KR20240046756A - Expandable thermoplastic composition, thermoplastic foam and method for producing the same - Google Patents

Abstract

A low density thermoplastic foam comprising: (a) thermoplastic polymer cells comprising cell walls comprising polyethylene furanoate, wherein at least about 50% by volume of the cells are closed cells; and (b) at least HFO-1336mzz(Z) contained in the closed cell.

Description

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

cross reference

This application is related to U.S. Provisional Application No. 63/233,720 (filed August 16, 2021); U.S. Provisional Application No. 63/252,110 (filed October 4, 2021); and U.S. Provisional Application No. 63/278,497, filed November 12, 2021, each of which is incorporated by reference.

Technology field

The present invention relates to expandable thermoplastic compositions, thermoplastic foams, foaming methods, and systems and articles made therefrom.

Foams are used in a wide variety of applications, but developing foams that have excellent performance properties and are cost-effective to produce is a desired but difficult goal to achieve. Achieving these goals while simultaneously developing environmentally friendly foams is more difficult. Producing environmentally friendly foam is particularly difficult because it contains both a resin component and a blowing agent that form the foam structure, and each of these components affects foam performance and environmental properties. Environmental considerations include the low environmental impact of the blowing agents used to form the foams, such as their global warming potential (GWP) and ozone depletion potential (ODP), as well as the recyclability and sustainability of the polymer resins that form the foam's structure. . Therefore, a major task is to develop a foam that has excellent performance and can be produced cost-effectively using eco-friendly blowing agents and eco-friendly resins.

Foams based on certain thermoplastics, including polyester resins, have been investigated for potential advantages in terms of recyclability and/or sustainability of supply. However, there have been difficulties associated with the development of these materials. For example, it has been difficult to develop polyester resins that are actually recyclable, can be produced from sustainable sources, and are compatible with blowing agents that, when combined with thermoplastics, can produce foams with good performance properties. Performance characteristics considered most desirable for many applications include the creation of high quality, closed cell foams that have low density (and therefore low weight in use) while simultaneously having relatively high mechanical integrity and strength.

With regard to the selection of thermoplastics, European Patent No. 3,231,836 was concerned with thermoplastics, especially polyester-based resins, but acknowledges that this interest has encountered difficulties in development, including difficulties in identifying suitable foaming grades of resins. there is. Furthermore, European Patent No. 3,231,836 discloses that certain polyethylene terephthalate (PET) resins, including recycled versions of PET, can be melt-extruded with suitable physical and/or chemical blowing agents to achieve closed cell densities and good mechanical properties. While it is stated that foams are produced, it is not disclosed that such resins are capable of producing foams with good environmental properties and good performance properties at the same time, nor that they can be formed from sustainable sources. This '836 can be used for the formation of open celled foams containing polyethylene terephthalate, polybutylene terephthalate, polycyclohexane terephthalate, polyethylene naphthalate, polyethylene furanoate or mixtures of two or more of these. Identify some possible polyester resins available. The use of polyester materials to produce foams that do not have essentially closed cells, as required by European Patent '836, can be advantageous for some applications, but the disadvantages of these structures generally include the relatively small size of open cell foams. This means that it exhibits poor mechanical strength properties.

Plastics based on 2,5-furandicarboxylic-acid-based polyesters are known to have some potential advantages in certain applications, such as good gas barrier properties, but the use of these plastic materials to form foam materials is limited. It is also recognized that there are significant problems with this. For example, Chinese Patent No. 108410000 teaches that 2,5-furandicarboxylic-acid-based polyesters have very poor foaming performance and extremely unfavorable processing conditions. This problem is said to be solved by using glassy (i.e. amorphous) polymer sheets and then subjecting these sheets to a special, relatively complex and cumbersome dual blowing agent process.

The process described in Chinese Patent No. 108410000 suffers from several drawbacks, including requiring undesirably long processing times to produce specially treated preforms and using a relatively complex dual blowing agent process. The process is also very disadvantageous in that it is not easy to apply with respect to the commercial extrusion equipment currently in use, thus requiring a high level of new capital expenditure which is undesirable for its implementation.

Chinese Patent No. 108484959 also recognizes that 2,5-furandicarboxylic-acid-based polyesters (e.g. PEF) have poor foaming properties and recognizes that 2,5-furandicarboxylic acid ethylene glycol ester is mixed with alcohol, An attempt is made to solve the above-mentioned important problems by combining and reacting with multifunctional monomers selected from esters, alkanes, carboxylic acids and anhydrides to form high melting viscosity polymers. The foaming properties of these materials are stated to be improved compared to PEF, but no information is provided on the foaming process.

US Patent No. 2020/0308363 and US Patent No. 2020/0308396, respectively, start with recycled polyester as the main component (only PET is illustrated) and then, through a series of processing steps, form an amorphous copolymer, i.e. a non-crystalline copolymer. Disclosed is the production of an amorphous polyester copolymer comprising obtaining a polymer. These publications indicate that it is not possible to easily form low density polyester foam from crystalline or semicrystalline polymers, and that this problem can be solved by forming an amorphous copolyester polymer material and using the amorphous material to form the foam. represents. The synthesis of poly(ethylene furanoate) (PEF) using ethylene glycol and 2,5-furanedicarboxylic acid is mentioned, but not illustrated. An essentially amorphous (i.e. amorphous according to 0 J/G Δh before foaming) ternary copolymer formed from PET, polytrimethylene furanoate and polycarbonate using CO2 as a blowing agent. They say it works. Foaming properties have not been disclosed. A variety of different classes of blowing agents are commonly mentioned for use with amorphous polymers, including CO2, HFO-1233zd, cyclopentane, acetone and methanol.

US Patent No. 9790342 discloses a foam formed from polyphenolic tannins, which can be combined with a number of possible monomers, among the list of monomers is 2,5-furandicarboxylic acid. These foams are said to be partially open cell and partially closed cell, with an open cell content of less than 50%. A number of potential blowing agents are disclosed, including the halogenated olefin HFO-1336mmz.

With regard to blowing agents, the use of halogenated olefin blowing agents, including hydrofluoroolefins (HFOs) and hydrochlorofluoroolefins (HCFOs), generally involves several specific methods, for example as disclosed in US Pat. No. 2009/0305876. Thermoplastic foams are known and have been assigned to the assignee of the present invention, which is incorporated herein by reference. Although '876 discloses the use of HFO and HFCO blowing agents with various thermoplastics to form foams including PET, there is no disclosure or suggestion regarding the use of these blowing agents with any other types of polyester resins.

Applicants have discovered that polyester resins disclosed herein in combination with a blowing agent comprising one or more hydrohaloolefins as disclosed herein can be used to form thermoplastic foams, particularly extruded thermoplastic foams, to provide advantageous environmental properties, i.e., high sustainability and Having solved the challenge of forming a high-performance foam that also has a low atmospheric impact, it has been recognized that the above-mentioned problems can be overcome and further that one or more unexpected advantages can be achieved.

As described above, there is a continuing need for polymer materials, especially polymer foams, that are sustainable and environmentally friendly, and that can provide low density and high strength at the same time. This combination of properties is particularly important in many applications that require foams that have low weight (i.e., low density) at a given volume but are required to provide strength in use. One example of the above-mentioned use relates to the construction of wind turbine blades, where light weight and high strength are important, and in this application both sustainability and environmental friendliness are also very important. As described above, for example, prior efforts to address this need have faced numerous technical problems and deficiencies, and a fully acceptable solution has not yet been achieved.

The present invention meets one or more of the above-mentioned needs, solves previous technical problems, and includes a low-density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% of the cells are closed cells and wherein ethylene furanoate moieties are present in the thermoplastic polymer. is at least 85% by weight of -; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 25% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least one of the thermoplastic polymers. 85% by weight -; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least one of the thermoplastic polymers. 85% by weight -; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least one of the thermoplastic polymers. 85% by weight -; and

(b) Gas in a closed cell, which contains 1336mzz(Z).

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least one of the thermoplastic polymers. 85% by weight -; and

(b) Gas in a closed cell, wherein the gas comprises at least about 25% by weight of 1336mzz(Z).

For convenience, the foam according to this paragraph is referred to herein as Foam 1D .

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least 15% by volume of the cells are closed cells and wherein ethylene furanoate moieties are at least one of the thermoplastic polymers. 85% by weight -; and

(b) Gas in a closed cell, wherein the gas comprises at least about 50% by weight of 1336mzz(Z).

