohols, C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers, C1-C4 esters, organic acids, and combinations of two or more of these.

[0103] CCBAG3 is made from 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) This refers to a co-foaming agent selected from the group consisting of 1,1,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and any two or more combinations thereof.

[0104] NR means not requested.

[0105] [Table 5-1]

[0106] [Table 5-2]

[0107] [Table 5-3]

[0108] [Table 5-4]

[0109] [Table 5-5]

[0110] Table 5-6

[0111] Table 5-7

[0112] Table 5-8

[0113] Table 5-9

[0114] Table 5-10

[0115] Table 6-1

[0116] Table 6-2

[0117] Table 6-3

[0118] Table 6-4

[0119] How to form vesicles To form the foams of the present invention, it is intended that one or more of the various known techniques for forming thermoplastic foams may be used, taking into account the disclosures contained herein, and the foams of the present invention include each of foams 1-4 and foaming compositions 1-11, all such techniques and all foams formed thereby, or all foams within the broad scope of the present invention. For clarity, it should be noted that all definitions of foams in the following table begin with the letter F, in contrast to the foams defined in the paragraph of the above summary of the invention which begins with the capital letter Foamable Composition.

[0120] Generally, the formation process involves first introducing a blowing agent of the present invention, containing each of blowing agents 1 to 31, into a PEF polymer of the present invention containing each of TPP1 to TPP22, thereby forming a foamy PEF composition containing PEF and a blowing agent. One preferred method for forming the foamy PEF composition of the present invention is to plasticize the PEF, which preferably involves heating the PEF to its melting temperature, preferably to a temperature higher than its melting temperature, and then exposing the PEF melt to the blowing agent under conditions that are effective in incorporating (preferably by solubilizing) a desired amount of blowing agent into the polymer melt.

[0121] In a preferred embodiment, the foaming method of the present invention includes providing an effervescent composition of the present invention containing each of FC1 to FC11, and foaming the provided effervescent composition. In a preferred embodiment, the foaming method of the present invention includes providing an effervescent composition of the present invention containing each of FC1 to FC11, and extruding the provided effervescent composition to form a foam of the present invention containing each of foams 1 to 4 and each of foams F1 to F8.

[0122] The foaming process of the present invention may include a batch process, a semi-batch process, a continuous process, and a combination of two or more of these. A batch process generally involves preparing at least a portion of an expandable polymer composition containing each of FC1 to FC11 in a storable state, and then using that portion of the expandable polymer composition at some point in the future to prepare a foam. A semi-batch process includes, all in a single process, preparing at least a portion of an expandable polymer composition containing each of FC1 to FC11, and intermittently expanding that expandable polymer composition into a foam containing each of foams 1 to 4 and each of foams F1 to F11. For example, U.S. Patent No. 4,323,528, incorporated herein by reference, discloses a process for producing a thermoplastic foam via a cumulative extrusion process. Accordingly, the present invention includes a process comprising: 1) mixing a PEF thermoplastic polymer containing each of TPP1 to TPP22 and a blowing agent of the present invention containing each of blowing agents 1 to 31 under conditions for forming a foamy PEF composition; 2) extruding the foamy PEF composition containing each of FC1 to FC11 into a holding zone maintained at a temperature and pressure that does not cause the foamy composition to foam, wherein the holding zone preferably includes a die defining an orifice that opens into a lower pressure zone in which the foamy polymer composition containing each of FC1 to FC11 foams, and an openable gate that closes the die orifice; 3) periodically opening the gate while substantially simultaneously applying mechanical pressure to the foamy polymer composition containing each of FC1 to FC11 with a movable ram, thereby discharging it from the holding zone through the die orifice to a lower pressure zone; and 4) expanding the discharged foamy polymer composition under the influence of a blowing agent to form a foam containing each of foams 1 to 4 and each of foams F1 to F8.

[0123] The present invention also allows the use of a continuous process to form a foam. For example, such a continuous process includes forming a foamable PEF composition containing each of FC1 to FC11, and then expanding the foamable PEF composition without substantial interruption. For example, a foamable PEF composition containing each of FC1 to FC11 can be prepared in an extruder by heating a selected PEF polymer resin containing each of TPP1 to TPP22 to form a PEF melt, incorporating a blowing agent of the present invention containing each of blowing agents 1 to 31 into the PEF melt, preferably by solubilizing the blowing agent in the PEF melt at an initial pressure, to form a foamable PEF composition containing a substantially homogeneous combination of PEF and a blowing agent containing each of FC1 to FC11, and then extruding the foamable PEF composition through a die into a zone of selected foaming pressure, foaming the foamable PEF composition and expanding it under the influence of the blowing agent into a foam containing each of foams 1 to 4 and each of foams F1 to F8 described below. Optionally, a foaming PEF composition comprising a PEF polymer containing each of FC1 to FC11 and an incorporated blowing agent containing each of blowing agents 1 to 31 may be cooled before the composition is extruded through a die to improve specific desired properties of the resulting foam, which includes each of foams 1 to 6 and each of foams F1 to F8.

[0124] This method can be carried out, for example, using a general type of extruder disclosed in Figure 1. Specifically, the extruder may include a raw material supply hopper 10 for holding the PEF polymer 15 of the present invention, each of TPP1 to TPP22, and one or more optional components (which may be added in the hopper or optionally elsewhere in the process with the PEF, depending on the specific needs of the user). The supply material 15, excluding the blowing agent, can be fed into the hopper and delivered to a screw extruder 10. The extruder 20 may include thermocouples (not shown) positioned at three points along its length and a pressure sensor (not shown) at the discharge end 20A of the extruder. A mixer section 30 may be located at the discharge end 20A of the extruder to receive the blowing agent components of the present invention, each of blowing agents 1 to 31, via one or more metering pumps 40A and 40B, and to mix these blowing agents into the PEF molten material in the mixer section. Sensors (not shown) may be included to monitor the temperature and pressure of the mixer section 30. The mixer section 30 can discharge the molten foaming agent composition of the present invention, including each of FC1 to FC11, into a pair of series-oriented molten coolers 50, with temperature sensors (not shown) located in each cooler to monitor the molten temperature. The molten material is then extruded through a die 60, which also has temperature and pressure sensors (not shown) to monitor the pressure and temperature at the die. The die pressure and temperature can be varied according to the requirements of each specific extrusion application for producing the foam 70 of the present invention, including each of foams 1 to 4 and each of foams F1 to F8 described below. The foam can then be carried out of the extruder by a conveyor belt 80.

[0125] The foaming polymer compositions of the present invention, each comprising FC1 to FC11, may optionally contain additional additives such as nucleating agents, foam control agents, glass and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR damping agents, and thermal insulation additives. Examples of nucleating agents include, in particular, materials such as talc, calcium carbonate, and sodium benzoate, as well as chemical blowing agents such as azodicarbonamide or sodium bicarbonate and citric acid. Examples of IR damping agents and thermal insulation additives include, in particular, carbon black, graphite, silicon dioxide, metal flakes, or powders. Examples of flame retardants include, in particular, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ethers. Each of the above additional optional additives can be introduced into the foam at various times and locations during the process according to known techniques, and all such additives and methods of introduction are within the broad scope of the present invention.

[0126] foam In a preferred embodiment, the foam of the present invention is formed using a commercially available extruder and has the properties shown in Table 4 below, the values ​​of which are measured as described in the examples of this specification.

[0127] [Table 7]

[0128] Foams that fall within the scope of the present invention and offer specific advantages are listed in Table 5 below, where all numerical values ​​in the table are understood to be preceded by the word “about”, and the symbol NR means “not required”.

[0129] [Table 8-1]

[0130] [Table 8-2]

[0131] Table 8-3

[0132] Table 8-4

[0133] Table 8-5

[0134] Table 8-6

[0135] Table 8-7

[0136] Table 8-8

[0137] Table 8-9

[0138] Table 8-10

[0139] Table 8-11

[0140] Table 8-12

[0141] Table 8-13

[0142] Table 8-14

[0143] Table 8-15

[0144] Table 8-16

[0145] Table 8-17

[0146] Table 8-18

[0147] Table 8-19

[0148] Table 8-20

[0149] Table 8-21

[0150] Table 8-22

[0151] Table 8-23

[0152] [Table 8-24]

[0153] [Table 8-25]

[0154] [Table 8-26]

[0155] [Table 8-27]

[0156] [Table 8-28]

[0157] The foams of the present invention have broad applicability. The foams, each comprising foams 1-4 and foams F1-F11, offer unexpected advantages in applications requiring low density and / or good compression and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recycled materials and recyclable. Specifically, the foams, each comprising foams 1-6 and foams F1-F8, offer unexpected advantages in wind energy applications (wind turbine blades (shear webs, shells, cores, and routes)), marine applications (hulls, decks, superstructures, bulkheads, longitudinal members, and interiors), industrial lightweight applications, and automotive and transport applications (interiors and exteriors of automobiles, trucks, trains, aircraft, and spacecraft).

[0158] PEF:PET copolymers can be formed by any means known to those skilled in the art, including but not limited to the procedures described in the examples herein.

[0159] The foams of the present invention, each comprising foams 1 to 4, are formed from any of the following: PEF homopolymer, PEF copolymer, PEF:PET copolymer, or a combination / mixture thereof.

[0160] In a preferred embodiment, the foams comprising each of foams 1 to 4 may be formed from a PEF homopolymer having at least 99.5% by weight or at least 99.9% by weight of an ethylene furanoate moiety.

[0161] The foams of the present invention, each comprising foams 1 to 3, are intended to be formed in preferred embodiments from a PEF copolymer, which is a polymer comprising a PEF copolymer having about 10% to about 99% by weight of an ethylene furanoate moiety. The present invention comprises foams, each comprising foams 1 to 3, and the thermoplastic polymer essentially consists of the components listed in the following table.

[0162] [Table 9-1]

[0163] [Table 9-2]

[0164] The foam of the present invention, comprising each of foams 1 to 3, may include closed-cell walls comprising each of the thermoplastic polymers of the present invention, comprising each of TMP1 to TMP12 as described in the table above.

[0165] With respect to these embodiments of the present invention, including PEF copolymers, those skilled in the art will find that, taking into account the teachings contained herein, they can select the type of copolymer material to be used in amounts within each of the ranges described herein in order to achieve the desired enhancement / modification of the polymer without excessive experimentation.

[0166] The TMP of the present invention is contemplated to be formed with various physical properties including polymer properties within the following ranges measured as described in the examples of this specification.

[0167] [Table 10]

[0168] Generally, those skilled in the art are contemplated to be able to formulate PEF polymers within the above property ranges without undue experimentation considering the teachings contained herein. However, in a preferred embodiment, the PEF polymers according to the present invention having these properties (including the PEF:PET copolymers of the present invention) are achieved by using one or more of the above synthesis methods in combination with various known auxiliary processing techniques including those by treatment with a chain extender such as PMDA and / or by SSP treatment.

[0169] An example of a process for chain extension treatment of polyester is provided in the document “Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process,” Firas Awaja, Fugen Daver, Edward Kosior, 16 August 2004, https: / / doi.org / 10.1002 / pen.20155, which is incorporated herein by reference. As described in U.S. Patent Application Publication No. 1009 / 0264545, incorporated herein by reference, chain extenders are generally compounds that are at least bifunctional with respect to reactive groups that can react with terminal groups or functional groups in polyester to extend the length of polymer chains. In particular cases, as disclosed herein, such treatments can favorably increase the average molecular weight of the polyester and improve its melt strength and / or other important properties. The degree of chain extension achieved is at least in part related to the structure and functionality of the compound used. A variety of compounds are useful as chain extenders. Non-limiting examples of chain extenders include trimellitic anhydride, pyromellitic dianhydride (PMDA), trimellitic acid, its haloformyl derivatives, or compounds containing polyfunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Nanocomposite materials, such as finely dispersed nanoclay, may optionally be used to control viscosity. Commercially available chain extenders include Clariant's CESA-Extend, BASF's Joncryl, or Arkema's Lotader. The amount of chain extender may vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to process the polymer can vary widely, in preferred embodiments ranging from about 0.1 to about 5% by weight, or preferably from about 0.1 to about 1.5% by weight. Examples of chain extenders are also described in U.S. Patent No. 4,219,527, which is incorporated herein by reference.

[0170] An example of a process for SSP treatment of poly(ethylene furanoate) is found in the paper "Solid-State Polymerization of Poly(ethylene furanoate) Biobased Polyester, I: Effect of Catalyst Type on Molecular Weight Increase." Provided to Nejib Kasmi, Mustapha Majdoub, George Z. Papageorgiou, Dimitris S. Achilias, and Dimitrios N. Bikiaris, which are incorporated herein by reference.

[0171] foaming agent As described in detail herein, the present invention includes the applicant's discovery that a foaming agent from a selected group can provide foaming PEF compositions and PEF foams comprising each of foams 1 to 3, each of which foaming compositions 1 have a difficult and remarkable combination of physical properties including low density and good mechanical strength properties.

[0172] Therefore, the blowing agent used in accordance with the present invention preferably contains trans-1234ze (hereinafter referred to as blowing agent 1 for convenience), is essentially made from trans-1234ze (hereinafter referred to as blowing agent 2 for convenience), or consists of trans-1234ze (hereinafter referred to as blowing agent 3 for convenience). Therefore, the blowing agent of the present invention, particularly blowing agents 1 and 2, is considered to contain a co-blowing agent in addition to trans-1234ze. Examples of possible co-blowing agents include 1234yf, 1336mzz, 1233zd, and 1224yd. In preferred embodiments, the foaming composition (including foaming composition 1), foam (including foams 1 to 3), and foaming method (including foaming method 1) of the present invention include a foaming agent comprising foaming agents 1 to 3, wherein trans 1234ze is present in an amount of at least about 50% by weight, preferably at least about 60% by weight, preferably at least about 70% by weight, preferably at least about 80% by weight, preferably at least about 90% by weight, preferably at least about 95% by weight, or preferably at least about 99% by weight, based on the total weight of all foaming agents present.

[0173] One or more co-foaming agents not mentioned herein may be included, however, it is intended and understood that the amount of such co-foaming agent used will not interfere with or impair the ability to achieve relatively low-density foams as described herein, and preferably further, not interfere with or impair the ability to achieve foams having the mechanical strength properties as described herein. Accordingly, in consideration of the teachings contained herein, it is conceivable that, as an example, without excessive experimentation, one or more saturated hydrocarbons or hydrofluorocarbons (HFCs), in particular one or more of the co-foaming agents known in the art, such as C4-C6 hydrocarbons or C1-C4 HFCs, can be selected for use in a particular application. Examples of such HFC co-blown agents include, but are not limited to, difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), trifluoroethane (HFC-143), tetrafluoroethane (HFC-134), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane (HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and one or a combination of all isomers of all such HFCs. With respect to hydrocarbons, the blowing agent compositions of the present invention may also, in certain preferred embodiments, include, for example, iso, n, and / or cyclopentane in thermosetting foams, and butane or isobutane in thermoplastic foams.Other materials may include, for example, water, CO2, CFCs (e.g., trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrochlorocarbons (HCCs, for example, dichloroethylene (preferably trans-dichloroethylene), ethyl chloride and chloropropane), HCFCs, C1-C5 alcohols (e.g., ethanol and / or propanol and / or butanol), C1-C4 aldehydes, C1-C4 ketones, C1-C4 ethers (including ethers (e.g., dimethyl ether and diethyl ether), diethers (e.g., dimethoxymethane and diethoxymethane)), and methyl formate, organic acids (e.g., formic acid, but not limited to these) (including any combination thereof), but such components are not necessarily preferred in many embodiments due to their adverse environmental impact.