For convenience, the foam according to this paragraph is referred to herein as Foam 1E .

At various places herein reference will be made to a numbered form (e.g., Foam 1) or a group of numbered forms defined herein, and such references shall include the suffixed numbering system, the group means each numbered system, including each numbered system within it. For example, a reference to Foam 1 includes separate references to each of Foams 1A, 1B, 1C, 1D, and 1E, and a reference to Foam 1 through Foam 2 includes Foams 1A, 1B, 1C, 1D, 1E. , are understood to include separate references to each of 2A, 2B, 2C, 2D, 2E and 2F. This convention is also used throughout this specification for other defined substances, including blowing agents.

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate, wherein at least 25% of the cells are closed cells; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least about 25% of the cells are closed cells and the thermoplastic polymer does not contain a tannin moiety or contains a tannin moiety; Tea is less than 20% by weight -; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least about 50% of the cells are closed cells and the thermoplastic polymer does not comprise a tannin moiety or contains a tannin moiety; Tea is less than 20% by weight -; and

(b) Gas in the closed cell - the gas containing 1336mzz(Z).

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least about 50% of the cells are closed cells and the thermoplastic polymer does not comprise a tannin moiety or contains a tannin moiety; Tea is less than 20% by weight -; and

(b) Gas in the closed cell, wherein the gas comprises about 25% to 100% by weight of 1336mzz(Z). For convenience, the foam according to this paragraph is referred to herein as Foam 2D .

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least about 50% of the cells are closed cells and the thermoplastic polymer does not comprise a tannin moiety or contains a tannin moiety; Tea is less than 20% by weight -; and

(b) a gas in the closed cell, the gas comprising 1336 mzz(Z) and at least one co-blowing agent. For convenience, the foam according to this paragraph is referred to herein as Foam 2E .

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 35%, wherein at least about 50% of the cells are closed cells and the thermoplastic polymer does not comprise a tannin moiety or contains a tannin moiety; Tea is less than 20% by weight -; and

(b) The gas within the closed cell, which gas consists essentially of 1336mzz(Z). For convenience, the foam according to this paragraph is referred to herein as Foam 2F .

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15%, wherein at least about 50% by volume of the cell is closed cell and ethylene furanoate moieties are 85% by weight of the thermoplastic polymer. or more, and the thermoplastic polymer does not contain a tannin moiety or the tannin moiety is in an amount of less than 20% by weight; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15% and a molecular weight of about 25,000 to about 170,000, wherein at least about 25% by volume of the cells are closed cells and the thermoplastic polymer comprises tannin Contains no moieties or the tannin moiety is in an amount of less than 20% by weight; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 15% and a molecular weight of about 80,000 to about 170,000, wherein at least about 25% by volume of the cells are closed cells and the thermoplastic polymer comprises tannin Contains no moieties or the tannin moiety is in an amount of less than 20% by weight; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 25% and a molecular weight of about 80,000 to about 170,000, wherein at least about 35% to about 90% by volume of the cell is a closed cell; the thermoplastic polymer does not contain tannin moieties or the amount of tannin moieties is less than 20% by weight; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of about 35% to about 65% and a molecular weight of about 80,000 to about 170,000 - about 35% to about 90% by volume of the cell; is closed cell and the thermoplastic polymer does not contain tannin moieties or the tannin moieties are in an amount of less than 20% by weight; and

(b) 1336mzz(Z) contained in a closed cell.

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

The present invention includes a low density closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising a cell wall comprising polyethylene furanoate, wherein the polyethylene furanoate contains no tannin moieties or contains tannin moieties in an amount of less than 20% by weight; and

(b) a blowing agent comprising 1336 mzz(Z) contained in the closed cells, wherein the foam has a relative foam density (RFD) of less than about 0.1 and a foam density of less than 0.3 g/cc. For convenience, the foam according to this paragraph is referred to herein as Foam 4A .

The present invention includes a low density closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate treated with a chain extender; and

(b) a blowing agent comprising 1336mzz(Z) contained in said closed cell;

- The foam has an RFD of less than about 0.1 and a density of less than 0.3 g/cc. For convenience, the foam according to this paragraph is referred to herein as Foam 4B .

The present invention includes a low density closed cell thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls forming closed cells, wherein the thermoplastic comprises a polyethylene furanoate-based polymer having a crystallinity of at least about 15% and a molecular weight greater than 25,000, wherein the polyethylene furanoate Contains no tannin moiety or the amount of tannin moiety is less than 20% by weight; and

(b) a blowing agent contained in the closed cells, wherein the blowing agent comprises 1336mzz(Z). For convenience, the foam according to this paragraph is referred to herein as Foam 5A .

The present invention includes a low density closed cell thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein the thermoplastic comprises a polyethylene furanoate-based polymer having a crystallinity of at least about 25% and a molecular weight of about 25,000 to about 170,000, and the polyethylene furanoate Noates do not contain tannin moieties or the amount of tannin moieties is less than 20% by weight; and

(b) a blowing agent contained in the closed cells, wherein the blowing agent comprises 1336mzz(Z). For convenience, the foam according to this paragraph is referred to herein as Foam 5B .

The present invention includes a low density closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate; and

(b) 1336mzz(Z) contained in the closed cell.

- the foam has a density of less than 0.3 g/cc -. For convenience, the foam according to this paragraph is referred to herein as Foam 6A .

The present invention includes a closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate, wherein at least about 50% by volume of the cell is a closed cell; and

(b) 1336mzz(Z) contained in the closed cell. For convenience, the foam according to this paragraph is referred to herein as Foam 6B .

The present invention includes a closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising cell walls consisting essentially of polyethylene furanoate, wherein at least about 75% by volume of the cells are closed cells; and

(b) 1336mzz(Z) contained in the closed cell. For convenience, the foam according to this paragraph is referred to herein as Foam 6C .

The present invention includes a closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising cell walls consisting essentially of polyethylene furanoate, wherein at least about 90% by volume of the cell is a closed cell; and

(b) 1336mzz(Z) contained in the closed cell. For convenience, the foam according to this paragraph is referred to herein as Foam 6D .

The present invention also provides foamable compositions, foaming methods and additional foams as described below.

본원에서 사용되는 탄닌 모이어티는 미국 특허 제9,890,342호에 개시된 바를 포함하여, 중합체를 형성하는 데 사용되는 탄닌에 상응하는 중합체 반복 단위를 의미한다.1 is a schematic diagram of an extrusion system and process in accordance with an embodiment of the invention and in accordance with examples herein.
Justice
1234ze refers to 1,1,1,3-tetrafluoropropene, without limitation to the isomeric form.
Trans1234ze and 1234ze(E) respectively mean trans1,3,3,3-tetrafluoropropene.
Cis1234ze and 1234ze(Z) each refer to cis1,3,3,3-tetrafluoropropene.
1234yf means 2,3,3,3-tetrafluoropropene.
1233zd refers to 1-chloro-3,3,3-trifluoropropene without limitation to the isomeric form.
Trans1233zd and 1233zd(E) respectively mean trans1-chloro-3,3,3-trifluoropropene.
1224yd refers to 1-chloro-2,3,3,3-tetrafluoropropane without limitation to the isomeric form.
cis1224yd and 1224yd(Z) refer to cis1-chloro-2,3,3,3-tetrafluoropropane.
1336mzz means 1,1,1,4,4,4-hexafluorobutene without limitation to isomeric form.
Trans1336mzz and 1336mzz(E) respectively mean trans1,1,1,4,4,4-hexafluorobutene.
Cis1336mzz and 1336mzz(Z) refer to cis1,1,1,4,4,4-hexafluorobutene, respectively.
Closed cell foam means that a substantial volume percentage of the cells in the foam are closed, for example, about 20 volume percent or more.
Crystallinity refers to the degree of crystallinity of the polymer measured by differential scanning calorimetry (DSC) according to ASTM D3418 and ASTM E1356.
Ethylene furanoate moiety refers to the structure:
.
FDCA means 2,5-furandicarboxylic acid and has the following structure:

FDME stands for dimethyl 2,5-furandicarboxylate and has the following structure:

MEG stands for monoethylene glycol and has the following structure:

As used herein, moiety refers to a distinct repeating unit within a polymer. Specifically, a copolymer with two repeat units A and B present in a 1:1 ratio will have 50 molal % A moieties and 50 molal % B moieties.
As used herein, other moieties refer to moieties that are not ethylene furanoate and are not formed from tannins.
Methyral means dimethoxymethane ((CH3O)2CH2).
PEF homopolymer refers to a polymer composed of ethylene furanoate moieties. Undoubtedly, PEF homopolymers contain levels of impurities that may be present.
PEF copolymer means a polymer having at least 50% by weight ethylene furanoate moieties and an amount of moieties other than ethylene furanoate moieties.
PEF stands for poly(ethylene furanoate) and is intended to encompass and reflect descriptions of PEF homopolymers and PEF copolymers.
SSP stands for solid-state polymerization.
PMDA means pyromellitic dianhydride, which has the following structure:

As used herein , tannin moiety refers to polymer repeat units corresponding to tannins used to form the polymer, including those disclosed in U.S. Pat. No. 9,890,342.