[0174] Foams and foaming processes The foam of the present invention is a thermoplastic foam, and generally, any one or more of the various known techniques for forming thermoplastic foams can be used in consideration of the disclosures contained herein, and it is considered that all such techniques and all foams formed thereby or all foams within the broad scope of the present invention can be used.

[0175] Generally, the forming step involves introducing a blowing agent to the PEF according to the present invention to form a foamy PEF composition comprising the PEF and the blowing agent. One preferred method for forming such a foamy composition is to plasticize the PEF, which preferably involves heating the PEF to its melting temperature, preferably to a temperature higher than its melting temperature, and then exposing the PEF melt to the blowing agent under conditions that are effective in incorporating (preferably by solubilizing) a desired amount of the blowing agent into the polymer melt.

[0176] The foaming processes of the present invention include batch processes, semi-batch processes, continuous processes, and combinations of two or more of these. A batch process generally involves preparing at least a portion of a foamable polymer composition in a storable state, and then using that portion of the foamable polymer composition at some point in the future to prepare a foam. A semi-batch process involves preparing at least a portion of a foamable polymer composition and intermittently foaming that foamable polymer composition to produce a foam, all in a single process. For example, U.S. Patent No. 4,323,528, incorporated herein by reference, discloses a process for producing a thermoplastic foam via a cumulative extrusion process. Accordingly, the present invention includes a process comprising: 1) mixing a PEF thermoplastic polymer and a blowing agent of the present invention under conditions that form a foamy PEF composition; 2) extruding the foamy PEF composition into a holding zone maintained at a temperature and pressure that does not cause the foamy composition to foam, wherein the holding zone preferably includes a die defining an orifice that opens into a lower pressure zone in which the foamy polymer composition foams, and an openable gate that closes the die orifice; 3) periodically opening the gate while substantially simultaneously applying mechanical pressure to the foamy polymer composition with a movable ram, thereby discharging it from the holding zone through the die orifice to a lower pressure zone; and 4) expanding the discharged foamy polymer composition under the influence of the blowing agent to form a foam.

[0177] The present invention also allows the use of a continuous process to form a foam. For example, such a continuous process includes forming a foamable PEF composition and then expanding the foamable PEF composition without substantial interruption. For example, a foamable PEF composition may be prepared in an extruder by heating a selected PEF polymer resin to form a PEF melt, incorporating the blowing agent of the present invention into the PEF melt, preferably by solubilizing the blowing agent in the PEF melt at an initial pressure, to form a foamable PEF composition containing a substantially homogeneous combination of PEF and blowing agent, and then extruding the foamable PEF composition through a die into a zone of selected foaming pressure to foam the foamable PEF composition and expand the foam under the influence of the blowing agent. Optionally, the foamable PEF composition containing the PEF polymer and the incorporated blowing agent may be cooled before the composition is extruded through the die to improve certain desired properties of the resulting foam.

[0178] A foaming composition according to a preferred embodiment of the present invention may optionally contain additional additives such as nucleating agents, foam control agents, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR damping agents, and thermal insulation additives. Examples of nucleating agents include, in particular, materials such as talc, calcium carbonate, and sodium benzoate, as well as chemical blowing agents such as azodicarbonamide or sodium bicarbonate and citric acid. Examples of IR damping agents and thermal insulation additives include, in particular, carbon black, graphite, silicon dioxide, metal flakes, or powders. Examples of flame retardants include, in particular, brominated materials such as hexabromocyclodecane and polybrominated biphenyl ethers. Each of the above-mentioned additional optional additives can be introduced into the foam at various times and locations during the process according to known techniques, and all such additives and methods of introduction are within the broad scope of the present invention.

[0179] In preferred embodiments, the foam of the present invention is formed by a commercially available extruder and has the properties shown in the following table, the values ​​of which are understood to be measured as shown in the table and supplemented in the “Examples” of this specification and modified by “Approximately”.

[0180] [Table 11]

[0181] The foams of the present invention have broad applicability. The foams of the present invention, comprising each of foams 1 to 3, have unexpected advantages in applications requiring low density and / or good compression and / or tensile and / or shear properties, and / or long-term stability, and / or sustainable sourcing, and / or being made from recycled materials and recyclable. Specifically, the foams of the present invention, comprising each of foams 1 to 3, have unexpected advantages in wind energy applications (wind turbine blades (shear webs, shells, cores, and nacelles)), marine applications (hulls, decks, superstructures, bulkheads, longitudinal members, and interiors), industrial lightweight applications, and automotive and transport applications (interiors and exteriors of automobiles, trucks, trains, aircraft, and spacecraft). [Examples]

[0182] Without limiting the full scope of the present invention, the applicants have demonstrated the utility of the PEF homopolymers and PEF-based copolymers of the present invention and conducted a series of experiments for the purpose of comparing the performance of the foams of the present invention made in accordance with the present invention with the foams made from PET. These tests included the synthesis of a series of PET polymers covering a range of physical properties such as molecular weight, crystallinity, and melting point. The applicants also prepared a series of PEF polymers (including homopolymers and copolymers) over a similar range of physical properties. A series of foams were produced using 1234ze(E), which is highly preferred as a blowing agent. Foams prepared using other halogenated C3 and C4 olefin blowing agents according to the present invention were also tested. A consistent set of processing conditions was utilized for a given range of comparable polymer properties. The details of each of these series of experimental results are described in detail in the following examples. As a summary, the following table provides an indication of some of the important polymer properties, processing conditions, and the advantages of the foams of the present invention over equivalent foams made using PET homopolymer.

[0183]

Table 12-1

[0184]

Table 12-2

[0185]

Table 12-3

[0186] As shown by the above table, for each polymer, a unique temperature pair (for melting and pre-foaming) was identified for the foaming experiments. These temperatures and all other conditions were maintained substantially constant except for the amount of blowing agent, and strength data was created as a function of polymer expansion or relative foam density (RFD) in these foaming experiments. The foaming conditions were selected to ensure proper expansion.

[0187] Throughout the embodiments of this application, the foams thus produced were tested, and the density of the foams was determined using a method generally corresponding to ASTM D71, except that hexane was used as a substitute for water. To facilitate the comparison of the densities of the foams produced in these embodiments, the applicants report the foam density as relative foam density (RFD), which is the density of the foam measured above divided by the density of the starting polymer. In this specification, all foam densities, whether they originate from PEF or PET homopolymer or PEF-PET copolymer, are corrected by the density of PEF polymer, which is 1.43 g / cc, and is about 7% lower than that of PET. In this way, when the strengths of various polymer foams are compared at the same RFD, they are also compared at the same overall density.

[0188] Furthermore, each of the foams produced in these examples was tested to determine its tensile and compressive strengths. The tensile and compressive strengths were measured according to the guidelines specified in ASTM C297 and ISO 844, respectively, and the measurements were performed in the direction of reduced pressure.

[0189] After performing these measurements, the applicants determined that the foam produced in Example C3B4-1 below was equal to the expected value (110 kg / m³) for commercially available PET foam samples tested under the applicants' experimental conditions. 3 It was found that the foams had tensile and compressive strength values ​​equal to (i.e., within approximately 10%) the baseline value. Therefore, to facilitate comparison of the test results provided herein, the tensile and compressive strength values ​​of the foam produced in Example C2B4-1 are set to 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 measured to have a tensile strength twice as great as the tensile strength measured for Example C2B4-1 is reported as having an RTS of 2.

[0190] Preparation of PET homopolymer with a molecular weight of 105.3 kg / mol using comparative example C1A-PMDA and SSP 1 Homopolymers of PET with molecular sizes starting from approximately 10⁵ kg / mol were prepared using the additives and polymer formation procedure described in synthesis example C1A below. 1 The designation of an example as “comparative” in this specification should not be interpreted as indicating that the example represents any item of the prior art, but rather is presented solely for comparison with preferred embodiments of the invention presented in other examples.

[0191] The homopolymer produced in this manner, referred to as PETC1, was tested and found to possess the characteristics reported in Table C1 below. 2

[0192] [Table 13] 2 Throughout these examples, the molecular weights determined and referenced herein refer to molecular weight determination by diffusion-ordered nuclear magnetic resonance spectroscopy (DOSY NMR) as described 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 a, except that the solvent used differs. The above reference used 3 mg of polystyrene and 0.5 mL of deuterated chloroform. In these examples, NMR measurements were performed using the soluble portion of 2-3 mg of polymer in a mixture of 0.6 mL of 50 vol% deuterated chloroform + 50 vol% trifluoroacetic acid.

[0193] Preparation of PET foam using Comparative Example C1B-PET1A with a 1234ze(E) blowing agent for a melting time of 60 minutes. In a series of experiments, 1 gram of polymer in a glass container (shown in Table C1A above) was placed in a 60cc autoclave and then dried under vacuum at a high temperature in the range of 130°C to 150°C for 6 hours. The dried polymer was then cooled to room temperature. In each case, a blowing agent (shown in Table C1B below) was then pumped into the autoclave containing the dried polymer, and the autoclave was subsequently heated to melt the polymer, with the melting pressure listed in Table C1B below. The PET / blowing agent mixture was maintained in a molten state at the molten pressure and temperature for approximately 60 minutes (hereinafter referred to as "melting time"), and then the temperature and pressure of the molten material / blowing agent were reduced over approximately 5 to 15 minutes to the pre-foaming temperature and pre-foaming pressure shown in Table C1B. The autoclave was then maintained at approximately this temperature and pressure for approximately 30 minutes to ensure that the amount of blowing agent incorporated into the molten material under these conditions reached equilibrium. The amount of foaming agent and the conditions used, such as melting temperature and pressure, were determined after several tests based on the ability to form an acceptable foam with an RFD value in the range of approximately 0.05 to 0.15. Then, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (approximately 22°C and 1 atm) (approximately 10 seconds for pressure reduction, and approximately 1 to 10 minutes for temperature reduction using chilled water) to induce foaming.

[0194] Thus, when the foam produced in this comparative example 1B was tested, it was found to have the properties reported in Table C1B below.

[0195] [Table 14]

[0196] The relative tensile strength, relative compressive strength, and combined results of relative tensile strength and compressive strength (hereinafter referred to as "RTS+RCS") of the foam reported in Table C1B above are plotted as a function of relative foam density (RFD) in Figures 2A to 2C, and the dashed line is used to show the linear representation of the tensile strength data as a function of relative foam density.

[0197] The graph above shows the generally expected increase in tensile and compressive strength of PET foam as foam density increases over this density range (the dashed line represents the linear trend of the data).

[0198] Comparative Example 2A - Preparation of PET homopolymers with molecular weights in the range of 80-96 kg / mol and crystallinity of 32-43 using PMDA and SSP Four types of PET homopolymers were prepared by polycondensation, yielding polymer products with molecular sizes ranging from approximately 80 kg / mol to approximately 96 kg / mol, using the procedures described in Synthesis Example C2A1, Synthesis Example C2A2, Synthesis Example C2A3, and the following modifications to achieve polymers with a molecular weight of 83,900, designated as PETC2A4.

[0199] The PET polymers referred to herein as PETC2A1, PETC2A2, PETC2A3, and PETC2A4 were tested and found to possess the properties reported in Table C2A below.

[0200] [Table 15]

[0201] As can be seen from the table above, each of the PET homopolymers was manufactured using the preferred high-crystallinity embodiment of the present invention, and therefore, as shown by comparison with the results of Comparative Example 1A, the PET foam manufactured using the blowing agent of the present invention exhibits unexpectedly high strength compared to PET foam manufactured from PET polymers that do not use this embodiment of the present invention.

[0202] Comparative Example 2B: Preparation of PET foam using PETC2A1, PETC2A2, PETC2A3, and PETC2A4 with a 1234ze(E) blowing agent for a melting time of 60 minutes. In a series of experiments, 1 gram of each polymer (shown in Table C2A above) in a glass container was placed in a 60 cc autoclave and then dried under vacuum at a high temperature in the range of 130°C to 150°C for 6 hours. The dried polymer was then cooled to room temperature. In each case, the blowing agent (shown in Table C2B below) was then pumped into the autoclave containing the dried polymer, and the autoclave was subsequently heated to melt the polymer, with the temperature, pressure, and time listed in Table C2B below. Note that the melting time in this experiment was 60 minutes. After the indicated melting time, the temperature and pressure of the molten material / blowing agent were then reduced over approximately 5 to 15 minutes to the pre-foaming temperature and pre-foaming pressure shown in Table C2B. The autoclave was then maintained at approximately this temperature and pressure for approximately 30 minutes to ensure that the amount of blowing agent incorporated into the molten material under these conditions reached equilibrium. The amount of foaming agent and the conditions used, such as melting temperature and pressure, were determined after several tests based on the ability to form an acceptable foam with an RFD value in the range of approximately 0.05 to 0.2. Then, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (approximately 22°C and 1 atm) (approximately 10 seconds for pressure reduction, and approximately 1 to 10 minutes for temperature reduction using chilled water) to induce foaming.

[0203] Thus, when the PET foam produced in this example C2B was tested, it was found to have the properties reported in Table C2B below.

[0204] [Table 16]

[0205] The unexpected ability to achieve relatively low-density, high-strength PET foams with relatively high molecular weight and improved crystallinity using preferred blowing agents of the present invention, including the HFO-1234ze blowing agent used in this example, is shown in Figures 3A and 3B, comparing the TS and RTS+RCS results of the C2B1, C2B2, and C2B3 data of this comparative example with those of Comparative Example 1B.

[0206] The data provided by this embodiment demonstrates aspects of the applicant's invention relating to the unexpected advantages achieved by forming high-strength, low-density thermoplastic foams containing both PET foams and PEF foams (including PEF copolymers) having relatively high crystallinity. In particular, by utilizing a PET polymer having about 20% higher, and more preferably about 30% higher, crystallinity, as in Example C2B, the tensile strength and RTS+RCS of the foam are unexpectedly improved by about twofold, even compared to polymers with high molecular weight but low crystallinity (i.e., 13.9%).

[0207] Example 1A - Preparation of PEF homopolymer with a MW of approximately 41-75 kg / mol and a crystallinity of 36-42% using PMDA and SSP Using the additives and polymer formation procedures described in Synthesis Examples 1A1 and 1A2, two homopolymers of PEF were prepared, yielding polymer products with molecular sizes ranging from approximately 41 kg / mol to approximately 75 kg / mol.

[0208] The PEF polymers, referred to herein as PEF1A1 and PEF1A2, were tested using the measurement protocol described in Comparative Example 1A above and found to have the properties reported in Table E1A below.

[0209] [Table 17]

[0210] The PEF polymers produced in these examples are referred to as PEF1A1 and PEF1A2 in Table E1 above, and hereafter.

[0211] Example 1B - Preparation of PEF foam using PEF1A1 and PEF1A2 with trans-1234ze blowing agent with a melting time of 60 minutes Using a foaming process designed with the same criteria as described in Comparative Example 1B, one type of foam was prepared using PEF1A1 and four types of foam were prepared using PEF1A2, as described herein. The foams thus produced were tested and found to have the properties reported in Table E1B below.

[0212] [Table 18]

[0213] As revealed by the data in Table E1B above, the applicants have surprisingly found that the PEF foam according to the present invention has unexpectedly high tensile and compressive strength values ​​when measured by RTS+RCS, even when the PET foam has a substantially higher molecular weight than the PEF foam, using the higher crystallinity values ​​according to the present invention, compared with the PET foam (based on the trend line) at nearly equivalent crystallinity. This is shown in Figure 4, for example, by comparison with the trend line of the foam formed from PET of Comparative Example 1A over a relative foaming density range of 0.04 to 0.13, taking into account that the molecular weight of the PEF foam in this embodiment is substantially lower than that of the PET foam.

[0214] As is evident from the graphs above and all the examples presented herein, the PEF foam of the present invention exhibits dramatically superior strength properties compared to PET foam. Referring particularly to the graphs above, even in cases where foam strength generally increases with increasing molecular weight, the PEF foam of the present invention is substantially stronger than PET foam (having the same range of crystallinity) despite the PEF foam having a substantially lower molecular weight than PET foam. Therefore, for example, the trend line for PEF in the graph above at an RFD of about 0.08 has an RTS+RCS 1.3 times greater than the PET trend line based on PET foam formed with a much higher molecular weight. This result is highly advantageous and unexpected.

[0215] Example 2A - Preparation of PEF homopolymers having a MW in the range of approximately 90-96 kg / mol (using PMDA and SSP) Using the additives and polymer formation procedures described in Synthesis Examples 2A1 and 2A2, two homopolymers of PEF were prepared, yielding polymer products with molecular sizes ranging from approximately 90 kg / mol to approximately 96 kg / mol.

[0216] The PEF polymer produced in this manner was tested using the measurement protocol described in Comparative Example 1A above, and it was found to have the properties reported in Table E2A below.

[0217] [Table 19]

[0218] The PEF polymers produced in these examples are referred to as PEF2A1 and PEF2A2 in Table E2A above, and hereafter.

[0219] Example 2B - Preparation of PEF foam using PEF1A1 and PEF1A2 with trans-1234ze blowing agent with a melting time of 60 minutes Using a foaming process designed with the same criteria as described in Comparative Example 1B, three types of foams were prepared using PEF2A1 and one type of foam was prepared using PEF2A2, as described herein. The foams thus produced were tested and found to have the properties reported in Table E2B below.

[0220] [Table 20]

[0221] As revealed by the data in Table E1B above, the applicants have surprisingly found that the PEF foam according to the present invention has unexpectedly high tensile strength and RTS+RCS values. This is shown, for example, by referring to the foam formed from PET in Comparative Example 2A, as shown in Figures 5A and 5B. The following graphs include, for comparative purposes, the PET data in Table C2B and trend lines for all of the PET data in Table C2B.

[0222] As can be seen from the results of this example, the PEF homopolymer foam of the present invention exhibits unexpectedly superior strength compared to PET homopolymer foam produced using the same foaming technique of the present invention, which contains the preferred HFO-1234ze blowing agent of the present invention.

[0223] One unexpected advantage of the present invention illustrated by this embodiment is the remarkably high relative tensile strength and RTS+RCS of the foam, as summarized in Table E2C below.

[0224] [Table 21]

[0225] The results summarized in Table E1C above are particularly unexpected, given that the PET foam of this example is not disclosed in the prior art, i.e., the PET results incorporate a preferred embodiment of the present invention using the preferred blowing agent of the present invention, namely HFO-1234ze(E), with respect to the formation of foams derived from polymers with relatively high crystallinity and high molecular weight. In addition, the PEF-based foam foamed with HFO-1234ze(E) of the present invention is also unexpectedly superior to the PEF-based foam of the present invention when foamed with other halogenated olefin blowing agents, as shown in Example 14 of this specification.

[0226] Example 3A - Preparation of PET9:PEF1 copolymer with a MW of approximately 117.9 kg / mol using PMDA A PET9:PEF1 block copolymer (9:1 molar ratio) with a target molecular weight of approximately 117,900 g / mol of the PET portion of the copolymer was prepared using the additives and polymer formation procedure described in Synthesis Example 3A.

[0227] The PET9:PEF1 copolymer produced in this manner was tested using the measurement protocol described in Comparative Example 1A above, and it was found to have the properties reported in Table E3A below.

[0228] [Table 22]

[0229] The resulting PET9:PEF1 copolymer is referred to as PET9PEF1-EX3A in these examples.

[0230] Preparation of PEF foam using Example 3B-PET9PEF1-EX3A with trans-1234ze blowing agent with a melting time of 60 minutes Six types of foams were prepared from PET9PEF1-EX3A using a foaming process designed with the same standards as described in Comparative Example 1. The foams thus produced were tested and found to possess the characteristics reported in Table E3B below.

[0231] [Table 23]

[0232] As revealed by the data in Table E3B above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX3B according to the present invention has unexpectedly high strength properties.

[0233] Figures 6A to 6D show the average tensile strength values ​​of foam in RFD in three density ranges, namely (i) 0.056 to 0.062, (ii) 0.077 to 0.079, and 0.171 to 0.177, as shown in Table E3B above. For comparison purposes, average data for the same range in PET data from Table C2B are also included.

[0234] As can be seen from the results of this embodiment, the PET9:PEF1 copolymer foam of the present invention exhibits unexpectedly superior strength over a wide range of relative densities, with respect to the foam's remarkably high relative tensile strength and remarkably high compressive strength, as exemplified by this embodiment. In particular, the extent of this unexpected advantage relating to this embodiment is summarized in Table E3C below.

[0235] [Table 24]

[0236] The context of these results includes the fact that the comparative examples incorporate preferred embodiments of the present invention relating to the formation of foams derived from polymers with relatively high crystallinity and high molecular weight, as well as the preferred blowing agent of the present invention (i.e., HFO-1234ze(E)).

[0237] Comparative Example 3B: Preparation of PET foam using PETC2A1 and PETC2A2 with a 1234ze(E) blowing agent for a melting time of 15 minutes. In a series of experiments, 1 gram of each polymer (shown in Table C2A for PETC2A1 and PETC2A2 above) in a glass container was placed in a 60 cc autoclave and then dried under vacuum at a high temperature in the range of 130°C to 150°C for 6 hours. The dried polymer was then cooled to room temperature. In each case, a blowing agent (shown in Table C3B below) was then pumped into the autoclave containing the dried polymer, and the autoclave was subsequently heated to melt the polymer, with the temperature, pressure, and time listed in Table C3B below. Note that the melting time in this experiment was 15 minutes. After the indicated melting time, the temperature and pressure of the molten material / blowing agent were then reduced over approximately 5 to 15 minutes to the pre-foaming temperature and pre-foaming pressure shown in Table C3B. The autoclave was then maintained at approximately this temperature and pressure for approximately 30 minutes to ensure that the amount of blowing agent incorporated into the molten material under these conditions reached equilibrium. The amount of foaming agent and the conditions used, such as melting temperature and pressure, were determined after several tests based on the ability to form an acceptable foam with an RFD value in the range of approximately 0.05 to 0.2. Then, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (approximately 22°C and 1 atm) (approximately 10 seconds for pressure reduction, and approximately 1 to 10 minutes for temperature reduction using chilled water) to induce foaming.

[0238] Thus, when the PET foam produced in this example C3B was tested, it was found to have the properties reported in Table C3B below.

[0239] [Table 25]

[0240] Example 4B - Preparation of PEF foam using PEF2A2 with trans-1234ze blowing agent with a melting time of 15 minutes Six types of foams were produced using PEF2A2 as described in Table E2A, a foaming process designed using the same criteria as that described in Comparative Example 1B, and the same basic process except that the melting time was 15 minutes. The foams thus produced were tested and found to have the properties reported in Table E4B below.

[0241] [Table 26]

[0242] As revealed by the data in Table E4B above, the applicants have surprisingly found that the PEF foam according to the present invention has unexpectedly high tensile and compressive strength values. This is illustrated, for example, by referring to the foam formed from PET in Comparative Example C3B2, and in particular, considering the fact that the comparative example incorporates preferred embodiments of the present invention relating to the formation of foam derived from a polymer with relatively high crystallinity and high molecular weight, as well as the preferred blowing agent of the present invention (i.e., HFO-1234ze(E)), and is illustrated by the following graph. Figure 7 shows the results of the foam data in the RFD region of approximately 0.116.

[0243] 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 foams produced using the same foaming technique of the present invention, which contains the preferred HFO-1234ze blowing agent of the present invention. For example, with respect to the remarkably high relative tensile strength and RTS+RCS of the foam, as illustrated by this embodiment. In particular, the extent of this unexpected advantage is summarized in Table E4C below.

[0244] [Table 27]

[0245] Example 5: Preparation of PET9:PEF1 copolymer with approximately 45 kg / mol MW and 28.6 CR% using PMDA. A PET9:PEF1 block copolymer (9:1 molar ratio) with a target molecular weight of approximately 45,000 g / mol for the PET portion of the copolymer was prepared using the additives and polymer formation procedure described in Synthesis Example 5Ae below.

[0246] The PET9:PEF1 copolymer produced in this manner was tested using the measurement protocol described in Example 1A above, and it was found to have the properties reported in Table E5A below.

[0247] [Table 28]

[0248] The resulting PET9:PEF1 copolymer is referred to as PET9PEF1-EX5A in these examples.

[0249] Preparation of PEF foam using Example 5B-PET9PEF1-EX5A with trans-1234ze blowing agent with a melting time of 15 minutes. Two types of foams were prepared from PET9PEF1-EX5A using a foaming process designed with the same standards as described in Comparative Example 1. The foams thus produced were tested and found to have the properties reported in Table E5B below.

[0250] [Table 29]

[0251] As revealed by the data in Table E5B above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX5B according to the present invention has unexpectedly high strength properties.

[0252] Figure 8 shows the foam strength values ​​compared to the average values ​​of PETC3B2 foam in the same density ranges included in Table E5B above, namely approximately 0.05-0.06 and approximately 0.13-0.15 (reported in Table C3B above).

[0253] As can be seen from the results of this embodiment, the PET9:PEF1 copolymer foam of the present invention exhibits unexpectedly excellent strength with respect to a remarkably high RCS in the RFD range of about 0.06 to about 0.14, as demonstrated by this embodiment. In particular, the extent of this unexpected advantage with respect to this embodiment is summarized in Table E5C below.

[0254] [Table 30]

[0255] Preparation of PET99:PEF1 copolymer with approximately 92-97 kg / mol of PET MW and 28.8-33.5% Cr% using Examples 6A1 and 6A2-PMDA and SSP. Two random copolymers of PET99:PEF1 (99:1 molar ratio), with target molecular weights of approximately 92 and 97 kg / mol for the PET portion and a target molecular weight of approximately 45,000 g / mol for the PET portion of the copolymer, were prepared using the additives and polymer formation procedure described in Synthesis Example 6A1 below, or a modified version thereof to achieve polymers with target molecular weights of 92,160.

[0256] The PET99:PEF1 copolymer was tested and found to possess the properties shown in Table E6A.

[0257] [Table 31]

[0258] The PET99:PEF1 copolymers thus produced are referred to as PET99PEF1-EX6A1 and PET99PEF1-EX6A2 in these examples.

[0259] Example 6B-PET99PEF1-EX6A1 and A2 were used with a trans-1234ze blowing agent for a melting time of 15 minutes to prepare a foam. Six types of foams were prepared from PET99PEF1-EX6B using a foaming process designed with the same standards as described in Comparative Example 1. The foams thus produced were tested and found to possess the characteristics reported in Table EB below.

[0260] [Table 32]

[0261] As revealed by the data in Table E6B above, the applicants surprisingly found that the foams produced with PET99:PEF1-EX6A1 and EX6A2 according to the present invention have unexpectedly high strength properties.

[0262] Figure 9 shows the tensile strength, compressive strength, and combinations of tensile strength + compressive strength for the foams shown in Table E6B above. For the convenience of comparison, it also includes the PET data from Table C1B.

[0263] As can be seen from the results of this example, the PET99:PEF1 copolymer foam of the present invention exhibits unexpectedly superior strength, as shown by comparing it to, for example, the PET homopolymer foam produced in Comparative Example 1 using the preferred HFO-1234ze blowing agent of the present invention. As can be seen from the results of this example, the PET99:PEF1 homopolymer foam of the present invention exhibits unexpectedly superior strength compared to the PET homopolymer foam produced using the same foaming technique of the present invention, which includes the preferred HFO-1234ze blowing agent of the present invention. In particular, the degree of this unexpected advantage is summarized in Table E6C below.

[0264] [Table 33]

[0265] Example 7: Preparation of PET19:PEF1 copolymer with approximately 46 kg / mol of PET MW and 30.2% Cr% using PMDA. A random copolymer of PET19:PEF1 (19:1 molar ratio), with a target molecular weight of approximately 46 kg / mol for the PET portion, was prepared using the same additives and basic polymer formation procedure as described in Synthesis Example 8A below, but modified to produce a target PET molecular weight of approximately 46 kg / mol.

[0266] The PET19:PEF1 copolymer was tested and found to possess the properties shown in Table E7A.

[0267] [Table 34]

[0268] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX7A1 in this example.

[0269] Preparation of foam using Example 7B-PET19PEF1-EX7A1 with trans-1234ze blowing agent with a melting time of 15 minutes A foam was prepared from PET19PEF1-EX7A using a foaming process designed with the same standards as described in Comparative Example 1. The foam thus produced was tested and found to have the properties reported in Table E7B below.

[0270] [Table 35]

[0271] As revealed by the data in Table E7B above, the applicants found that foams prepared with PET19:PEF1-EX7A1 according to the present invention possess excellent strength properties. For example, foams prepared with the relatively low-density copolymer of the present invention have strength values ​​that are favorably comparable to the average results of PET homopolymer foams identified as C3B2-14 (having an RFD of 0.063) and C3B2-2 (having an RFD of 0.088) in Table C3B above, which have approximately twice the molecular weight of the PET19:PEF1 copolymer of the present invention. This unexpected result is shown in Figure 10 with respect to RTS+RCS.

[0272] If the molecular weight of the PET homopolymer is more than twice that of the PET19:PEF1 of the present invention, then it is unexpected that the strength values ​​of PET19:PEF1 are equivalent.