Poly(ethylene furanoate)

The present invention relates to foams and foam articles comprising cell walls comprising PEF.

The PEF forming the cell walls of the foams and foam articles of the present invention may be PEF homopolymers or PEF copolymers.

PEF homopolymers are materials known to be formed by one of the following, for example as illustrated below: (a) esterification and polycondensation of MEG with FDCA; or (b) transesterification and polycondensation of MEG and FDME:

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

form

Foams of the present invention are formed from PEF homopolymers, PEF copolymers, or combinations/blends thereof.

The foam may be formed from a PEF homopolymer in a preferred embodiment, wherein the polymer has at least 99.9% by weight, or at least 99.5% by weight, ethylene furanoate moieties.

It is contemplated that the foam may be formed from a PEF copolymer in a preferred embodiment, the polymer comprising from about 60% to about 99% by weight ethylene furanoate moieties, from about 70% to about 99% by weight ethylene furanoic acid. ate moiety, from about 85% to about 99% ethylene furanoate moiety, from about 90% to about 99% ethylene furanoate moiety, or from about 95% to about 99.5% ethylene fura. and PEF copolymers with noate moieties. The invention also includes foams formed from PEF having less than 20% by weight of tannin moieties, or less than 15% by weight of tannin moieties, or less than 10% by weight of tannin moieties, or less than 5% by weight of tannin moieties. Or, it does not contain essentially a tannin moiety.

For embodiments of the present invention involving PEF copolymers, one skilled in the art, in light of the teachings contained herein, will be able to select the amount and type of copolymer material used in each of the ranges described herein, thereby making the polymer known without undue experimentation. It is believed that the desired improvement/change can be achieved.

For embodiments of the invention involving the use of PEF homopolymers or PEF copolymers, it is believed that such materials can be formed to have a wide variety of molecular weights and physical properties within the scope of the invention. In a preferred embodiment, the foams, including each of Foam 1 to Foam 6, are formed from PEF having the range of properties identified in Table 1 below, which are measured as described in the Examples herein:

[Table 1]

In general, it is believed that one skilled in the art, in light of the teachings contained herein, will be able to formulate PEF polymers within the range of properties described above without undue experimentation. However, in a preferred embodiment, PEF in general, and PEF homopolymers having these properties in particular, are prepared in combination with various known complementary processing techniques, including treatment with a chain extender such as PMDA and/or treatment with SSP. This can be accomplished using one or more of the synthetic methods described. In light of the disclosure contained herein, including the polymer synthesis described in the Examples below, it is believed that one skilled in the art will be able to produce PEF polymers within the property ranges set forth in the tables and elsewhere herein.

An example of a chain extension treatment process for polyester is described in “Recycled poly(ethylene terephthalate) chain extension by a reactive extrusion process,” Firas Awaja, Fugen Daver, Edward Kosior, 16 August 2004, available at https://doi.org/ 10.1002/pen.20155, which is incorporated herein by reference. As described in US Pat. No. 1009/0264545, which is incorporated herein by reference, chain extenders are generally compounds that are at least di-functional to the terminal groups of the polyester or reactive groups capable of reacting with the functional groups. Extends the length of the polymer chain. In certain cases, as disclosed herein, such treatments can advantageously increase the average molecular weight of the polyester, thereby improving its melt strength and/or other important properties. The degree of chain extension achieved is at least partially related to the structure and function 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, haloformyl derivatives thereof, or multifunctional epoxy (e.g., glycidyl) or oxazoline functional groups. Containing compounds are included. Nanocomposite materials such as finely dispersed nanoclay can optionally be used for viscosity control. Commercial chain extenders include CESA-Extend from Clariant, Joncryl from BASF, or Lotader from Arkema. The amount of chain extender may vary depending on the type and molecular weight of the polyester component. The amount of chain extender used to treat the polymer can vary widely, and in preferred embodiments is from about 0.1 to about 5 weight percent, or preferably from about 0.1 to about 1.5 weight percent. Examples of chain extenders are also described in U.S. Pat. No. 4,219,527, which is incorporated herein by reference.

An example of an SSP treatment process for poly(ethylene furanoate) is described in "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, incorporated herein by reference.

PEF thermoplastic polymers that are particularly advantageous for preparing the foamable compositions and foams of the invention are identified in the following thermoplastic polymer table (Table 2), wherein all numerical values are understood to be preceded by the word "about".

[Table 2]

To define terms used herein, reference will be made to the thermoplastic polymer identified in the first column of each row of the above TPP table at various locations herein, with a reference to each of these numbers being made to the thermoplastic polymer defined in the corresponding column of that row. It should be noted that references will be made to Reference to a group of TPPs defined in the table above by reference to a TPP number means each TPP numbered separately and individually, including each TPP with the number indicated, including any number with a suffix. Thus, for example, a reference to TPP1 is a separate and independent reference to TPP1A, TPP1B, TPP1C, TPP1D and TPP1E. References to TPP1 to TPP2 are separate and independent references to TPP1A, TPP1B, TPP1C, TPP1D, TTP1E, TPP2A, TPP2B, TPP2C, TPP1D and TTP1E. These rules of use are also used in the foam tables and foamable composition tables below.

blowing agent

As described in detail herein, the present invention provides that a selected group of blowing agents can provide expandable PEF compositions and PEF foams with a surprising and difficult to achieve combination of physical properties, including low density and good mechanical strength properties. , including but not limited to Applicant's findings.

The blowing agent used according to the invention preferably comprises at least one hydrohaloolefin having 3 or 4 carbon atoms. For convenience, the blowing agent according to this paragraph is sometimes referred to herein as blowing agent 1 .

The blowing agent used according to the invention preferably comprises one or more of 1234ze, 1234yf, 1336mzz(Z), 1336mzz(E), 1233zd and 1224yd (hereinafter referred to as blowing agent 2 for convenience); or one or more of trans1234ze, 1336mzz(Z), 1336mzz(E), trans1233zd and cis1224yd (hereinafter referred to as blowing agent 3 for convenience); or one or more of trans1234ze, 1336mzz(Z), trans1233zd and cis1224yd (hereinafter referred to as blowing agent 4 ); or one or more of trans1234ze and 1336mzz(Z) (hereinafter referred to as blowing agent 5 for convenience); or 1336mzz(Z) (hereinafter referred to as blowing agent 6 for convenience); or 1234yf (hereinafter referred to as blowing agent 7 ); or 1224yd (hereinafter referred to as blowing agent 8 ); or trans1233zd (hereinafter referred to as blowing agent 9 for convenience).

Accordingly, the blowing agent of the present invention, comprising each of blowing agents 1 to 9, may comprise a co-blowing agent comprising, in addition to each of the blowing agent(s) identified above, one or more of the optional potential co-blowing agents as described below. It is believed that it can be included. In a preferred embodiment, the foamable compositions, foams and foaming methods of the present invention comprise a blowing agent as described herein, wherein the indicated blowing agent (including the compound or group of compounds specifically identified in each of Foaming Agents 1 to 9) is present is present in an amount of at least about 50% by weight, or preferably at least about 60% by weight, based on the total weight of all blowing agents, and preferably at least about 70% by weight, or preferably at least It is present in an amount of about 80% by weight, or preferably at least about 90% by weight, or preferably at least about 95% by weight, or preferably at least about 99% by weight.