[0273] Preparation of PET19:PEF1 copolymer with approximately 72-79 kg / mol of PET MW and 27.62-32% using Examples 8A1 and 8A2-PMDA and SSP. Two types of random copolymers of PET19:PEF1 (19:1 molar ratio), with target molecular weights of approximately 72 kg / mol and 79 kg / mol for the PET portion, were prepared using the additives and polymer formation procedures described in Synthesis Examples 8A1 and 8A2.

[0274] The PET19:PEF1 copolymer was tested and found to possess the properties shown in Table E8A.

[0275] [Table 36]

[0276] The resulting PET19:PEF1 copolymers are referred to as PET19PEF1-EX8A1 and PET19PEF1-EX8A2 in this example.

[0277] Preparation of foam using Example 8B-PET19PEF1-EX8A1 and EX8A2 with trans-1234ze blowing agent with a melting time of 15 minutes Foams were prepared from PET19PEF1-EX8A1 and EX8A2 respectively using a foaming process designed with the same standards as described in Comparative Example 1. The foams thus produced were tested and found to have the properties reported in Table E8B below.

[0278] [Table 37]

[0279] As revealed by the data in Table E8B above, the applicants found that foams prepared with PET19:PEF1-EX8A1 and EX8A2 according to the present invention possess excellent strength properties. For example, the foam of the present invention with an average RFD of 0.091 exhibits strength values ​​that are favorably comparable to the PET homopolymer foams identified as C3B1-2 and C3B2-2 in Table C3B above, and has the same average density compared to the RFD of the PET19:PEF1 copolymer of this example. This unexpected result is shown in Figure 11.

[0280] Assuming that the crystallinity of the PET homopolymer is 1.3 times higher than that of PET19:PEF1, and that the MW of the PET homopolymer is 1.2 times higher than that of PET19:PEF1 in this embodiment, it is completely unexpected that the strength value of PET19:PEF1 is comparable to that of the foam formed from the PET homopolymer. Furthermore, it is particularly unexpected that the relative compressive strength of the present invention is greater than that of the PET homopolymer, resulting in a higher combined RTS+CTS value than that of the PET homopolymer.

[0281] Example 9: Preparation of PET19:PEF1 copolymer with approximately 62 kg / mol of PET MW and 26.1% Cr% using A1-PMDA and SSP. A random copolymer of PET19:PEF1 (19:1 molar ratio), with a target molecular weight of approximately 62 kg / mol for the PET portion, was prepared using the same additives and basic polymer formation procedure as described in Synthesis Example 8A below, but modified to produce a target PET molecular weight of approximately 62 kg / mol.

[0282] The PET19:PEF1 copolymer was tested and found to possess the properties shown in Table E9A.

[0283] [Table 38]

[0284] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX9A1 in this example.

[0285] Preparation of foam using Example 9B-PET19PEF1-EX9A1 with trans-1234ze blowing agent with a melting time of 15 minutes A foam was prepared from PET19PEF1-EX9A using a foaming process designed with the same standards as described in Comparative Example 1. The foam thus produced was tested and found to have the properties reported in Table E9B below.

[0286] [Table 39]

[0287] As revealed by the data in Table E9B above, the applicants found that foams produced with PET19:PEF1-EX9A1 according to the present invention possess excellent strength properties. For example, foams produced with the relatively low-density copolymer of the present invention have a density of 0.104 and therefore have strength values ​​that are very close to the density of the PET19:PEF1 copolymer of the present invention and are favorably comparable to the PET homopolymer foams identified as C3B1-3 in Table C3B above. This unexpected result is shown in Figure 12.

[0288] If the molecular weight of the PET homopolymer is more than 1.5 times larger than the molecular weight of PET19:PEF1 of the present invention, then it is completely unexpected that each of the reported strength values ​​of PET19:PEF1 is essentially equivalent to the strength values ​​of the PET homopolymer.

[0289] Example 10: Preparation of PET19:PEF1 copolymer with approximately 79 kg / mol of PET MW and 32.4% Cr% using PMDA and SSP. A random copolymer of PET19:PEF1 (19:1 molar ratio), with a target molecular weight of approximately 79 kg / mol for the PET portion, was prepared by modifying the additives and basic polymer formation procedure described in Synthesis Example 8A below to produce a target PET molecular weight of approximately 79 kg / mol.

[0290] The PET19:PEF1 copolymer was tested and found to possess the properties shown in Table E10A.

[0291] [Table 40]

[0292] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX10A in this example.

[0293] Preparation of foam using Example 10B-PET19PEF1-EX10A with transformer 1234ze blowing agent with a melting time of 15 minutes A foam was prepared from PET19PEF1-EX10A using a foaming process designed with the same standards as described in Comparative Example 1. The foam thus produced was tested and found to have the properties reported in Table E10B below.

[0294] [Table 41]

[0295] As revealed by the data in Table E10B above, the applicants found that the foam prepared with PET19:PEF1-EX10A according to the present invention exhibits excellent strength properties. For example, the foam in this example had a density of 0.13, but showed strength values ​​that were well comparable to PET homopolymers with substantially the same density but a much higher molecular weight. In particular, the PET homopolymer foam identified as C3B1-4 in Table C3B above had a density of 0.129 and a molecular weight 20% higher than the PET19:PEF1 copolymer used to prepare the foam of the present invention. Nevertheless, as shown in Figure 13, the strength values ​​of the two foams were unexpectedly comparable.

[0296] If we assume that the molecular weight of the PET homopolymer is approximately 20% larger than that of PET19:PEF1 in this invention, then it is completely unexpected that each of the reported strength values ​​of PET19:PEF1 is almost the same as that of the PET homopolymer.

[0297] Example 11: Preparation of PET19:PEF1 copolymer with approximately 83 kg / mol of PET MW and 20.7% Cr% using PMDA and SSP. A PET19:PEF1 block copolymer (19:1 molar ratio) with a target molecular weight of approximately 83 kg / mol for the PET portion was prepared as described in Synthesis Example 11A below.

[0298] The PET19:PEF1 copolymer was tested and found to possess the properties shown in Table E11A.

[0299] [Table 42]

[0300] The resulting PET19:PEF1 copolymer is referred to as PET19PEF1-EX11A in this example.

[0301] Preparation of foam using Example 11B-PET19PEF1-EX10A with transformer 1234ze blowing agent with a melting time of 15 minutes A foam was prepared from PET19PEF1-EX11A using a foaming process designed with the same standards as described in Comparative Example 1. The foam thus produced was tested and found to have the properties reported in Table E11B below.

[0302] [Table 43]

[0303] As evident from the data in Table E11B above, the applicants found that foams prepared with PET19:PEF1-EX11A according to the present invention possess excellent strength properties. For example, the foam in this example was prepared from a copolymer having a PET portion with a molecular weight of approximately 83 kg / mol and a crystallinity of approximately 21%, yet it exhibited strength values ​​that were well comparable to or even exceeding those of PET homopolymers prepared from polymers with substantially the same density but 1.2 times higher molecular weight and 1.6 times higher crystallinity. In particular, the PET homopolymer foam identified as C3B1-4 in Table C3B above had a density of 0.129 and exhibited a relative compressive strength substantially lower than the lower density compressive strengths of the PET19:PEF1 data in this example, as shown in Figure 14.

[0304] If the molecular weight of the PET homopolymer is approximately 20% greater than that of the PET19:PEF1 of the present invention, and its crystallinity is approximately 60% higher, then it is completely unexpected that each of the reported strength values ​​of PET19:PEF1 is approximately the same as or slightly higher than that of the PET homopolymer.

[0305] Preparation of PET9:PEF1 copolymer with approximately 57-69 kg / mol MW and 28-34 CR% using Examples 12A1 and 12A2-ADR, PMDA, talc, and SSP. Two types of block copolymers (9:1 molar ratio) of PET9:PEF1, with a target molecular weight of approximately 57 to 69 kg / mol for the PET portion of the copolymer, were prepared using the additives and polymer formation procedures described in Synthesis Examples 12A1 and 12A2.

[0306] The PET9:PEF1 copolymer produced in this manner was tested using the measurement protocol described in Comparative Example 1A above, and it was found to have the properties reported in Table E12A below.

[0307] [Table 44]

[0308] The resulting PET9:PEF1 copolymers are referred to as PET9PEF1-EX12A1, PET9PEF1-EX12A2, and PET9PEF1-EX12A3 in these examples.

[0309] Preparation of PEF foam using Example 12B-PET9PEF1-EX12A1 with trans-1234ze blowing agent with a melting time of 15 minutes. Three types of foams were prepared from PET9PEF1-EX12A1 using a foaming process designed with the same standards as described in Example 5A. The foams thus produced were tested and found to have the properties reported in Table E12B1 below.

[0310] [Table 45]

[0311] As revealed by the data in Table E12B above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX12A1 according to the present invention has unexpectedly high strength properties.

[0312] Figure 15 shows the strength values ​​of the foam compared to the PET9:PEF1 foam produced using PMDA in Example 5, in the same density range encompassed in Table E5B above, namely approximately 0.05 to 0.06 and approximately 0.13 to 0.15.

[0313] As can be seen from the results of this example, PET9:PEF1-EX12 produced an acceptable foam with good expansion.

[0314] Example 12: Preparation of PEF foam using C-PET9PEF1-EX12A2 with trans-1234ze blowing agent with a melting time of 15 minutes. A foam was prepared from PET9PEF1-EX12A2 using a foaming process designed with the same standards as described in Example 5A. The foam thus produced was tested and found to have the properties reported in Table E12B2 below.

[0315] [Table 46]

[0316] As revealed by the data in Table E12B2 above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX12A2 according to the present invention has unexpectedly high strength properties.

[0317] Figure 16 shows the strength values ​​of the foam compared to the PET9:PEF1 foam produced using PMDA in Example 5, in the density range between the density ranges shown in Table E5B above, i.e., approximately 0.055 to approximately 0.144.

[0318] As can be seen from the results of this example, PET9:PEF1-EX12 produced an acceptable foam with good expansion.

[0319] Preparation of PET9:PEF1 and PET19:PEF1 copolymers with a MW of approximately 47-12 kg / mol using Examples 13A1 and 13A2-PMDA and SSP A first block copolymer of PET9:PEF1 (9:1 molar ratio), in which the target molecular weight of the PET portion is approximately 47 kg / mol and the PET and PEF oligomer blocks are 1-5 (monomers), 1-5 (monomers), was prepared using a PENTA additive as described in Synthesis Example 13A along with the polymer formation procedure to achieve a target molecular weight of 47,030, or by using a modified version of Synthesis Example 13A to achieve a target molecular weight of approximately 45,000 or approximately 12,000 kg / mol.

[0320] The PET:PEF copolymer produced in this manner was tested using the measurement protocol described in Example 1A above, and it was found to have the properties reported in Table E13A below.

[0321] [Table 47]

[0322] 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.

[0323] Example 13: Preparation of PEF foam using B1-PET9PEF1-EX13A1 with trans-1234ze blowing agent with a melting time of 15 minutes. A foam was prepared from PET9PEF1-EX13A1 using a foaming process designed according to the same standards as described in Comparative Example 5, except that PENTA was used instead of PMDA. The foam thus produced was tested and found to have the properties reported in Table E13B below.

[0324] [Table 48]

[0325] As revealed by the data in Table E13B1 above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX13A1 according to the present invention has unexpectedly high strength properties.

[0326] Figure 17 shows the strength values ​​of the foam compared to the PET9:PEF1 foam produced using PMDA in Example 5, within the density range of the foam shown in Table E5B above, which has a value of approximately 0.055.

[0327] As can be seen from the results of this example, PET9:PEF1-EX12 produced an acceptable foam with good expansion.

[0328] Example 13: Preparation of PET19:PEF1 copolymer with approximately 45 kg / mol MW using B2-PENTA A foam was prepared from PET19PEF1-EX13A2 using a foaming process designed according to the same standards as described in Example 7, except that PENTA was used instead of PMDA. The foam thus produced was tested and found to have the properties reported in Table E13B2 below.

[0329] [Table 49]

[0330] As revealed by the data in Table E13B2 above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX13A2 according to the present invention has unexpectedly high strength properties.

[0331] Figure 18 shows the strength values ​​of the foam compared to the PET9:PEF1 foam produced using PMDA in Example 7, within the density range of the foam shown in Table E7B above, which has a value of approximately 0.08.

[0332] As can be seen from the results of this example, PET9:PEF1-EX12 produced an acceptable foam with good expansion.

[0333] Example 13: Preparation of PET19:PEF1 copolymer with approximately 11.69 kg / mol MW using B3-PENTA and SSP A foam was prepared from PET19PEF1-EX13A3 using a foaming process designed according to the same standards as described in Example 9B, except that PENTA was used instead of PMDA. The foam thus produced was tested and found to have the properties reported in Table E13B3 below.

[0334] [Table 50]

[0335] As revealed by the data in Table E13B3 above, the applicants surprisingly found that the foam produced with PET9:PEF1-EX13A3 according to the present invention possesses unexpectedly high strength properties.

[0336] Figure 19 shows the strength values ​​of the foam compared to the PET9:PEF1 foam produced using PMDA in Example 9, within the density range of the foam shown in Table E97B above, which has a value of approximately 0.107.

[0337] As can be seen from the results of this example, PET9:PEF1-EX12 produced an acceptable foam with good expansion.

[0338] Example 14B - Preparation of PET9:PEF1 foam using PET9:PEF1_Ex3A, trans-123zd, trans-1233zd, and cis-1336 blowing agents, and a melting time of 60 minutes. A series of foams using PET9:PEF1_Ex3A were prepared using a foaming process designed with the same standards as those described in Comparative Example 1B. The foams thus produced were tested and found to possess the properties reported in Table E14B below.

[0339] [Table 51]

[0340] As evident from the data in Table E1B above, the applicants have found that, surprisingly, the PET:PEF foam according to the present invention generally exhibits superior strength properties compared to other blowing agents such as 1233zd and 1336 when the blowing agent contains, is essentially derived from, or consists of 1234ze(E), as is evident from the data in the table above. Nevertheless, when the blowing agent contains, is essentially derived from, or consists of 1233zd(E) or 1336mzz(Z), an acceptable foam is produced with substantial utility, as is also evident from the data above.

[0341] Comparative Example 4A: Preparation of PET homopolymer with a molecular weight of 46.4 kg / mol using PMDA and SSP. PET homopolymers were prepared using the same design conditions as specified in Comparative Example 1, but the process conditions were targeted to produce polymer molecular weights in the range of 40,000 to 50,000 g / mol. Similar to Comparative Example 1, the polymer was treated with 0.7 wt% of the chain extender PMDA according to known techniques, and then subjected to solid-phase polymerization as described in Comparative Example 1 to produce PET homopolymers. The PET homopolymers were tested and found to possess the characteristics reported in Table C4A below.

[0342] [Table 52]

[0343] The PET polymer produced in this manner is referred to as PETC4A in these examples.

[0344] Preparation of PET foam using Comparative Example 4B-PETC4A with 1234ze(E) blowing agent Two types of foams were prepared by drying 1 gram of polymer (shown in Table C4B below) in a glass container at 130°C for 6 hours under vacuum, then filling an autoclave with the polymer and cooling it to room temperature. Next, for each polymer, a blowing agent (shown in Table C4B below) was pumped into the autoclave containing the dried polymer, and the autoclave was then heated to the molten state and pressure shown in Table C4B. The PET / blowing agent mixture was maintained in a molten state for approximately 1 hour, and then the temperature and pressure of the molten material / blowing agent were reduced over approximately 5-15 minutes to the pre-foaming temperature and pressure shown in Table C4B. The autoclave was then maintained at approximately this temperature and pressure for approximately 30 minutes to allow the amount of blowing agent incorporated into the molten material to reach equilibrium under these conditions. The amount of blowing agent and the conditions used, such as melting temperature and pressure, were determined after several tests based on the ability to form an acceptable foam with an RFD value of approximately 0.2 or less. Next, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (approximately 22°C and 1 atmosphere) (the pressure reduction took about 10 seconds, and the temperature reduction using chilled water took about 1 to 10 minutes), causing foaming.

[0345] The foam produced in Comparative Example 4 was tested and found to have the properties reported in Table C4B below.

[0346] [Table 53]

[0347] Example 15A - Preparation of a PEF homopolymer with approximately 49 kg / mol MW using PMDA and SSP PEF homopolymers were prepared using the same additives and basic polymer formation procedure as those used in Comparative Example 3 for PET homopolymer formation, achieving a polymer molecular weight of approximately 49,000 g / mol. Specifically, the 49 kg / mol MW PEF homopolymer was formed by esterification and polycondensation of 75 grams of 2,5-franzicarboxylic acid (FDCA) and 59.8 grams of monoethylene glycol (EG). The reactants were added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After vacuuming and backfilling with nitrogen, 0.067 grams of titanium(IV) isopropoxide catalyst were added to the flask. The flask was then lowered into a salt bath at 180°C, and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under nitrogen, vacuum was initiated after 30 minutes at this temperature. After 40 minutes under vacuum, the temperature was raised to 230°C and maintained for 1 hour. Under a nitrogen stream, 0.58 grams (0.7 wt%) of PMDA were slowly added over approximately 5 minutes. To perform SSP, an aliquot (30 g) of the product was pulverized and heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer as described below. When the PEF homopolymer was tested using the same measurement technique as described in Comparative Example 1, it was found to have the properties reported in Table E15 below.

[0348] [Table 54]

[0349] The PEF polymer produced in this manner will be referred to as PEF15A in Table E3 and the following examples.

[0350] Example 15B-PEF3 and preparation of PEF foam using Trans 1234ze as a blowing agent Three types of foams were prepared from PEF2 using a foaming process designed with the same standards as those described in Comparative Example 1, as described herein. When the foams thus produced were tested, they were found to have the properties reported in Table 15A below.

[0351] [Table 55]

[0352] The initial observation regarding the test results shown in the table above is that, for PET foams, a decrease in molecular weight to 46.5K resulted in a substantial decrease in foam strength compared to PET foams made from higher molecular weight PET. For example, Comparative Example C2G, using PET with a molecular weight of 83.9K, produced a foam with an RFD of 0.09 and an RTS of 1.0. The 46.5K PET foam of this example produced a foam with an RTS of less than half its value, even with a higher RFD.

[0353] Surprisingly, foams made from low molecular weight PEF showed no substantial decrease in tensile strength compared to PEF foams made from high molecular weight PEF. This result is unexpected. Consequently, the tensile strength of foams made from a PEF homopolymer with a molecular weight of 49K and a 1234ze(E) blowing agent was dramatically superior to that of foams made from a PET homopolymer with a molecular weight of 46.5K and a 1234ze(E) blowing agent. This unexpected result can be demonstrated, for example, by observing that the average RFD of three PEF data points according to the present invention results in an average density of 0.079 and an average relative tensile strength of 1.34. Nevertheless, compared to PET foams with a density more than 200% greater than the average PEF foam density, the PEF foams of the present invention exhibit an average tensile strength four times greater than the average relative tensile strength of high-density PET foam (0.35). This is a very significant and unexpected result.

[0354] Example 16 - Preparation of PET9:PEF1 copolymer with approximately 133.8 kg / mol MW using PMDA and SSP A random copolymer of PET9:PEF1 (9:1 molar ratio) was prepared by adding 8.7 grams (0.0472 mol) of methyl frangic acid carboxylate (FDME), 106.8 grams (0.42 mol) of bis(2-hydroxyethyl) terephthalate (BHET), and 6.2 grams (0.1 mol) of EG to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condenser. After evacuating and refilling with N2, 0.046 grams of Ti(IV) isopropoxide catalyst was added. The reactor was then placed in a salt bath at 180°C, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was increased to 220°C. After 30 minutes under N2, vacuum was initiated. After 40 minutes under vacuum, the temperature was increased to 250°C and continued for 40 minutes. Under an N2 atmosphere, 0.59 grams of PMDA (0.0.0027 moles) were slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped. An aliquot (30 g) of the above product was pulverized, and then solid-phase polymerization was carried out by heating in a rotary evaporator at 180°C under vacuum for 3 days. When the PEF polymer was tested, it was found to have the characteristics shown in Table E7.

[0355] [Table 56]

[0356] The resulting PET9:PEF1 random copolymer is referred to as PET9PEF1-EX16 in these examples.

[0357] Examples 16B1-16B3: Preparation of PETPEF copolymer foam using PET9PEF1-EX16B and trans-1234ze as a blowing agent Three types of foams were prepared from PET9PEF1-EX16B using a foaming process designed with the same standards as described in Comparative Example 1. The foams thus produced were tested and found to have the properties reported in Table E16B below.

[0358] [Table 57]

[0359] As revealed by the data in Table E16B above, the applicants surprisingly found that the foam produced from PEF9:PET1-EX16B according to the present invention has unexpectedly superior tensile strength compared to foams formed from PET homopolymers, as shown in Figure 20, which includes PET tensile strength data from comparative examples for comparison.

[0360] As shown in Figure 20, the relative tensile strength of the foam produced from PET9PEF1-EX16B copolymer containing a relatively low proportion of PEF (approximately 10 mol%) and using 1234ze(E) as a blowing agent was superior to that of foams produced from PET1A and PET1B homopolymers and the 1234ze(E) blowing agent.

[0361] One aspect of this unexpected result can be illustrated, for example, by noting that at an RFD of approximately 0.062, the two foams prepared using the PET9PEF1-EX16B copolymer had an average relative tensile strength of 0.89. In contrast, at this same RFD of approximately 0.062, the PET homopolymer had a relative tensile strength of approximately 0.52, based on the trend line of the PET data, as shown by the dashed line in the graph above. This represents a relative tensile strength of approximately 1.7 times greater for the PET9PEF1 foam of this embodiment compared to the foam prepared from the PET homopolymer. Similarly, at an RFD of approximately 0.088, the PET9PEF1 foam had a relative tensile strength of 1.41. In contrast, at this same RFD of approximately 0.088, the PET homopolymer foam had a relative tensile strength of approximately 0.75, according to the PET trend line. This represents a relative tensile strength of approximately 1.9 times greater for the applicant's PET9PEF1 foam. These are important and unexpected results.

[0362] Preparation of PET homopolymer with a molecular weight of approximately 38 kg / mol using comparative example C5-PMDA and SSP PET homopolymer was prepared by adding approximately 93 grams (0.3659 mol) of bis(2-hydroxyethyl) terephthalate (BHET) to a 500 mL round-bottom flask. After vacuuming and refilling with N2, the flask was lowered into a 180°C salt bath and overhead mixing was started at 100 rpm under N2 flow. 0.13 grams (0.00045 mol) of titanium isopropoxide catalyst was added to the flask. After 1 hour, the bath temperature was raised to 230°C. After 30 minutes at this temperature under N2, vacuum was started and continued for 1 hour, and then the temperature was further raised to 285°C. After 2 hours at 285°C, pyromellitic dianhydride PMDA (0.49 g, 0.0022 mol) was slowly added over approximately 10 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. An aliquot (30g) of the above product was pulverized, and then solid-phase polymerization was carried out by heating under vacuum at 180°C in a rotary evaporator for 3 days. When the PET homopolymer produced in this way was tested, it was found to have the characteristics reported in Table C5 below.

[0363] [Table 58]

[0364] The PET polymer produced in this manner is referred to as PETC3 in these examples.

[0365] Comparative Example 6 - Preparation of PEF foam using PETC3 together with 1234ze(E) blowing agent One gram of polymer (shown in Table C6 below) in a glass container was placed in an autoclave and dried under vacuum at 130°C for 6 hours. The dried polymer was then cooled to room temperature and placed in a glass container within the autoclave. Next, for each polymer, a blowing agent (shown in Table C6 below) was pumped into the autoclave containing the dried polymer, and the autoclave was subsequently heated to the molten state and pressure shown in Table C6. The PET / blowing agent mixture was maintained in a molten state for approximately 1 hour, and then the temperature and pressure of the molten material / blowing agent were reduced over approximately 5-15 minutes to the pre-foaming temperature and pressure shown in Table C6. The autoclave was then maintained at approximately this temperature and pressure for approximately 30 minutes to allow the amount of blowing agent incorporated into the molten material to reach equilibrium under these conditions. The amount of blowing agent and the conditions used, such as melting temperature and pressure, were determined after several tests based on the ability to form an acceptable foam with an RFD value of approximately 0.2 or less. Next, the temperature and pressure inside the autoclave were rapidly reduced to ambient conditions (approximately 22°C and 1 atmosphere) (the pressure reduction took about 10 seconds, and the temperature reduction using chilled water took about 1 to 10 minutes), causing foaming.

[0366] The foam produced in this Comparative Example 6 was tested and found to have the properties reported in Table C6 below.

[0367] [Table 59]

[0368] Example 17: Preparation of a PEF homopolymer with a MW of 33 kg / mol using PMDA and SSP A PEF homopolymer was prepared using the same additives and basic polymer formation procedure as used in Comparative Example 3, achieving a polymer molecular weight of approximately 30,000 kg / mol. Specifically, the PEF homopolymer was formed by esterifying and polycondensing 2,5-franzicarboxylic acid with monoethylene glycol according to a method consistent with that described herein, and then treated with 0.7 wt% PMDA according to known techniques. The polymer then underwent solid-phase polymerization consistent with the previous examples to produce a PEF homopolymer. When the PEF polymer was tested using the same measurement techniques as described in Comparative Example 1, it was found to have the properties reported in Table E17A below.

[0369] [Table 60]

[0370] The PEF polymer produced in this example will be referred to as PEF-Ex17A in Table E17A above, and hereafter.

[0371] Examples 17B-1 and 17B: Preparation of PEF foam using PEF-Ex17A and Trans 1234ze as a blowing agent Two foams were prepared from PEF-EX17A using a foaming process designed with the same standards as those described in these examples. The foams thus produced were tested and found to have the properties reported in Table E17A below.

[0372] [Table 61]

[0373] Surprisingly, the tensile strength of the foam produced from the PEF homopolymer and the 1234ze(E) blowing agent was dramatically superior to that of the foam produced from the PET homopolymer and the 1234ze(E) blowing agent. In this regard, it is important to note that the molecular weight of the PET used to produce the PET foam (37.6K) is reasonably close to the molecular weight of the PEF foam (33K), and therefore the data are comparable in terms of molecular weight. This unexpected result can be demonstrated, for example, by first taking the average of two PEF data points according to the present invention having an RFD of 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. Nevertheless, compared to a PET foam having a density more than 2.4 times that of the foam produced from the PEF of the present invention, the PEF foam of the present invention yields an average tensile strength equal to that of the PET foam. This is a very significant and unexpected result.

[0374] Surprisingly, the compressive strength of the foam produced from the PEF homopolymer and the 1234ze(E) blowing agent was dramatically superior to that of the foam produced from the PET homopolymer and the 1234ze(E) blowing agent. This unexpected result can be demonstrated, for example, by first taking the average of two PEF data points according to the present invention having an RFD of less than 0.1, noting that the average density of these two points is 0.0805 and the average relative compressive strength is 0.84. Nevertheless, compared to PET foam having a density more than twice that of the average PEF foam density, the PEF foam of the present invention yields an average tensile strength equal to that of PET foam. This is a very significant and unexpected advantage of the PEF foam compared to PET foam.

[0375] Example 18: Preparation of PET9:PEF1 copolymer with approximately 133.8 kg / mol of PET MW using PMDA and SSP. A random copolymer of PET9:PEF1 (9:1 molar ratio) was prepared by adding 8.7 grams (0.0472 mol) of methyl frangic acid carboxylate (FDME), 106.8 grams (0.42 mol) of bis(2-hydroxyethyl) terephthalate (BHET), and 6.2 grams (0.1 mol) of EG to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condenser. After evacuating and refilling with N2, 0.046 grams of Ti(IV) isopropoxide catalyst was added. The reactor was then placed in a salt bath at 180°C, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was increased to 220°C. After 30 minutes under N2, vacuum was initiated. After 40 minutes under vacuum, the temperature was increased to 250°C and continued for 40 minutes. Under an N2 atmosphere, 0.59 grams of PMDA (0.0.0027 moles) were slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped. An aliquot (30 g) of the above product was pulverized, and then solid-phase polymerization was carried out by heating in a rotary evaporator at 180°C under vacuum for 3 days. When the PEF polymer was tested, it was found to have the characteristics of Table E18A.

[0376] [Table 62]

[0377] The resulting PET9:PEF1 random copolymer is referred to as PET9PEF1-EX18A in these examples.

[0378] Examples 18B1, 18B2, and 18C3: Preparation of PETPEF copolymer foam using PET9PEF1-EX18A and trans-1234ze as a blowing agent Three types of foams were prepared from PET9PEF1-EX18A using a foaming process designed with the same standards as described in Comparative Example 1. The foams thus produced were tested and found to have the properties reported in Table E18B below.

[0379] [Table 63]

[0380] As revealed by the data in Table E18B above, the applicants surprisingly found that the foam produced from PEF9:PET1-EX18A according to the present invention has unexpectedly superior tensile strength compared to foams formed from PET homopolymers, as shown in Figure 21, which includes PET tensile strength data from comparative examples for comparison.

[0381] As shown in Figure 21, the relative tensile strength of the foam produced from the PET9PEF1-EX18A copolymer containing a relatively low percentage of PEF (approximately 10 mol%) and using 1234ze(E) as a blowing agent was superior to that of the foam produced from the comparative PET homopolymer foam, despite being formed from the preferred 1234ze(E) blowing agent of the present invention.

[0382] One aspect of this unexpected result can be illustrated, for example, by noting that at an RFD of approximately 0.062, the two foams prepared using the PET9PEF1-EX7 copolymer had an average relative tensile strength of 0.89. In contrast, at this same RFD of approximately 0.062, the PET homopolymer had a relative tensile strength of approximately 0.52, based on the trend line of PET data, as shown by the dashed line in the graph above. This represents a relative tensile strength of approximately 1.7 times greater for the PET9PEF1 foam of this embodiment compared to the foam prepared from the PET homopolymer. Similarly, at an RFD of approximately 0.088, the PET9PEF1 foam had a relative tensile strength of 1.41. In contrast, at this same RFD of approximately 0.088, the PET homopolymer foam had a relative tensile strength of approximately 0.75, according to the PET trend line. This represents a relative tensile strength of approximately 1.9 times greater for the applicant's PET9PEF1 foam. These are important and unexpected results.