The blowing agent used according to the invention also preferably consists essentially of one or more of 1234ze, 1234yf, 1336mzz(Z), 1233zd and 1224ydf (hereinafter referred to as blowing agent 10 for convenience); or consists essentially of one or more of trans1234ze, 1336mzz(Z), trans1233zd and cis1224yd (hereinafter referred to as blowing agent 11 for convenience); or consists essentially of one or more of trans1234ze, 1336mzz(Z), trans1233zd and cis1224yd (hereinafter referred to as blowing agent 12 for convenience); or consists essentially of one or more of trans1234ze and 1336mzz(Z) (hereinafter referred to as blowing agent 13 for convenience); or consists essentially of trans1234ze (hereinafter referred to as blowing agent 14 ); or consists essentially of 1336mzz(Z) (hereinafter referred to as blowing agent 15 ); or consists essentially of 1336mzz (E) (hereinafter referred to as blowing agent 16 ); or consists essentially of 1234yf (hereinafter referred to as blowing agent 17 ); or consists essentially of 1224yd (hereinafter referred to as blowing agent 18 ); or consists essentially of trans1233zd (hereinafter referred to as blowing agent 19 ).

It is believed and understood that the blowing agents of the present invention, including each of Foaming Agents 1 to 19, may include one or more co-blowing agents not included in the indicated selection, provided that the co-blowing agent in the amount used is Foam 1 to Foam should not interfere with or negate the ability to achieve the relatively low density foams described herein, including each of 6, and preferably also do not interfere with or negate the ability to achieve foams with the mechanical strength properties described herein. Accordingly, in light of the teachings contained herein, it is believed that one skilled in the art will be able to select one or more of the following potential co-blowing agents for use in a particular application without undue experimentation, for example: One or more known saturated hydrocarbons or hydrofluorocarbons (HFCs), especially C4-C6 hydrocarbons or C1-C4 HFCs. Examples of the HFC co-blowing agent include, but are not limited to, difluoromethane (HFC-32), fluoroethane (HFC-161), difluoroethane (HFC-152), and 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 of these HFCs. With regard to hydrocarbons, the blowing agent compositions of the present invention may also, in certain preferred embodiments, comprise, for example, iso, normal and/or cyclopentane and butane and/or isobutane. For example, water, CO2, CFCs (e.g. trichlorofluoromethane (CFC-11) and dichlorodifluoromethane (CFC-12)), hydrocarbons (dichloroethylene (preferably trans-dichloroethylene), HCCs such as 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 (e.g. (including dimethyl ether and diethyl ether), diethers (e.g. dimethoxymethane and diethoxymethane)), and methyl formate, organic acids (e.g. but not limited to formic acid), any of these. Other materials may be included, including combinations of, but such ingredients are not necessarily preferred in many embodiments due to negative environmental impacts.

The blowing agent used according to the invention also preferably consists of one or more of 1234ze, 1234yf, 1336mzz(Z), 1233zd and 1224ydf (hereinafter referred to as blowing agent 20 for convenience); or consists of one or more of trans1234ze, 1336mzz(Z), trans1233zd and cis1224yd (hereinafter referred to as blowing agent 21 for convenience); or consists of one or more of trans1234ze, trans1336mzz(Z), trans1233zd and cis1224yd (hereinafter referred to as blowing agent 22 for convenience); or consists of one or more of trans1234ze and 1336mzz (hereinafter referred to as blowing agent 23 ); or 1336mzz(Z) (hereinafter referred to as blowing agent 24 ); or trans1336mzz(Z) and 1336mzz(E) (hereinafter referred to as blowing agent 25 ).

Foam and foaming process

Foams of the present invention may generally be formed from the foamable compositions of the present invention. Generally, the foamable composition of the present invention can be formed by combining the PEF polymer with the foaming agent of the present invention, including each of Foaming Agents 1 to 25.

Foamable compositions encompassed by the invention and which provide particular advantages with respect to forming the foam of the invention are set forth in the following Table of Foamable Compositions (Table 3), wherein all numerical values in the table are understood to be preceded by the word "about". The following terms used in the table have the following meanings:

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

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

CCBAG3 is water, CO2, isobutane, n-butane, isopentane, cyclopentane, cyclohexane, trans-dichloroethylene, ethanol, propanol, butanol, acetone, dimethyl ether, diethyl ether, dimethoxymethane, diethoxymethane, Methyl formate, difluoromethane (HFC-32), fluoroethane (HFC-161), 1,1-difluoroethane (HFC-152a), trifluoroethane (HFC-143), 1,1 ,1,2-tetrafluoroethane (HFC-134a), pentafluoroethane (HFC-125), pentafluoropropane (HFC-245), hexafluoropropane (HFC-236), heptafluoropropane ( refers to a co-blowing agent selected from the group consisting of HFC-227ea), pentafluorobutane (HFC-365), hexafluorobutane (HFC-356), and combinations of two or more of these.

NR means not required.

[Table 3]

How to form foam

In view of the disclosure contained herein, each of Foams F1 to Foams F6 and each of Foams 1 to Foams 6, and all such techniques and all foams formed thereby, or those within the broad scope of the present invention Thus, it is believed that any one or more of the various known techniques for forming thermoplastic foam may be used. For clarity, note that the definitions of the tabular forms below all begin with the letter F only, in contrast to the forms defined by the paragraphs in the summary above that begin with the letter Foam.

Generally, the forming step is first by introducing the foaming agent of the present invention, including each of the foaming agents 1 to 31, into the PEF polymer of the present invention, including each of the present TPP1 to TPP6, to form a foamable PEF containing PEF and the foaming agent. It includes forming the composition. One example of a preferred method for forming the foamable PEF composition of the present invention is to plasticize the PEF, preferably comprising heating the PEF to its melting temperature, preferably above its melting temperature, and and then exposing the PEF melt to the blowing agent under conditions effective to incorporate (preferably by dissolving) the desired amount of blowing agent into the polymer melt.

In a preferred embodiment, the foaming method of the present invention comprises providing a foamable composition of the present invention comprising each of FC1 to FC6 and foaming the provided foamable composition. In a preferred embodiment, the foaming method of the present invention comprises providing a foamable composition of the present invention comprising each of FC1 to FC6, and extruding the provided foamable composition to form foams F1 to Foam 1 to Foam 6, respectively. and forming a foam of the present invention comprising each of Foam F6.

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. The batch process generally involves producing in a storable state at least a portion of the foamable polymer composition, including each of FC1 to FC6, and using said portion of the foamable polymer composition to produce a foam at some point in the future. . The semi-batch process is a step of preparing at least a portion of a foamable polymer composition comprising each of FC1 to FC6, and, in a single process, forming the foam comprising each of Foam 1 to Foam 6 and each of Foam F1 to Foam F6. and intermittently expanding the foamable polymer composition. For example, U.S. Pat. No. 4,323,528, incorporated herein by reference, discloses a process for making thermoplastic foam via an accumulation extrusion process. Accordingly, the present invention includes a process comprising the following: 1) mixing a PEF thermoplastic polymer comprising each of TPP1 to TPP6 and a foaming agent of the present invention including each of foaming agents 1 to 31 under conditions to produce a foamable PEF composition. forming step; 2) Extruding the foamable PEF composition comprising each of FC1 to FC6 into a holding zone maintained at a temperature and pressure that does not allow foaming of the foamable composition - the holding zone is preferably FC1 to FC6. a die defining an orifice that opens to a zone of low pressure where the foamable polymer composition is foamed, and an openable gate closing the die orifice, comprising each of the following: 3) Applying mechanical pressure substantially in parallel by means of a movable ram to the foamable polymer composition comprising each of FC1 to FC6 while periodically opening the gate to discharge the foamable polymer composition comprising each of FC1 to FC6 from the holding zone to the low pressure zone through the die orifice. steps; and 4) the released foamable polymer composition expands under the influence of the blowing agent to form a foam comprising each of Foam 1 to Foam 6 and each of Foam F1 to Foam F6.

The present invention can also use a continuous process to form the foam. For example, such a continuous process includes forming a foamable PEF composition comprising each of FC1 to FC6, and expanding the foamable PEF composition without substantial interruption. For example, a foamable PEF composition comprising each of FC1 to FC6 can be prepared by heating selected PEF polymer resins comprising each of TPP1 to TPP6 in an extruder to form a PEF melt, comprising each of Foaming Agents 1 to 31. It can be prepared by incorporating the blowing agent of the present invention into the PEF melt, preferably by dissolving the blowing agent in the PEF melt at an initial pressure to form a substantially homogeneous combination of the blowing agent comprising each of FC1 to FC6 and PEF. forming a foamable PEF composition comprising: and extruding said foamable PEF composition through a die into a selected region of foaming pressure, wherein under the influence of a foaming agent, the foamable PEF composition is formed of each of the foams Foam 1 to Foam 6 and foams described below. It can be manufactured by a step of allowing it to expand into a foam comprising each of foams F1 to foam F6. Optionally, the foamable PEF composition comprising a PEF polymer comprising each of FC1 to FC6 and an incorporated blowing agent comprising each of Foaming Agents 1 to 31 may be prepared by mixing each of Foam 1 to Foam 6 prior to extruding the composition through a die. and each of Foams F1 to F6.