[0383] Example 19: Preparation of PET1:PEF9 copolymer with approximately 85 kg / mol MW using A-PMDA and SSP A random copolymer of PET1:PEF9 (1:9 molar ratio) with a target molecule 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-bottom steel reactor equipped with an overhead stirrer and a distillation / condenser. After evacuating and refilling with N2, 0.074 g of Ti(IV) isopropoxide catalyst was added. The flask was then lowered into a salt bath at 180°C, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under N2, vacuum was initiated after 30 minutes at this temperature. After 40 minutes under vacuum, the temperature was raised to 250°C and maintained for 2 hours. Under an N2 atmosphere, 0.68 grams of PMDA were slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped. An aliquot (30 g) of the above product was pulverized and then solid-phase polymerization was carried out by heating in a rotary evaporator at 180°C under vacuum for 3 days. The copolymer thus produced was a random copolymer with a total molar ratio of PET:PEF of 1:9 and a PET to PEF ratio of 1,1. Testing of the PEF polymer revealed that it had a molecular weight of approximately 85,100.

[0384] The resulting PET1:PEF9 copolymer is referred to as PET1PEF9-EX19A in these examples.

[0385] Example 19B - Preparation of PET1PEF9 copolymer foam using PET1PEF9EX11 and trans-1234ze as a foaming agent One type of foam was prepared from PET1PEF9-EX19A using a foaming process designed with the same standards as those described in the comparative example. The foam thus produced was tested and found to have the properties reported in Table E19B below.

[0386] [Table 64]

[0387] As revealed by the data in Table E19B above, the applicants surprisingly found that foams produced using the PET1:PEF9-EX19A copolymer according to the present invention had unexpectedly superior tensile strength compared to foams formed from PET homopolymers. The tensile strength of foams made from PET1PEF9-EX19A copolymer containing approximately 10% PET and using 1234ze(E) as a blowing agent was dramatically superior to that of comparative PET homopolymers made using 1234ze(E) as a blowing agent. In this regard, it is important to note that the molecular weights of the PET homopolymers used to produce the PET foams (83.9 kg / mol and 105.3 kg / mol) were sufficiently close to the molecular weight of foams made using PET1PEF9-EX19A copolymer (85.1 K), making it possible to compare data favorable to PET homopolymers from the standpoint of molecular weight.

[0388] One aspect of this unexpected result can be illustrated, for example, by noting that a foam prepared using the PET1PEF9 copolymer at an RFD of approximately 0.063 yielded a tensile strength of 1.2. In contrast, at this same RFD of approximately 0.063, the PET homopolymer exhibited a tensile strength of approximately 0.6 based on the trend line. This represents approximately twice the tensile strength of the PET1PEF9 foam in this embodiment compared to the foam prepared from the PET homopolymer. This is a significant and unexpected result.

[0389] Example 20 - Preparation of PET9:PEF1 copolymer with approximately 65.7 kg / mol MW using PMDA chain extender and SSP A PET9:PEF1 block copolymer (9:1 molar ratio) was prepared with a target molecular weight of approximately 65,000 g / mol and PET to PEF block ratios of 1-5 and 1-3. Specifically, 498 grams of FDCA (2.7 mol) and 417 grams of EG (6.72 mol) were added to a 1000 mL cylindrical glass reactor equipped with an overhead stirrer and a distillation / condenser, and PEF was prepared by immersion in a salt bath at 190°C. After purging with nitrogen, 0.414 grams of Ti(IV) isopropoxide catalyst was added to the flask, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under N2, vacuum was started after 30 minutes at this temperature. After 40 minutes under vacuum, the temperature was raised to 240°C and continued for 2 hours before the reaction was stopped to produce PEF.

[0390] PEF oligomers were prepared by adding 109 grams of EG and 0.45 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated to a boil (196°C), and then an aliquot of PEF (160 grams) from the above step was added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The resulting mixture was PEF oligomer.

[0391] 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 an overhead stirrer. The mixture was heated to a boil (196 °C). Then, 170 g of commercially available PET was added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The result was a PET oligomer mixture.

[0392] Copolymers were prepared by rapidly adding 7.14 grams of PEF oligomer and 67.9 grams of PET oligomer to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and distillation / condenser immersed in a salt bath at 220°C, followed by the addition of 0.84 grams of Ti(IV) isopropoxide. Immediately thereafter (<2 minutes), EG was removed by applying vacuum. After 40 minutes, the temperature was raised to 270°C and the reactor contents were maintained under vacuum for 40 minutes. Under an N2 atmosphere, 0.46 grams of PMDA were slowly added over approximately 5 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. Subsequently, aliquots (30 g) of the product were pulverized and solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 3 days.

[0393] Tests of the PET9:PEF1 copolymer revealed that it possesses the properties shown in Table E20A.

[0394] [Table 65]

[0395] The resulting PET:PEF block copolymer is referred to as PET9PEF1-EX20A in these examples.

[0396] Examples 20B1, 20B2, and 20B3: Preparation of PETPEF copolymer foam using PET9PEF1-EX20A and trans-1234ze as a blowing agent. Three types of foams were produced from PET9PEF1-EX20A using a foaming process designed with the same standards as those described in the above examples. The foams thus produced were tested and found to have the properties reported in Table E20B below.

[0397] [Table 66]

[0398] As revealed by the data in Table E20B above, the applicants surprisingly found that the PET9:PEF1-EX20B copolymer foam according to the present invention had unexpectedly superior tensile strength compared to foams formed from comparative PET homopolymers, as shown in Figure 20, which includes PET tensile strength data from comparative examples for comparison. As shown in the figure, the compressive strength of foams made using the PET9PEF1 copolymer and 1234ze(E) of the present invention was as good as, or substantially and unexpectedly better than, the compressive strength shown by foams made from PET homopolymers, or in the case of foams with an RFD greater than 0.07. Referring to data with an RFD greater than 0.07, foams made from PET9PEF1 copolymer showed an average relative compressive strength of 1.065, while PET foams at this RFD had a compressive strength of approximately 0.7 based on the trend line. Therefore, at densities above 0.07, foams prepared using PET9PEF1 copolymer and 1234ze(E) yielded 1.5 times higher compressive strength than foams prepared using PET homopolymer, based on the PET data trend line. This is an important and unexpected result.

[0399] Example 21 - Preparation of PET1:PEF9 copolymer with approximately 25 kg / mol MW using PMDA and SSP A random copolymer of PET1:PEF9 (1:9 molar ratio) was prepared, with a target molecule of approximately 25,000 g / mol and a PET to PEF block ratio of 1:1. 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 stirring bar. After vacuuming and refilling with N2, the flask was lowered into a salt bath at 180°C, and overhead mixing was started at 100 rpm under N2 flow. Next, 0.04 g of Ti(IV) isopropoxide catalyst was added. After 2.5 hours, the bath temperature was raised to 230°C. Under N2, after 30 minutes at this temperature, vacuum was started and continued for 2 hours. Under an N2 atmosphere, 0.313 g of PMDA was slowly added over approximately 10 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. Aliquots (20g) of the above product were pulverized, and then solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 3 days. When the PET1:PEF9 copolymer was tested, it was found to have the properties shown in Table E21A.

[0400] [Table 67]

[0401] The resulting PET1:PEF9 random copolymer is referred to as PET1PEF9-EX21A in these examples.

[0402] Examples 21B1 and 21B2: Preparation of PETPEF copolymer foam using PET1PEF9-EX21A and trans-1234ze as a blowing agent A foam was prepared from PET1PEF9-EX21A using a foaming process designed with the same standards as those described in the above examples. The foam thus produced was tested and found to have the properties reported in Table E21B below.

[0403] [Table 68]

[0404] As revealed by the data in Table E21B above, the applicants have surprisingly found that the PEF foam made from the PET1PEF9-EX21B copolymer of the present invention has unexpectedly superior tensile strength compared to foams formed from PET, as shown in Figure 26, which includes PET tensile strength data from comparative examples for comparison.

[0405] Synthesis example Synthesis Example 1A1 41.2 kg / mol of PEF homopolymer was formed by esterification and polycondensation of 75 g of 2,5-franzicarboxylic acid (FDCA) and 55 g of monoethylene glycol (EG). The reactants were added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After vacuuming and backfilling with nitrogen, 0.228 g of titanium(IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180°C, and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under nitrogen, after 30 minutes at this temperature, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 250°C and continued for 1 hour. Under a nitrogen stream, PMDA (0.5732 g) was slowly added over approximately 5 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. To perform SSP, aliquots of the product were pulverized and heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer with a molecular weight of 41 kg / mol, as reported in Example 1A.

[0406] Synthesis example 1A2-75000 Specifically, 75 kg / mol of PEF homopolymer was formed by esterification and polycondensation of 350 g of 2,5-franzicarboxylic acid (FDCA) and 279 g of monoethylene glycol (EG). The reactants were added to a 1-liter cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After vacuuming and backfilling with nitrogen, 0.228 g of titanium(IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180°C, and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under nitrogen, after 30 minutes at this temperature, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 230°C and continued for 1 hour. Under a nitrogen stream, PMDA (2.73 g - 0.7 wt%) was slowly added over approximately 5 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. To perform SSP, an aliquot (30g) of the product was pulverized and heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer with a molecular weight of 75 kg / mol, as reported in Example 1A.

[0407] Synthesis Example 2: Preparation of PEF homopolymer with a MW range of approximately 90 kg / mol using A1-PMDA and SSP For 90.8 kg / mol MW of polymer, FDCA (75 g) and EG (54.6 g) were added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condenser. After vacuuming and backfilling with nitrogen, 0.100 g of titanium(IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180°C, and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under nitrogen, after 30 minutes at this temperature, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 250°C and continued for 2 hours. Under a nitrogen stream, PMDA (0.587 g) was slowly added over approximately 5 minutes. After mixing for a further 30 minutes at this temperature, the reaction was stopped. The product was removed from the vessel. γ-valerolactone was added to dissolve the polymer remaining in the reactor and on the impeller. The mixture was stirred at 190°C for several hours. γ-valerolactone was distilled from the polymer under vacuum to obtain a solid. For SSP, an aliquot (30 g) of the product was pulverized and heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer with a molecular weight of 90.8 kg / mol, as reported in Example 2A.

[0408] Synthesis Example 2: Preparation of PEF homopolymer with a MW range of approximately 96 kg / mol using A2-PMDA and SSP For 96,078 g / mol MW of polymer, 75 g of 2,5-franzicarboxylic acid (FDCA) and 55 g of monoethylene glycol (EG) were added. The reactants were added to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condensation apparatus. After vacuuming and backfilling with nitrogen, 0.228 g of titanium(IV) isopropoxide catalyst was added to the flask. The flask was then lowered into a salt bath at 180°C, and overhead mixing was started at 200 rpm under a nitrogen atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under nitrogen, after 30 minutes at this temperature, vacuum was initiated. After 40 minutes under vacuum, the temperature was raised to 250°C and continued for 1 hour. Under a nitrogen stream, PMDA (0.5732 g) was slowly added over approximately 5 minutes. After mixing for a further 30 minutes at this temperature, the reaction was stopped. To perform SSP, aliquots of the product were pulverized and heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer as reported below. The product was removed from the container. γ-valerolactone was added to dissolve the polymer remaining in the reactor and on the impeller. The mixture was stirred at 190°C for several hours. γ-valerolactone was distilled from the polymer under vacuum to obtain a solid. To perform SSP, aliquots of the product were pulverized and heated in a rotary evaporator under vacuum at 180°C for 3 days to produce a PEF homopolymer with a molecular weight of 96,078 as reported in Example 2A.

[0409] Synthesis Example 3: Preparation of PET9:PEF1 copolymer with a MW of approximately 117.9:90.4 kg / mol using PMDA and SSP. A PET9:PEF1 block copolymer (9:1 molar ratio) was prepared with a target molecular weight of approximately 117,900 g / mol and 4 PET and 4 PEF blocks, respectively. Specifically, 498 grams of FDCA (2.7 mol) and 417 grams of EG (6.72 mol) were first added to a 1000 mL cylindrical glass reactor equipped with an overhead stirrer and a distillation / condenser, and PEF was prepared by immersion in a salt bath at 190°C. After purging with nitrogen, 0.414 grams of Ti(IV) isopropoxide catalyst was added to the flask, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under N2, vacuum was started after 30 minutes at this temperature. After 40 minutes under vacuum, the temperature was raised to 240°C and continued for 2 hours before the reaction was stopped to produce PEF.

[0410] PEF oligomers were prepared by adding 109 grams of EG and 0.45 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated in a salt bath at 230 °C until boiling. An aliquot (160 grams) of PEF derived from the above process was added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The resulting mixture was PEF oligomer.

[0411] PET oligomers were prepared by adding 103 grams of EG and 0.45 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated in a salt bath at 230 °C. Then, 160 grams of commercially available recycled PET flakes were added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The result was a PET oligomer mixture.

[0412] The copolymer was prepared by rapidly adding 12.0 grams of PEF oligomer and 111.7 grams of PET oligomer to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and distillation / condenser immersed in a salt bath at 220°C, followed by the addition of 0.9083 grams of Ti(IV) isopropoxide. Immediately thereafter (<2 minutes), the EG was removed by applying vacuum. After 40 minutes, the temperature was raised to 270°C and the reactor contents were maintained under vacuum for 40 minutes. Under an N2 atmosphere, 0.483 grams of PMDA was slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped. An aliquot (30 g) of the above product was pulverized and then solid-phase polymerization was carried out by heating 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.

[0413] Synthesis Example 5A: Preparation of PET9:PEF1 block copolymer with approximately 44.9 kg / mol MW using PMDA and SSP. A PET9:PEF1 block copolymer (9:1 molar ratio) was prepared with a target molecular size of approximately 44,900 g / mol, and the PET and PEF blocks were 6 and 7, respectively.

[0414] PEF oligomers were prepared by adding 40.5 grams of EG and 0.174 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated to 230°C until the catalyst was completely dissolved. Commercial PEF (59.5 grams) was added, and the mixture was refluxed under N2 for 2 hours. The resulting mixture was PEF oligomer.

[0415] PET oligomers were prepared by adding 235 grams of EG and 1.0 gram of sodium carbonate to a 1000 mL cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated to 230°C until the catalyst was completely dissolved. Commercial PET (364 g) was added, and the mixture was refluxed under N2 for 2 hours. The result was a PET oligomer mixture.