The method can be performed, for example, using extrusion equipment of the general type disclosed in Figure 1. In particular, the extrusion device may include a feed hopper 10 for holding the PEF polymers 15 of the present invention, including each of TPP1 to TPP6, and may include one or more optional configurations (depending on the user's specification). Depending on the purpose, PEF can be added to the hopper or optionally to other locations). The feed material 15, excluding the blowing agent, can be charged into a hopper and conveyed to the screw extruder 10. The extruder 20 may include thermocouples (not shown) located at three points along its length and a pressure sensor (not shown) at the discharge end 20A of the extruder. The mixer section 30 receives the blowing agent components of the present invention, including each of blowing agents 1 to 31, via one or more metering pumps 40A and 40B and discharges the extruder to mix these blowing agents with the PEF melt in the mixer section. It may be located at the end 20A. Sensors (not shown) may be included to monitor the temperature and pressure of mixer section 30. The mixer section 30 may then discharge the foamable composition melt of the present invention comprising each of FC1 to FC6 to a pair of serially oriented melt coolers 50, where a temperature sensor (not shown) monitors the melt temperature. It is located in each cooler to do this. The melt is then extruded through die 60, which is also equipped with temperature and pressure sensors (not shown) to monitor pressure and temperature in the die. Die pressure and temperature can be varied depending on the purpose of each particular extrusion application to produce the foam 70 of the present invention, including each of Foam 1 through Foam 6 and each of Foam F1 through F6 described below. there is. The foam can then be transported from the extrusion equipment by conveyor belt 80.

The foamable polymer composition of the present invention comprising each of FC1 to FC6 optionally includes nucleating agents, cell control agents, glass and carbon fibers, dyes, pigments, fillers, antioxidants, extrusion aids, stabilizers, antistatic agents, flame retardants, IR attenuation. It may contain additional additives such as additives and thermal insulation additives. Nucleating agents include, among others, substances such as talc, calcium carbonate, sodium benzoate, and chemical blowing agents such as azodicarbonamide or sodium dicarbonate and citric acid. IR attenuators and insulating additives may include, among others, carbon black, graphite, silicon dioxide, metal flakes or powders. Flame retardants may include brominated materials such as hexabromocyclodecane and polybrominated biphenyl ethers, among others. Each of the additional optional additives mentioned above can be introduced into the foam at various locations and at various times during the process according to known techniques, and all such additives and methods of addition are included within the broad scope of the present invention.

form

In a preferred embodiment, the foam of the present invention is formed in a commercial extrusion equipment and has the properties as shown in Table 4 below, the values being measured as described in the Examples herein:

[Table 4]

Foams encompassed by the invention and providing particular advantages are listed in Table 5 below, wherein all numerical values in the table are understood to be preceded by the word "about", where NR means "not required".

[Table 5]

The foam of the present invention has a wide range of utility. The foams of the present invention, comprising each of Foam 1 to Foam 6 and each of Foam F1 to Foam F6, have low density and/or good compressive properties and/or tensile properties and/or shear properties and/or long-term stability and/or durability. This has unexpected advantages in applications that require availability of materials and/or that require them to be made from recycled materials and have the potential to be recycled. In particular, the foams of the present invention comprising each of Foam 1 to Foam 6 and each of Foam F1 to Foam F6 have unexpected advantages in the following respects: Wind energy applications (wind turbine blades (shear webs, shells, core and nacelle); Marine applications (hull, deck, superstructure, bulkhead, stringers and interior); Industrial light duty applications; Automotive and transportation applications (interior and exterior of cars, trucks, trains, aircraft and spacecraft).

Example

Example 1 - Preparation of PEF of MW 114,000 using PMDA chain extender and SSP

Bio-based polyethylene furanoate homopolymers were prepared through esterification and polycondensation of 2,5-furandicarboxylic acid and monoethylene glycol according to known methods for producing PEF homopolymers, as described in Examples 47 and 49 below. and 51, followed by treatment with 0.6% by weight of the chain extender PMDA followed by solid phase polymerization according to known techniques to produce the PEF homopolymer. PEF polymer has been tested and found to have the following properties1 ^:

¹ The molecular weights measured and referred to herein are 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 al.] refers to molecular weight measurements by diffusion ordered nuclear magnetic resonance spectroscopy (DOSY NMR), with final fitting performed with two functions: log D = α log M + log A (according to Grubb's Group, Macromolecules 2012, 45, 9595-9603), R2 = 0.977, and log D = α log M + β [log (M)]2 + A (R2). =0.998) and using the final fit of the data as follows: α: 0.4816276533; β: -0.064669629A: -21.74524435. Decomposition temperature was measured by thermogravimetric analysis (TGA) based on ASTM E1131. The density of the polymer was measured according to ASTM D71). The remaining properties, including crystallinity, were determined according to ASTM D3418 and ASTM E1356.

Molecular Weight - 114,000

Density (g/cc) - 1.43

Glass transition temperature - 86℃

Melt temperature - 214℃

Decomposition temperature - 347℃

Crystallinity - 46%

The PEF polymer thus produced is referred to as PEX1 in this example.

Example 1B - Closed cell PEF foams obtained from PEX1 and blowing agents over a range of relative densities

The present invention includes the advantage of forming PEF foams using a variety of blowing agents and having a high volume percentage of closed cells over a wide range of relative foam densities (RFD). Applicants are not bound by any theory of operation, but it is believed that one or more of the advantageous foam properties of the present invention arise, at least in part, as a result of the ability to form foams with a high closed cell content. In particular, the following Table E1B shows the volume percentage of closed cells for several foams manufactured by the applicant:

[Table E1B]

Comparative Example 1 - Preparation of PEF foam using PEX1 and CO2 as blowing agent

1 g of PEX1 placed in a glass container was loaded into a 60 cc autoclave and then dried at 130°C under vacuum for 6 hours. The dried polymer was cooled to room temperature and placed in a glass container inside the autoclave. About 0.25 mole (11 grams) of CO2 blowing agent was then pumped into the autoclave containing the dried polymer, and the autoclave was then heated to bring the polymer to a molten state at a temperature of about 240° C. and a pressure of more than about 610 psig. The polymer/CO ₂ blowing agent was maintained in this molten state for about 1 hour and the temperature and pressure of the melt/blowing agent were reduced to about 190° C. and 610 psig over a period of about 5 to 15 minutes (hereinafter referred to as pre-foaming, respectively). (referred to as temperature and pre-foaming pressure) and then maintained at approximately this temperature and pressure for about 30 minutes so that the amount of blowing agent introduced into the melt at these conditions reaches equilibrium. The temperature and pressure of the autoclave were then rapidly reduced to ambient conditions (approximately 22° C. and 1 atm) (pressure reduction over a period of approximately 10 seconds, temperature reduction using coolant over a period of approximately 1 to 10 minutes) and foaming occurred. The resulting form was tested to determine the following properties:

압축 강도("CS")(ISO 844에 따라 평면에 수직으로 측정(발포제와 직접 접촉))

Compressive strength (“CS”) (measured perpendicular to the plane (direct contact with foam) according to ISO 844)

Compressive modulus (“CM”) (measured perpendicular to the plane (direct contact with blowing agent) according to ISO 844)

Tensile Strength (“TS”) (measured perpendicular to the plane (direct contact with blowing agent) per ASTM C297)

Tensile Modulus (“TM”) (measured perpendicular to the plane (direct contact with blowing agent) per ASTM C297)

Relative Foam Density (“RFD”).

As used herein, RFD is the density of the resulting foam divided by the density of the starting polymer. Density is generally measured in these examples using a method corresponding to ASTM D71, except that hexane is used as a substitute for water.

The foam produced in this Comparative Example 1 was tested and found to have the properties reported in Table C1 below:

[Table C1]

As reported above, the foam made using CO ₂ at the reported conditions has an RFD of 0.25, i.e. the density is 25% of that of the starting polymer. This is too high a foam density for many important applications.