[0416] Copolymers were prepared by rapidly adding 12 grams of PEF oligomer and 111.7 grams of PET oligomer (both soluble at 160°C) to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and distillation / condenser immersed in a 220°C salt bath, followed by the addition of 0.8847 grams of Ti(IV) isopropoxide. Immediately thereafter (<2 minutes), the EG was removed by slowly applying vacuum. After 40 minutes, the temperature was raised to 270°C and the reactor contents were maintained under vacuum for 40 minutes. Under an N2 atmosphere, 0.483 grams of PMDA were slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped, yielding a polymer with a molecular weight of ~34,900 g / mol. Aliquots of this sample were made to a size of 60 M and crystallized under N2 at 165°C for 4 hours. Next, solid-phase polymerization was carried out on the above crystallized product by heating it under vacuum at 180°C for one day in a rotary evaporator to produce a PET9:PEF1 copolymer having a PET molecular weight of 117.9 kg / mol, as reported in Example 5A.

[0417] Synthesis Example 6: Preparation of PET99:PEF1 random copolymer with approximately 97.2 kg / mol MW using PMDA and SSP. A random copolymer of PET99:PEF1 (99:1 molar ratio) was prepared by adding 0.68 g (0.0037 mol) of methyl frangic acid carboxylate (FDME), 93.0 g (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET), and 0.46 g (0.0074 mol) of EG to a 500 mL round-bottom flask equipped with an overhead stirrer and a distillation / condensation apparatus. After evacuating and refilling with N2, 0.138 g of Ti(IV) isopropoxide catalyst was added. The reactor was then placed in a salt bath at 180°C, and overhead mixing was started at 100 rpm under an N2 atmosphere. After 1 hour, the bath temperature was increased to 230°C. After 30 minutes, the temperature was increased to 270°C. After 2.5 hours at this temperature under N2, vacuum was started and continued for 3 hours. Under an N2 atmosphere, 0.50 grams of PMDA (0.0.0023 moles) were slowly added. After mixing at this temperature for a further 25 minutes, the mixer was stopped to obtain a polymer with a molecular weight of ~58,000 g / mol. Aliquots of the above product were pulverized and then solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 1 day to produce a PET99:PEF1 copolymer having a PET molecular weight of 97,190 g / mol as reported in Example 6A.

[0418] Using a modified version of this method, a PET99:PEF1 copolymer having a PET molecular weight of 92,190 g / mol, as reported in Example 6A, was produced.

[0419] Preparation of PET19:PEF1 random copolymers with MW values ​​of approximately 72 and 79 kg / mol using synthesis examples 8A1 and 8A2-PMDA and SSP. A random copolymer of PET95:PEF5 (95:5 molar ratio) was prepared by adding 3.54 g (0.0192 mol) of methyl frangic acid carboxylate (FDME), 93.0 g (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET), and 2.39 g (0.0385 mol) of EG to a 500 mL round-bottom flask equipped with an overhead stirrer and a distillation / condensation apparatus. After evacuating and refilling with N2, 0.144 g of Ti(IV) isopropoxide catalyst was added. The reactor was then placed in a salt bath at 180°C, and overhead mixing was started at 100 rpm under an 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, vacuum was started and continued for 2 hours. Under an N2 atmosphere, 0.515 grams of PMDA (0.0.0024 moles) were slowly added. The mixture was further mixed at that temperature for 30 minutes to obtain a polymer with a molecular weight of ~40,000 g / mol. Aliquots of the above product were pulverized and then solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 1 day to produce a PET19:PEF1 copolymer with a PET molecular weight of 72.6 kg / mol, as reported in Example 7A1.

[0420] Using a modified version of this method, a PET19:PEF1 copolymer having a PET molecular weight of 79 kg / mol, as reported in Example 7A2, was prepared. Specifically, a random copolymer of PET95:PEF5 (95:5 molar ratio) was prepared by adding 3.54 g (0.0192 mol) of methyl frangic acid (FDME), 93.0 g (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET), and 2.39 g (0.0385 mol) of EG to a 500 mL round-bottom flask equipped with an overhead stirrer and a distillation / condensation apparatus. After evacuating and refilling with N2, 0.144 g of Ti(IV) isopropoxide catalyst was added. The reactor was then placed in a salt bath at 180°C, and overhead mixing was started at 100 rpm under an N2 atmosphere. After 1 hour, the bath temperature was increased to 230°C. After 30 minutes, the temperature was raised to 270°C. At this temperature, under N2 conditions for 1 hour, vacuum was initiated and maintained for 2 hours. Under an N2 atmosphere, 0.515 grams of PMDA (0.0.0024 moles) were slowly added. The mixture was mixed at that temperature for a further 30 minutes to obtain a polymer with a molecular weight of ~40,000 g / mol. Aliquots of the above product were pulverized and then solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 1 day to produce a PET19:PEF1 copolymer with a PET molecular weight of 79 kg / mol, as reported in Example 7A2.

[0421] Preparation of PET95:PEF5 block copolymer with approximately 83 kg / mol MW using synthesis example 11A-PMDA A PET95:PEF5 block copolymer (95:5 molar ratio) was prepared with a target molecular size of approximately 83,000 g / mol, and with 7 PET and 7 PEF blocks, respectively. The PEF oligomer was prepared by adding 40.5 grams of EG and 0.174 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated to 230°C until the catalyst was completely dissolved. Commercially available PEF (59.5 grams) was added, and the mixture was refluxed under N2 for 2 hours. The resulting mixture was the PEF oligomer.

[0422] PET oligomers were prepared by adding 235 grams of EG and 1.0 gram of sodium carbonate to a 1000 mL cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated to 220°C until the catalyst was completely dissolved. Commercial PET (364 g) was added, and the mixture was refluxed under N2 for 2 hours. The result was a PET oligomer mixture.

[0423] The copolymer was prepared by rapidly adding 6 grams of PEF oligomer and 117.9 grams of PET oligomer (both soluble at 160°C) to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and distillation / condenser immersed in a salt bath at 220°C, followed by the addition of 0.892 grams of Ti(IV) isopropoxide. Immediately thereafter (<2 minutes), the EG was removed by slowly applying vacuum. After 40 minutes, the temperature was raised to 270°C and the reactor contents were maintained under vacuum for 40 minutes. Under an N2 atmosphere, 0.483 grams of PMDA were slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped to produce a PET19:PEF1 copolymer with a PET molecular weight of 83.033 g / mol, as reported in Example 11A.

[0424] Preparation of PET9:PEF1 copolymer with approximately 56 kg / mol MW using synthesis example 12A1-ADR A random copolymer of PET9:PEF1 (9:1 molar ratio) was prepared by adding 8.7 grams (0.0472 mol) of methyl frangic acid (FDME), 107.6 grams (0.42 mol) of bis(2-hydroxyethyl) terephthalate (BHET), and 6.22 grams (0.1 mol) of EG to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and a distillation / condenser. After evacuating and refilling with N2, 0.0503 grams of Ti(IV) isopropoxide catalyst was added. The reactor was then placed in a salt bath at 180°C, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was increased to 220°C. After 30 minutes under N2, vacuum was initiated. After 40 minutes under vacuum, the temperature was increased to 250°C and continued for 2 hours. Under an N2 atmosphere, 1.1507 grams of ADR-4468 were slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped. Aliquots (30 g) of the above product were pulverized and then solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 3 days to produce a PET9:PEF1 copolymer having a PET molecular weight of 56,794 g / mol as reported in Example 12A1.

[0425] Synthesis Example 12: Preparation of a PEF homopolymer with a MW of approximately 70 kg / mol using A2-PMDA + talc and SSP. A PET9:PEF1 block copolymer (9:1 molar ratio) was prepared with a target molecular weight of approximately 117,900 g / mol and PET and PEF blocks of 5 and 4, respectively. Specifically, 498 grams of FDCA (2.7 mol) and 417 grams of EG (6.72 mol) were first added to a 1000 mL cylindrical glass reactor equipped with an overhead stirrer and a distillation / condenser, and PEF was prepared by immersion in a salt bath at 190°C. After purging with nitrogen, 0.414 grams of Ti(IV) isopropoxide catalyst was added to the flask, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 2.5 hours, the bath temperature was raised to 220°C. Under N2, vacuum was started after 30 minutes at this temperature. After 40 minutes under vacuum, the temperature was raised to 240°C and continued for 2 hours before the reaction was stopped to produce PEF.

[0426] PEF oligomers were prepared by adding 109 grams of EG and 0.45 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated in a salt bath at 230 °C until boiling. An aliquot (160 grams) of PEF derived from the above process was added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The resulting mixture was PEF oligomer.

[0427] PET oligomers were prepared by adding 136 grams of EG and 0.68 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated in a salt bath at 230°C. Then, 210 grams of commercially available recycled PET flakes were added. The mixture was reacted under reflux for 2 hours until the reaction stopped. The result was a PET oligomer mixture.

[0428] Copolymers were prepared by rapidly adding 10.15 grams of PEF oligomer and 97.64 grams of PET oligomer to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and distillation / condenser immersed in a salt bath at 220°C, followed by the addition of 0.957 grams of Ti(IV) isopropoxide. Immediately thereafter (<2 minutes), EG was removed by applying vacuum. After 40 minutes, the temperature was raised to 270°C and the reactor contents were maintained under vacuum for 40 minutes. Under an N2 atmosphere, a mixture of 0.4615 grams of PMDA and 0.3317 grams of talc was slowly added. After mixing at this temperature for a further 30 minutes, the reaction was stopped. Aliquots of the above product were pulverized, and then solid-phase polymerization was carried out by heating in a rotary evaporator under vacuum at 180°C for 3 days to produce a PET9:PEF1 copolymer having a PET molecular weight of 69,900 g / mol as reported in Example 12A2.

[0429] Synthesis Example 13: Preparation of PET9:PEF1 block copolymer with approximately 47 kg / mol MW using A-pentaerythritol A PET9:PEF1 block copolymer (9:1 molar ratio) was prepared with a target molecular size of approximately 47,000 g / mol, and the PET and PEF blocks were 6 and 7, respectively.

[0430] PEF oligomers were prepared by adding 40.5 grams of EG and 0.174 grams of sodium carbonate to a 500 mL cylindrical reactor equipped with a reflux condenser and an overhead stirrer. The mixture was heated to 230°C until the catalyst was completely dissolved. Commercial PEF (59.5 grams) was added, and the mixture was refluxed under N2 for 2 hours. The resulting mixture was PEF oligomer.

[0431] PET oligomers were prepared by adding 235 grams of EG and 1.0 gram of sodium carbonate to a 1000 mL cylindrical reactor equipped with a condenser and an overhead stirrer. The mixture was heated to 230°C until the catalyst was completely dissolved. Commercial PET (364 g) was added, and the mixture was refluxed under N2 for 2 hours. The result was a PET oligomer mixture.

[0432] Copolymers were prepared by rapidly adding 12 grams of PEF oligomer and 111.7 grams of PET oligomer (both soluble at 160°C) to a 500 mL cylindrical steel reactor equipped with an overhead stirrer and distillation / condenser immersed in a salt bath at 220°C, followed by the addition of 0.332 grams of pentaerythritol and 0.9 grams of Ti(IV) isopropoxide. Immediately thereafter (<2 minutes), EG was removed by slowly applying vacuum. After 40 minutes, the temperature was raised to 270°C and the reactor contents were maintained under vacuum for 40 minutes.

[0433] Preparation of a PET homopolymer with approximately 105 kg / mol MW using synthesis example C1A-PMDA and SSP Approximately 163 grams of bis(2-hydroxyethyl) terephthalate (BHET) and 0.114 grams of titanium(IV) isopropoxide were added to a 500 mL cylindrical reactor. The reactor was then lowered to a salt bath at 180°C, and overhead mixing was started at 200 rpm under an N2 atmosphere. After 1.5 hours, the bath temperature was raised to 250°C. Under an N2 atmosphere, vacuum was initiated after 30 minutes at this temperature. After 40 minutes under vacuum, the temperature was raised to 280°C and continued for 1 hour. Under an N2 atmosphere, 0.66 grams of PMDA were slowly added over approximately 5 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. Aliquots (30 g) of the above product were pulverized, and solid-phase polymerization was carried out by heating in a rotary evaporator at 180°C under vacuum for 3 days.

[0434] Synthesis Example: Preparation of PET homopolymer with a molecular weight of 95.6 kg / mol using C2A1-PMDA and SSP PET homopolymers were prepared by polycondensation to obtain a product with a molecular size of 48.3 kg / mol. Approximately 93 grams (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET) were added to a 500 mL round-bottom flask. After vacuuming and refilling with N2, the flask was lowered into a salt bath at 180°C, and overhead mixing was started at 100 rpm under N2 flow. 0.129 grams (0.0005 mol) of titanium isopropoxide catalyst were added to the flask. After 50 minutes, the bath temperature was raised to 285°C. Under N2 flow, after 2 hours at this temperature, vacuum was started and continued for 2 hours. Under N2 flow, pyromellitic dianhydride PMDA (0.49 g, 0.0022 mol) was slowly added over approximately 10 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. A 30g aliquot of the above product was pulverized, and then solid-phase polymerization was carried out by heating under vacuum at 180°C in a rotary evaporator for 3 days to obtain a polymer with a molecular weight of 95.6 kg / mol.

[0435] Synthesis Example: Preparation of PET homopolymer with a molecular weight of 80.87 kg / mol using C2A2-PMDA and SSP PET homopolymers were prepared by polycondensation to obtain a product with a molecular size of 80,871 g / mol. Approximately 93 grams (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET) were added to a 500 mL round-bottom flask. After vacuuming and refilling with N2, the flask was lowered into a salt bath at 180°C, and overhead mixing was started at 100 rpm under N2 flow. 0.123 grams (0.0004 mol) of titanium isopropoxide catalyst were added to the flask. After 3 hours, the bath temperature was raised to 285°C. Under N2 flow, after 1 hour at this temperature, vacuum was started and maintained for 1 hour. Under N2 flow, pyromellitic dianhydride PMDA (0.49 g, 0.0022 mol) was slowly added over approximately 10 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. Aliquots of the above product were pulverized, and then solid-phase polymerization was carried out by heating under vacuum at 180°C for 3 days in a rotary evaporator to obtain a polymer having a molecular weight of 80.9 kg / mol.

[0436] Synthesis Example: Preparation of PET homopolymer with a molecular weight of 80.9 kg / mol using C2A3-PMDA and SSP PET homopolymers were prepared by polycondensation to obtain a product with a molecular size of 61.1 kg / mol. Approximately 93 grams (0.366 mol) of bis(2-hydroxyethyl) terephthalate (BHET) were added to a 500 mL round-bottom flask. After vacuuming and refilling with N2, the flask was lowered into a salt bath at 180°C, and overhead mixing was started at 100 rpm under N2 flow. After heating under N2 for 3 hours, 0.123 grams (0.0004 mol) of titanium isopropoxide catalyst were added to the flask. After 50 minutes, the bath temperature was raised to 285°C. Under N2, after 1.5 hours at this temperature, vacuum was started and continued for 2 hours. Under N2 flow, pyromellitic dianhydride PMDA (0.49 g, 0.0022 mol) was slowly added over approximately 10 minutes. After mixing at this temperature for a further 30 minutes, the reaction was stopped. An aliquot (30g) of the above product was pulverized, and then solid-phase polymerization was carried out by heating under vacuum at 180°C for 3 days in a rotary evaporator to obtain a polymer having a molecular weight of 81 kg / mol.