Examples 2 to 4 - PEF foam preparation using PEX1 and trans-1233zd and cis1336mzz as blowing agents

Comparative Example 1 was repeated except as follows: In a separate run, the CO ₂ blowing agent was replaced with each of trans-1233zd and cis1336mzz, and operating conditions were adjusted to achieve similar RFD for each foam. The resulting foam was observed to be a good, high quality foam and was subsequently tested and found to have the properties reported in Table E2-4 below:

[Table E2-4]

As can be seen from the results reported in Table E2-4, the use of 1336mzz(Z) blowing agent with PEF polymer without tannin moieties resulted in foams with a dramatic and unexpected improvement in density compared to foams made using _CO2. was created, that is, the density of the foam created using 1336mzz(Z) was on average about two times lower (about half) than the density of the CO ₂ foam. Additionally, the use of 1336mzz(Z) unexpectedly produced foams that were dramatically superior to the other HFO blower foams tested in this example in terms of both tensile and compressive strengths. For example, foam using 1336mzz(Z) had, on average, about 6.3 times better tensile strength and about 2.7 times better compressive strength than 1233zd foam.

Examples 5 to 9 - Preparation of PEF foam using PEF with MW 25,000 to 125,000

Comparative Example 1 was repeated except as follows: Using the blowing agents indicated in the table on a molar equivalent (i.e., within 15%) basis, the conditions and materials were varied as shown in Tables E5 to E9 below (all values are "approximately" understood as the indicated value).

[Table E5]

[Table E6]

[Table E7]

[Table E8]

[Table E9]

In each case of Tables E5 to E9 above, the thermoplastic polymer used to make the foam has properties (measured following the same procedure as found in Comparative Example 1 above) within the ranges indicated below:

Glass transition temperature - 75 to 95°C

Melting temperature - 190 to 240°C

Decomposition temperature - 320 to 400°C

Crystallinity - 30 to 60%

All foams produced according to these examples were observed to be of acceptable quality.

Comparative Example 2 - PEF foam preparation using PEX1 and HFC-134a as blowing agent

1 g of PEX1 in a glass container was loaded into an autoclave and then dried at 130°C under vacuum for 6 hours. The dried polymer was cooled to room temperature and placed in a glass container inside the autoclave. About 0.25 mole (25.3 g) of R-134a blowing agent was then pumped into the autoclave containing the dried polymer, and the autoclave was then heated to bring the polymer to a molten state at a temperature of about 240° C. and a pressure of at least about 570 psig. The polymer/R134a blowing agent is maintained in this molten state for about 1 hour and then the temperature and pressure of the melt/blowing agent are reduced to about 190° C. and 570 psig over about 5 to 15 minutes (hereinafter referred to as pre-foam temperature and, respectively, for convenience). (referred to as pre-foaming pressure), and then maintained at this temperature and pressure for about 30 minutes to allow the amount of blowing agent contained in the melt to reach equilibrium under these conditions. The temperature and pressure of the autoclave were then rapidly reduced to ambient conditions (approximately 22° C. and 1 atm) (pressure reduction over a period of approximately 10 seconds, temperature reduction using coolant over a period of approximately 1 to 10 minutes) and foaming occurred. The resulting foam had a relatively acceptable foam structure and was tested to determine relative foam density (RFD) and strength and modulus properties. The RFD of the foam was 0.12.

Example 10 - Preparation of PEF foam using PEX1 and cis-1336mzz as blowing agent

Comparative Example 2 was repeated except: (i) with HFC-134a foam cis1336mmzz; (ii) In two separate runs, process conditions were changed in a manner that produced foams with RFD values within about 10% of the RFD produced using HFC-134a in Comparative Example 2. The foam produced was tested to determine a variety of properties, including strength and modulus properties, and was found to be dramatically superior to foam made using HFC-134a in each measured property, as reported in Table E10 below:

[Table E10]

As can be seen in Table E10 above, foam made using cis1336mzz was surprisingly and dramatically superior to foam made using HFC-134a in all physical strength and modulus properties tested. For example, foams made using cis1336mzz produced foams with both tensile and compressive strengths and moduli that were in all cases >15 times better than foams made using HFC-134a. These results show a dramatic and unexpected improvement in the physical properties of the foam.

Comparative Example 3 - PEF foam preparation using PEX1 and isopentane as a blowing agent

1 g of PEX1 in a glass container was loaded into an autoclave and then dried at 130°C under vacuum for 6 hours. The dried polymer was cooled to room temperature and then placed in a glass container inside the autoclave. About 0.25 mole (27.8 g) of isopentane blowing agent was then pumped into the autoclave containing the dried polymer, and the autoclave was then heated to bring the polymer to a molten state at a temperature of about 240° C. and a pressure of at least about 443 psig. The polymer/isopentane blowing agent was maintained in this molten state for about 1 hour and then the temperature and pressure of the melt/blowing agent were reduced to about 190° C. and 443 psig over about 5 to 15 minutes (hereinafter referred to as prefoam temperature, respectively). and pre-foaming pressure), and then maintained at this temperature and pressure for about 30 minutes to allow the amount of blowing agent contained in the melt to reach equilibrium under these conditions. The temperature and pressure of the autoclave were then rapidly reduced to ambient conditions (approximately 22° C. and 1 atm) (pressure reduction over a period of approximately 10 seconds, temperature reduction using coolant over a period of approximately 1 to 10 minutes) and foaming occurred. The resulting foam had a relatively acceptable foam structure and was tested to determine relative foam density (RFD) and strength and modulus properties. The RFD of the foam was 0.13.

Examples 11 and 12 - PEF foam preparation using PEX1 and cis-1336mzz as blowing agent

Comparative Example 3 was repeated except: (i) the isopentane blowing agent was replaced by cis1336mmzz in the process; (ii) In two separate runs, process conditions were changed in a manner that produced foams with RFD values within about 10% of the RFD produced using isopentane in Comparative Example 3. The resulting foam was tested to determine a variety of properties, including strength and modulus properties, and was found to be dramatically superior in each property measured, as reported in Tables E11-12 below:

[Table E11-12]

As can be seen in Tables E11-12 above, foam made using cis1336mzz was surprisingly superior to foam made using isopentane in terms of all tensile strengths, and compressive strength and tensile modulus. For example, foam made using cis1336mzz produced foam that was, on average, 1.5 times better in both tensile and compressive strength than foam made using isopentane. These results show that unexpected improvements in the physical properties of foams can be achieved according to the present invention.

Examples 13 to 24 - Preparation of PEF foam using PEF with MW 25,000 to 125,000 and blowing agent comprising cis1336mzz and co-blowing agent

The foam made using 1336mzz(Z) of Example 11 was repeated with a closed cell volume greater than 90% except as follows: Instead of using a blowing agent consisting of 1336mzz(Z), a co-blowing agent shown in the following table was used. , replaces a portion of 1336mzz(Z) ranging from 5% to 45% on a molar basis, as indicated in Tables E13 - 24 below (all values are to be understood as "approximately" the indicated values).

[Table E13-24]

Example 25 - Preparation of PEF of MW 75,000 using PMDA chain extender and SSP

Bio-based polyethylene furanoate homopolymers were prepared through esterification and polycondensation of 2,5-furanedicarboxylic acid and monoethylene glycol according to known methods for producing PEF homopolymers, which were subsequently detailed in Example 1. Processing according to techniques generally corresponding to those described, the PEF homopolymer was produced by treatment with 0.7% by weight of the chain extender PMDA followed by solid phase polymerization according to known techniques. PEF polymer has been tested and found to have the following properties2 ^:

Molecular Weight - 75,000

Density (g/cc) - 1.43

Glass transition temperature - 90.2℃

Melt temperature - 222℃

Decomposition temperature - 346℃

Crystallinity - 42%

The PEF polymer thus produced is referred to in this example as PEX15.

Examples 26A and 26B - PEF foam preparation using PEX15, trans-1233zd and cis1336mzz as blowing agents

Using a procedure generally corresponding to that described in Comparative Example 1, 1 gram of PEX15 was placed in a glass container to form a foam, which was loaded into a 60 cc autoclave and dried under vacuum at 130° C. for 6 hours. . The dried polymer was cooled to room temperature and then placed in a glass container inside the autoclave. Then, in two separate runs, 55 grams (Ex26A) and 25 grams (Ex26B) were pumped into an autoclave containing the dried polymer, and the autoclave was then heated to a temperature of approximately 240° C. and a pressure above the prefoam pressure. The polymer was brought to a molten state. The polymer/1336mzz(Z) blowing agent was maintained in this molten state for about 1 hour and then the temperature and pressure of the melt/blowing agent was adjusted to about 190° C. and 590 psig (Ex26A) and 267 psig (Ex26B) over about 5 to 15 minutes. (hereinafter referred to as pre-foaming temperature and pre-foaming pressure, respectively, for convenience), and then maintained at this temperature and pressure for about 30 minutes so that the amount of foaming agent contained in the melt could reach equilibrium under these conditions. The temperature and pressure of the autoclave were then rapidly reduced to ambient conditions (approximately 22° C. and 1 atm) (pressure reduction over a period of approximately 10 seconds, temperature reduction using coolant over a period of approximately 1 to 10 minutes) and foaming occurred. The resulting foam was tested and found to have the properties reported in Table E26 below:

[Table E26]

As can be seen from the results reported in Table E26, by using the 1336mzz(Z) blowing agent in combination with the PEF polymer without tannin moieties according to the present invention, the CO ₂ of Comparative Example 1 was used. Compared to foam, the foam was produced with a dramatic and unexpected improvement in density, even though the foam was made from a much higher molecular weight polymer. In particular, the density of the foam produced using 1336mzz(Z) in this example was on average about two times lower (about half) than the density of the CO ₂ foam of Comparative Example 1. Additionally, the use of 1336mzz(Z) in this low molecular weight foam resulted in dramatically superior foam performance over the CO ₂ foam of Comparative Example 1, even though the foam had a much higher density and was made using a much higher molecular weight PEF polymer. The form was created unexpectedly. For example, the foam using 1336mzz(Z) had, on average, about 1.5 times better tensile strength and about 1.7 times better compressive strength than the foam of Comparative Example 1.

The following provisions provide an explanation within the scope of the present invention.

Article 1. Low-density thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein the ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Clause 2. The low density thermoplastic foam of clause 1, wherein the cell walls consist essentially of polyethylene furanoate treated with a chain extender.

Clause 3. The low density thermoplastic foam of clause 1, wherein the cell walls consist essentially of polyethylene furanoate having a molecular weight greater than 25,000.

Clause 4. The low density thermoplastic foam of clause 1, wherein the ethylene furanoate moieties are at least 70% by weight of the thermoplastic polymer.

Clause 5. The low density thermoplastic foam of clause 1, wherein the ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer.

Clause 6. The low density thermoplastic foam of clause 1, wherein the foam has a relative foam density (RFD) of less than or equal to about 0.2.

Clause 7. The low density thermoplastic foam of clause 1, wherein the foam has a foam density of less than 0.4 g/cc.

Clause 8. The low density thermoplastic foam of clause 1, wherein the foam has a foam density of less than 0.2 g/cc.

Clause 9. The low density thermoplastic of clause 1, wherein the one or more blowing agents contained in the closed cell comprise one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E), and 1336mzz(Z). Form.

Clause 10. The low density thermoplastic foam of clause 9, wherein the cell walls consist essentially of polyethylene furanoate having a molecular weight greater than 100,000.

Clause 11. The low density thermoplastic foam of clause 1, wherein the one or more blowing agents contained in the closed cells comprise at least 1234ze(E).

Clause 12. The low density thermoplastic foam of clause 11, wherein the cell walls consist essentially of polyethylene furanoate having a molecular weight greater than 100,000, and the foam has a relative foam density (RFD) of less than or equal to about 0.2.

Clause 13. The low density thermoplastic foam of clause 1, wherein the one or more blowing agents contained in the closed cells comprise at least 1336 mzz(Z).

Clause 14. The low density thermoplastic foam of clause 13, wherein the cell walls consist essentially of polyethylene furanoate having a molecular weight greater than 100,000, and the foam has a relative foam density (RFD) of less than or equal to about 0.2.

Clause 15. The low density thermoplastic foam of clause 1, wherein the one or more blowing agents contained in the closed cells comprise at least 1336mzz(Z) and/or 1234ze(E).

Clause 16. The low density thermoplastic foam of clause 15, wherein the cell walls consist essentially of polyethylene furanoate having a molecular weight greater than 100,000, and the foam has a relative foam density (RFD) of less than or equal to about 0.2.

Clause 17. Wind energy turbine blades and/or nacelle comprising foam according to any one of clauses 1 to 16.

Clause 18. A wall for a motor vehicle comprising foam according to any one of clauses 1 to 16.

Clause 19. A marine vessel comprising a foam according to any one of clauses 1 to 16.

Clause 20. An aircraft or aerospace vessel comprising a foam according to any of clauses 1 to 16.

Article 21. Low-density thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein the ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 22. Low-density thermoplastic foam containing:

(a) a closed thermoplastic cell comprising cell walls forming a closed cell, the cell walls consisting essentially of polyethylene furanoate treated with a chain extender and having a molecular weight greater than 25,000; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 23. Low-density thermoplastic foam containing:

(a) a closed thermoplastic cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 25,000, wherein the ethylene furanoate moieties are at least 70% by weight of the thermoplastic polymer; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 24. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 25,000, wherein the ethylene furanoate moieties are at least 90% of the thermoplastic containing ethylene furanoate moieties. -; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 25A. A comprises a low density closed cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate treated with a chain extender; and

(b) a blowing agent contained in the closed cell

- The foam has a relative foam density (RFD) of less than about 0.2 and a foam density of less than 0.3 g/cc.

Article 25B. A comprises a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls, wherein at least about 50% by volume of the cells are closed cells and ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 25C. A comprises a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 25,000, wherein the ethylene furanoate moieties are at least 50% of the thermoplastic and at least about 50% by volume of the cell is a closed cell -; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 25D. A comprises a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 25,000, wherein the ethylene furanoate moieties are at least 50% of the thermoplastic and at least about 75% by volume of the cell is a closed cell -; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 25E. A comprises a low density thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 25,000, wherein the ethylene furanoate moieties are at least 50% of the thermoplastic and at least about 90% by volume of the cell is a closed cell -; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Clause 26. A includes low-density closed-cell thermoplastic foam comprising:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate treated with a chain extender; and

(b) a blowing agent contained in the closed cell

- The foam has an RFD of less than about 0.2 and a density of less than 0.3 g/cc.

Article 27. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate treated with a chain extender; and

(b) a blowing agent contained in the closed cell

- the foam has a density of less than 0.25 g/cc -.

Article 28A. Low density closed cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 50,000, wherein the ethylene furanoate moieties are at least 50% of the thermoplastic and at least about 50% by volume of the cell. is a closed cell -; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 28B. Low density closed cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls treated with a chain extender and comprising polyethylene furanoate having a molecular weight greater than 50,000, wherein the ethylene furanoate moieties are at least 50% of the thermoplastic and at least about 75% by volume of the cell. is a closed cell -; and

(b) at least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in a closed cell.

Article 28C. Low density closed cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall treated with a chain extender and consisting essentially of polyethylene furanoate having a molecular weight greater than 100,000; and

(b) a blowing agent contained in the closed cells, wherein the foam has a density of less than 0.3 g/cc.

Article 29 Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate treated with a chain extender; and

(b) a blowing agent contained in the closed cells and comprising at least one HFO having 3 or 4 carbon atoms and/or at least one HFCO having 3 or 4 carbon atoms, wherein the foam has a concentration of less than 0.3 g/cc. It has a density of -.

Article 30. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate treated with a chain extender; and

(b) a blowing agent contained in the closed cells and comprising at least one HFO having 3 or 4 carbon atoms and/or at least one HFCO having 3 or 4 carbon atoms, wherein the foam has a concentration of less than 0.25 g/cc. It has a density of -.

Article 31. Low-density closed-cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer, said thermoplastic being treated with a chain extender and having a molecular weight greater than 25,000; -Includes based polymers -; and

(b) one or more blowing agents contained in the closed cells, wherein the blowing agents include one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E), and 1336mzz(Z).

Article 32. Low-density closed-cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein ethylene furanoate moieties are at least 70% by weight of the thermoplastic polymer, said thermoplastic being treated with a chain extender and having a molecular weight greater than 100,000; -Includes based polymers -; and

(b) one or more blowing agents contained in the closed cells, wherein the blowing agents include one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E), and 1336mzz(Z).