[0437] Usage example Comparative Example 7: Wind turbine made using PET foam A wind turbine with the general configuration shown in Figures ____~____ of this specification is constructed on land with a nacelle located approximately 150 meters above the ground (relative to the centerline of the nacelle). The blade span of each blade from the hub axis to the blade tip is approximately 100 meters, and the rotor diameter is approximately 200 meters. The generator produces approximately 13 MW of power under peak design conditions. In the blade design, where PET is the only core material used, each of the three blades has a capacity of 26.4 m per blade shell. 3 It has commercially available PET foam with a surface treatment, and a total of 79.2m for all three blades. 3 Therefore, PET is approximately 100 kg / m³. 3Due to its density, the total weight of the PET foam for wind turbines is 7900 kg. Based on the technical data sheet provided by the commercially available PET foam supplier, namely Gurit, AArmacel, the PET foam yields a foam core compressive strength of 1.5 MPa and a foam core tensile strength of 2.5 MPa.

[0438] Example 22A: Wind turbine made using the PEF homopolymer foam of the present invention A wind turbine having the configuration described in Comparative Example 7 is constructed, except that the foam core is one of the foams of the present invention containing each of foams 1 to 4, or a foam made from the PEF polymer of the present invention containing the thermoplastic polymers TPP1A to TPP22E, or one of the foams described in Examples 1 to 22. The high relative tensile strength of the preferred PEF foam of the present invention compared to PET foam allows the PEF foam of the present invention to have a density about 1.2 to about 1.4 times lower than commercially available PET foam, while being comparable in tensile strength to high-density PET foam. Considering these strength advantages, the PEF-based wind turbine blade of this embodiment is 1.3 times lighter than the foam portion of the PET-based blade of Comparative Example 4, while achieving the same energy production. According to the 2011 Sandia Report SAND2011-3779 (https: / / energy.sandia.gov / wp-content / gallery / uploads / 113779.pdf), a 13MW wind turbine blade (100m blade) has a 20 wt% foam core. A 1.3-fold reduction in foam weight results in a 5% reduction in blade weight. To balance the torque, this weight reduction in the turbine blades leads to a further reduction in the weight of the nacelle, the final value depending on the distance between the nacelle's centers of mass and the tower. This overall weight reduction for wind turbines, as a result of using any of the foams of the present invention, including each of foams 1-4, or foams made from the PEF polymers of the present invention, including thermoplastic polymers TPP1A-TPP22E, or foams described in Examples 1-22, is highly advantageous and an unexpected result.

[0439] Example 15B: Wind turbine fabricated in a blade shell using the PET:PEF copolymer foam of the present invention A wind turbine having the configuration described in Comparative Example 4 is fabricated, except that the foam core is made of the foam of the present invention containing each of Foams 1 to 4, or a foam made of the PEF polymer of the present invention containing thermoplastic polymers TPP1A to TPP22E, or any of the foams described in Examples 1 to 22. The preferred copolymer foam exhibits a tensile strength and a compressive strength approximately twice as high as those of the PET foam of the comparative example at a density comparable to that of the PET foam of the comparative example. Based on information publicly available from a supplier of commercially available PET foams as a baseline for comparison, the preferred PET-PEF copolymer foam of the present invention is considered to have an advantage in shear strength that is approximately the average of the advantages in tensile strength and compressive strength, which is approximately twice that of the PET foam. This two-fold advantage in shear strength is an unexpectedly very advantageous result because, at least in part, as long as the bending stiffness of the foam core remains acceptable, the thickness of the core foam can be reduced to one-half. This is shown by the following calculation described in Chapter 3 of Introduction to Sandwich Structures, Student Edition, 1995, Dan Zenkert. τ c =T x / d Wherein, T x is the direct load in Newtons (per width of the beam which is 1 cm in this case), causing bending of the beam (blade in this case). d is the thickness of the core foam + skin, approximately equal to the thickness of the core foam in cm. τ c is the shear stress that the core foam experiences as a result of the direct load. Since the load here is in Newtons / cm, the stress has units of pressure, Newtons / cm 2 [[ID=2,2]]resulting in. A high shear strength means a high shear stress (τ c ), allowing a thinner core foam thickness while still coping with the same direct load on the beam.

[0440] Based on data published by suppliers of commercially available PET foam, the density of PET foam is 80 kg / m³. 3 From 135 kg / m 3 Increasing the material strength by 2.5 times and 1.5 times increases the compressive and tensile strengths of the PET foam, respectively. At this interval, the shear strength increases by approximately two times, which is roughly the average of the benefits in tensile and compressive strength. The benefits determined in this embodiment are based on information and data contained in the following publicly available sources, each of which is incorporated herein by reference: https: / / www.gurit.com / - / media / Gurit / Datasheets / Kerdyn-Green.pdf;(https: / / local.armacell.com / fileadmin / cms / pet-foams / ArmaPET_website / Product_Flyer / ArmaPET_Struct_GR)

[0441] Example 23: Wind turbine made using the PET:PEF copolymer foam of the present invention in the blade shell A wind turbine having the configuration described in Comparative Example 7 is constructed, except that the foam core is one of the foams of the present invention containing each of foams 1 to 4, or a foam made from the PEF polymer of the present invention containing the thermoplastic polymers TPP1A to TPP22E, or one of the foams described in Examples 1 to 22. The copolymer foam of the present invention has a relative tensile strength about 1.7 times higher than that of the PET foam of the Comparative Example at comparable density. The copolymer foam of the present invention also has a relative compressive strength about 1.5 times higher than that of the PET foam of the Comparative Example at comparable density. These results indicate that the copolymer foam of the present invention has a shear strength about 1.6 times higher than that of a comparable PET foam, which is expected to allow for a reduction in the thickness of the foam core by about 1.6 times, provided that the bending stiffness of the foam core remains adequate. Reducing the thickness of the foam core results in a significant weight reduction, which is very advantageous but an unexpected result. The present invention includes the following embodiments. [1] A low-density thermoplastic foam, (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, wherein the thermoplastic polymer essentially consists of an ethylene furanoate moiety and an optional ethylene terephthalate moiety, and the polymer comprises about 1 mol% to about 100 mol% of the ethylene furanoate moiety and optionally at least about 1 mol% of the ethylene terephthalate moiety, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms, contained within the closed cells. [2] The low-density thermoplastic foam according to claim 1, wherein the thermoplastic polymer has a degree of crystallinity of at least about 5%. [3] The low-density thermoplastic foam according to claim 1, wherein the polymer essentially consists of about 1 mol% to about 100 mol% of an ethylene furanoate moiety and at least about 1 mol% of an ethylene terephthalate moiety. [4] The low-density thermoplastic foam according to claim 1, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, the polymer comprising about 1 mol% to about 20 mol% of an ethylene furanoate moiety and at least about 80 mol% of an ethylene terephthalate moiety. [5] The low-density thermoplastic foam according to claim 1, wherein the thermoplastic polymer has a molecular weight of at least about 10,000 kg / mol and a degree of crystallinity of at least about 5%, and is essentially composed of an ethylene furanoate moiety and an ethylene terephthalate moiety, the polymer comprising about 0.5 mol% to about 2 mol% of an ethylene furanoate moiety and about 98 mol% to about 99.5 mol% of an ethylene terephthalate moiety. [6] The low-density thermoplastic foam according to item 1, comprising one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms, one or more of 1234ze(E), 1336mzz, and 1233zd. [7] The low-density thermoplastic foam according to item 1, wherein one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms essentially consist of one or more of 1234ze(E), 1336mzz(Z), and 1233zd(E). [8] A method for forming a thermoplastic foam for use in wind energy devices, (a) A foaming composition, wherein the foaming composition is (c) A thermoplastic material comprising essentially an ethylene furanoate portion and an optional ethylene terephthalate portion, wherein the thermoplastic material includes about 1 mol% to about 100 mol% of an ethylene furanoate portion and at least about 1 mol% of an optional ethylene terephthalate portion. (d) To provide a method for extruding a foaming composition comprising a foaming agent containing one or more HFOs having three or four carbon atoms and / or one or more HFCOs having three or four carbon atoms, (b) A method comprising foaming the foaming composition.

[10] A method for forming a thermoplastic composition having improved crystallinity, (d) Forming a thermoplastic material comprising a polymer chain containing an ethylene furanoate moiety and / or an ethylene terephthalate moiety, (e) 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 furanoate portion and optionally at least about 1 mol% of an ethylene terephthalate portion. (f) A method comprising distilling the solvent from the thermoplastic material.

Claims

1. A low-density thermoplastic foam, (a) A thermoplastic polymer bubble comprising a cell wall forming a closed cell, wherein the thermoplastic polymer essentially consists of an ethylene furanoate portion and an optionally selected ethylene terephthalate portion, and the polymer comprises 1 mol% to 100 mol% of an ethylene furanoate portion and optionally at least 1 mol% of an ethylene terephthalate portion, (b) A low-density thermoplastic foam comprising one or more HFOs having three or four carbon atoms and / or one or more HCFOs having three or four carbon atoms contained within the closed cells, wherein one or more HFOs having three or four carbon atoms and / or one or more HCFOs having three or four carbon atoms contain one or more of 1234 ze(E) and 1336 mzz(E).

2. The low-density thermoplastic foam according to Claim 1, wherein one or more HFOs having three or four carbon atoms and / or one or more HCFOs having three or four carbon atoms contain 1234ze(E).

3. The low-density thermoplastic foam according to claim 1, further comprising one or more co-blown agents selected from the group consisting of 1336mzz(Z), 1336mzzm(E), 1224yd(Z), 1233zd(E), and 1234yf.

4. The low-density thermoplastic foam according to claim 1, further comprising one or more co-blown agents selected from one or more saturated hydrocarbons or hydrofluorocarbons (HFCs) contained within the closed cells.

5. The low-density thermoplastic foam according to claim 4, wherein the saturated hydrocarbon is a C4-C6 hydrocarbon and the HFC is a C1-C4 HFC.

6. The low-density thermoplastic foam according to claim 4, wherein the HFC comprises one or a combination of 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), and hexafluorobutane (HFC-356), and / or the saturated hydrocarbon is selected from butane or isobutane.

7. The low-density thermoplastic foam according to claim 1, further comprising one or more of the following contained within the closed cells: water, CO2, CFC, hydrochlorocarbon (HCC), HCFC, C1-C5 alcohol, C1-C4 aldehyde, C1-C4 ketone, C1-C4 ether, methyl formate, and organic acid.

8. The low-density thermoplastic foam according to claim 7, wherein the HCC is selected from dichloroethylene, trans-dichloroethylene, ethyl chloride, and chloropropane.

9. The low-density thermoplastic foam according to claim 7, wherein the C1 to C5 alcohol is selected from one or more of ethanol, propanol, and butanol, and / or the C1 to C4 ether is selected from one or more of dimethyl ether, diethyl ether, dimethoxymethane, and diethoxymethane, and / or the organic acid is formic acid.

10. The low-density thermoplastic foam according to claim 1, wherein one or more HFOs having three or four carbon atoms and / or one or more HCFOs having three or four carbon atoms essentially consist of one or more of 1234ze(E) and 1336mzz(Z).

11. The low-density thermoplastic foam according to claim 10, wherein one or more HFOs having three or four carbon atoms and / or one or more HCFOs having three or four carbon atoms are one or more of 1234ze(E) and 1336mzz(Z).

12. The low-density thermoplastic foam according to claim 11, wherein one or more HFOs having three or four carbon atoms and / or one or more HCFOs having three or four carbon atoms are 1234ze(E).

13. The low-density thermoplastic foam according to any one of claims 1 to 12, wherein the polymer essentially consists of 1 mol% to 100 mol% of an ethylene furanoate portion and at least 1 mol% of an ethylene terephthalate portion.

14. The low-density thermoplastic foam according to claim 13, wherein the thermoplastic polymer consists of an ethylene furanoate portion.

15. The low-density thermoplastic foam according to claim 13, wherein the thermoplastic polymer comprises 1 mol% to 40 mol% of ethylene furanoate and at least 99 mol% to 60 mol% of ethylene terephthalate.

16. The low-density thermoplastic foam according to claim 13, wherein the thermoplastic polymer comprises 1 mol% to 20 mol% of ethylene furanoate and at least 99 mol% to 80 mol% of ethylene terephthalate.

17. The low-density thermoplastic foam according to claim 13, wherein the thermoplastic polymer comprises 1 mol% to 10 mol% of an ethylene furanoate portion and at least 99 mol% to 90 mol% of an ethylene terephthalate portion.

18. The low-density thermoplastic foam according to claim 1, wherein the thermoplastic polymer has a crystallinity of at least 5%.

19. The low-density thermoplastic foam according to claim 1, wherein the thermoplastic polymer has a molecular weight of at least 10,000 kg / mol and a degree of crystallinity of at least 5%, and is essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, the polymer comprising 1 mol% to 20 mol% of an ethylene furanoate portion and at least 80 mol% of an ethylene terephthalate portion.

20. The low-density thermoplastic foam according to claim 1, wherein the thermoplastic polymer has a molecular weight of at least 10,000 kg / mol and a degree of crystallinity of at least 5%, and is essentially composed of an ethylene furanoate portion and an ethylene terephthalate portion, the polymer comprising 0.5 mol% to 2 mol% of an ethylene furanoate portion and 98 mol% to 99.5 mol% of an ethylene terephthalate portion.

21. A method for forming a thermoplastic foam according to Claim 1, (a) A foaming composition, wherein the foaming composition is (c) A thermoplastic material comprising essentially an ethylene furanoate portion and an optional ethylene terephthalate portion, wherein the thermoplastic material includes 1 mol% to 100 mol% of an ethylene furanoate portion and an optional at least 1 mol% of an ethylene terephthalate portion. (d) A blowing agent containing one or more of 1234ze(E) and 1336mzz(E), The foaming composition containing, (b) A method comprising foaming the foaming composition.

22. The method according to claim 21, wherein the thermoplastic foam is for use in a wind energy device.

23. The method according to claim 21, wherein the foaming agent comprises 1234ze(E).

24. The method according to claim 21, wherein the blowing agent comprises 1234ze(E) and is present in an amount of at least 50% by weight based on the total weight of all blowing agents present.

25. The method according to claim 21, wherein the blowing agent comprises 1234ze(E) and is present in an amount of at least 60% by weight based on the total weight of all blowing agents present.

26. The method according to claim 21, wherein the blowing agent comprises 1234ze(E) and is present in an amount of at least 80% by weight based on the total weight of all blowing agents present.

27. ​​The method according to claim 21, wherein the blowing agent comprises 1234ze(E) and is present in an amount of at least 95% by weight based on the total weight of all blowing agents present.

28. The method according to claim 21, wherein the blowing agent comprises 1234ze(E) and is present in an amount of at least 99% by weight based on the total weight of all blowing agents present.

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