Article 33. Low-density closed-cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming closed cells, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer, said thermoplastic being treated with a chain extender and having a molecular weight greater than 100,000; -Includes based polymers -; and

(b) one or more blowing agents contained in the closed cells, wherein the blowing agents include one or more of 1224yd, 1233zd(E), 1234yf, 1234ze(E), 1336mzz(E), and 1336mzz(Z).

Article 34. Low-density closed-cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein the thermoplastic has a molecular weight greater than 100,000; and

(b) one or more blowing agents contained in the closed cells, wherein the blowing agents include one or more of 1234ze(E), 1336mzz(E), and 1336mzz(Z).

Article 35. Low-density closed-cell thermoplastic foam containing:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein the thermoplastic has a molecular weight greater than 100,000; and

(b) at least one blowing agent contained in said closed cell, said blowing agent consisting essentially of 1234ze(E).

Clause 36. A includes low-density closed-cell thermoplastic foam comprising:

(a) a thermoplastic polymer cell comprising cell walls forming a closed cell, wherein ethylene furanoate moieties are at least 90% by weight of the thermoplastic polymer and wherein the thermoplastic has a molecular weight greater than 100,000; and

(b) one or more blowing agents contained in said closed cells, said blowing agents consisting essentially of 1336mzz(E).

Article 37. Low-density closed-cell thermoplastic foams containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate; and

(b) trans-1234ze contained in the closed cell

- the foam has a density of less than 0.3 g/cc -.

Article 38. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate; and

(b) HFO-1234yf contained in the closed cell

- the foam has a density of less than 0.3 g/cc -.

Article 39. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate; and

(b) 1336mzz(E) contained in the closed cell.

- the foam has a density of less than 0.3 g/cc -.

Article 40. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate; and

(b) 1336mzz(Z) contained in the closed cell.

- the foam has a density of less than 0.3 g/cc -.

Article 41. Low-density closed-cell thermoplastic foam containing:

(a) a closed thermoplastic cell comprising a cell wall consisting essentially of polyethylene furanoate; and

(b) 1224yd included in the closed cell.

- the foam has a density of less than 0.3 g/cc -.

Article 42. A foamable thermoplastic composition comprising:

(a) a thermoplastic material consisting essentially of polyethylene furanoate treated with a chain extender and having a molecular weight greater than 25,000, wherein at least 50% of the thermoplastic comprises ethylene furanoate moieties; and

(b) One or more HFOs with 3 or 4 carbon atoms and/or one or more HFCOs with 3 or 4 carbon atoms.

Article 43. A foamable thermoplastic composition comprising:

(a) a thermoplastic material consisting essentially of polyethylene furanoate having a molecular weight greater than 100,000, wherein at least 50% of the thermoplastic comprises ethylene furanoate moieties; and

(b) One or more HFOs with 3 or 4 carbon atoms and/or one or more HFCOs with 3 or 4 carbon atoms.

Article 44. A foamable thermoplastic composition comprising:

(a) a thermoplastic material consisting essentially of chain-extended polyethylene furanoate having a molecular weight greater than 100,000, wherein at least 90% of the thermoplastic comprises ethylene furanoate moieties; and

(b) At least one HFO with 3 or 4 carbon atoms and/or at least one HFCO with 3 or 4 carbon atoms contained in the closed cell.

Clause 45. A method of forming a thermoplastic foam comprising foaming the foamable composition of the present invention, comprising each of clauses 42-44.

Clause 46. A method of forming an extruded thermoplastic foam comprising extruding a foamable composition of the present invention comprising each of clauses 42-44.

Claims (28)

Low-density thermoplastic foam containing:
(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate, wherein at least about 50% by volume of the cells are closed cells and the thermoplastic polymer is free of tannin or includes less than 20% tannin; and
(b) at least 1336 mzz(Z) contained in the closed cell. 2. The low density thermoplastic foam of claim 1, wherein the foam has a density of from about 0.05 to less than 0.2 g/cc. 3. The low density thermoplastic foam of claim 2, wherein the tensile strength of the foam is from about 1.5 to about 3.5 Mpa. 3. The low density thermoplastic foam of claim 2, wherein the foam has a compressive strength of about 0.65 to about 1.5 Mpa. 4. The low density thermoplastic foam of claim 3, wherein the foam has a compressive strength of about 0.65 to about 1.5 Mpa. 3. The low density thermoplastic foam of claim 2, wherein the foam has a density of less than about 0.05 to 0.1 g/cc. 6. The low density thermoplastic foam of claim 5, wherein the foam has a density of less than about 0.05 to 0.1 g/cc. 3. The low density thermoplastic foam of claim 2, wherein ethylene furanoate moieties are at least 50% by weight of the thermoplastic polymer. 3. The low density thermoplastic foam of claim 2, wherein the cell walls consist essentially of polyethylene furanoate. 3. The low density thermoplastic foam of claim 2, wherein the cell walls consist essentially of polyethylene furanoate having a molecular weight of at least about 90,000. 3. The low density thermoplastic foam of claim 2, wherein the ethylene furanoate moieties are at least 85% by weight of the thermoplastic polymer. 3. The low density thermoplastic foam of claim 2, wherein at least about 75% of the cells are closed cells. Thermoplastic foam containing:
(a) a thermoplastic polymer cell comprising cell walls comprising polyethylene furanoate having a crystallinity of at least 10%, wherein at least about 50% by volume of the cells are closed cells and the thermoplastic polymer does not contain tannin moieties or is 20% by weight. Contains tannin moieties in an amount less than % -; and
(b) Gas within the closed cell containing 1336mzz(Z) contained within the closed cell. 14. The method of claim 13, wherein the gas in the closed cell is one or more of 1234ze(E), 1336mzz(E), 1224yd(E), 1224yd(Z), 1233zd(E), 1234yf, and combinations of two or more thereof. Additionally comprising: thermoplastic foam. 15. The thermoplastic foam of claim 14, wherein at least about 75% of the cells are closed cells. 14. The thermoplastic foam of claim 13, wherein the gas within the closed cells comprises at least 60% by weight of 1366mzz(Z) and the cell walls consist essentially of polyethylene furanoate having a molecular weight of at least about 90,000. 14. The thermoplastic foam of claim 13, wherein the gas within the closed cell consists essentially of 1336mzz(Z). A wind energy turbine blade and/or nacelle, or a wall for an automobile vehicle, or an aircraft or aerospace vessel, comprising the foam of any one of claims 1 to 17. A foamable composition comprising:
(a) a thermoplastic polymer comprising polyethylene furanoate containing no tannin moieties or containing tannin moieties in an amount of less than 20% by weight; and
(b) Blowing agent containing 1336mzz(Z). 20. The foamable composition of claim 19, wherein the blowing agent comprises from about 5% to about 95% of the 1336mzz(Z). 20. The foamable composition of claim 19, wherein the polyethylene furanoate has a molecular weight of from about 25,000 to at least about 180,000 and a crystallinity of from 30% to 60% by volume. 20. The foamable composition of claim 19, wherein the polyethylene furanoate has a molecular weight of from about 80,000 to at least about 130,000 and a crystallinity of from 30% to 60% by volume. 21. The foamable composition of claim 20, wherein the polyethylene furanoate has a molecular weight of from about 80,000 to at least about 130,000 and a crystallinity of from 30% to 60% by volume. 24. The method of claim 23, wherein the polyethylene furanoate has a molecular weight of about 90,000 to at least about 120,000, has a crystallinity of 30% to 60% by weight, and the blowing agent has at least about 60% by weight of 1336mzz(Z). A foamable composition comprising. 21. The foamable composition of claim 20, wherein the polyethylene furanoate has a molecular weight of from about 25,000 to at least about 180,000 and a crystallinity of from 30% to 60% by volume. 28. The foamable composition of claim 27, wherein the polyethylene furanoate has a molecular weight of from about 80,000 to at least about 130,000 and a crystallinity of from 30% to 60% by volume. 21. The foamable composition of claim 20, wherein the polyethylene furanoate has a molecular weight of from about 80,000 to at least about 130,000 and a crystallinity of from 30% to 60% by volume. 21. The method of claim 20, wherein the polyethylene furanoate has a molecular weight of about 90,000 to at least about 120,000 and a crystallinity of 30% to 60% by volume, and the blowing agent has at least about 60% by weight of 1336mzz(Z). A foamable composition comprising: