Chemically modified polyesters and manufacturing processes

Abstract

Chemically modified polyesters, foamable compositions thereof for forming low-density foams, and methods for producing the foamable compositions and foams are disclosed. The compositions include amorphous copolyesters, or amorphous copolyester polycarbonates, amorphous copolyester polyethers, or combinations thereof. Additionally, applications for the low-density foams are disclosed.

Description

[Technical Field]

[0001] Described herein are chemically modified polyesters and methods for making the same. More specifically, the chemically modified polyesters are amorphous copolymers. Additionally, methods for making and using these compositions are described herein. The methods disclosed herein can utilize virgin or recycled polyester polymers, such as semi-crystalline polyethylene terephthalate (PET), including recycled PET, as a source polymer to form amorphous copolyesters that can be used as components of foamable compositions. The resulting low density foams (e.g., 0.1 g / cm) disclosed herein can be used to form amorphous copolyesters that can be used as components of foamable compositions. 3 The following densities) can be utilized, for example, in extruded expanded bead foams, which may find use, for example, as insulation and / or other construction and industrial applications. [Background technology]

[0002] Crystalline and semi-crystalline polyester polymers cannot be easily foamed to produce low density foams because their crystalline or semi-crystalline nature means that high temperatures are required to prevent the material from recrystallizing as the gas expands to produce the foam. In the molten state, above its recrystallization temperature, the viscosity of semi-crystalline polyesters such as PET is too low to allow significant expansion of the gas bubbles before curing. This limits the foam density that can be achieved (e.g., densities below 0.1 g / cm). 3 (The present invention solves the problem of producing low density foams by foaming crystalline or semi-crystalline polyesters to convert the semi-crystalline polyester, such as PET, into an amorphous copolyester polymer material that can produce low density foams from the polymer melt or from extruded and expanded beads.) Summary of the Invention [Problem to be solved by the invention]

[0003] By producing expandable polyesters or copolyesters derived from semi-crystalline PET, the starting material can be sourced from a "recycled" stream (from bottles and other post-consumer PET sources). For purposes of this invention, "recycled" refers to both post-consumer and post-industrial source materials. Recycled PET is in abundant supply. Thus, one particularly desirable objective is to utilize recycled semi-crystalline PET and convert it into an amorphous polymer that can be expanded to produce low-density foams. Therefore, there is a need for expandable compositions comprising amorphous polymers derived from semi-crystalline polyesters, either virgin or recycled polyesters, such as recycled PET, methods for preparing the amorphous polymers and expandable compositions, and methods for using them. The present invention is directed to these and other important objectives. [Means for solving the problem]

[0004] In one embodiment, the present invention provides a polymeric material comprising different polyester units, or polyester units and polycarbonate or polyether units, or both, and optionally further comprising one or more binders; and (i) polymerized units of one or more aromatic diacid monomers; (ii) 10 mol % to 40 mol % of the sum of polymerized units of one or more aliphatic diols (mol % is the sum of the moles of polymerized units of one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized units comprising the copolymer); (iii) a primary Tg between 85°C and 125°C measured from the second heat inflection point of the DSC curve using a heating / cooling rate of 10°C / min; and (iv) a heat of fusion ΔH of less than 10 J / g after exposure to a hydrostatic pressure of 1000 psi CO2 at 135°C for 4 hours m The present invention relates to a copolyester, copolyester polycarbonate or copolyester polyether copolymer characterized by having a peak.

[0005] In another embodiment, the copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a B[X] or B[X+X'] value of 0.20 or greater, where B is the Konig B value for randomness of the copolymer, [X] is the mole fraction of comonomer polyester structural units, or the mole fraction of comonomer polycarbonate and / or polyether structural units, and [X+X'] is the mole fraction of comonomer polyester structural units, or the mole fraction of comonomer polycarbonate and / or polyether structural units, in the copolymer, including any units containing residue fragments thereof.

[0006] The present invention also relates to a foamable composition comprising a copolyester, copolyester polycarbonate or copolyester polyether copolymer and one or more blowing agents.

[0007] The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and, together with the description, serve to explain the principles of the invention. [Brief explanation of the drawings]

[0008] [Figure 1] Figure 1 shows the increase in the Konig B value for monomer distribution within the polymer chain as a function of reaction time (in minutes) for the catalyzed transesterification of a 75 / 25 blend (by weight) of virgin polyethylene terephthalate with virgin polycarbonate (Makrolon® 3158) at 275°C. The catalyst is monobutyltin oxide, MBTO (2,000 ppm - parts by weight of MBTO per million parts by weight of the total weight of the two reactant polymers). [Figure 2] Figure 2 shows the transesterification reaction between polycarbonate (PC) and polyethylene terephthalate (PET) and two side reactions. [Figure 3]Figure 3 shows a representative quantitative C NMR spectrum and peak assignments for a PC / PET copolymer. Numerical labels indicate the assignments for individual carbons. Letter labels overlaid on the NMR resonance peaks indicate the integral regions for calculating the mole fraction of structural units (overall copolymer composition). DETAILED DESCRIPTION OF THE INVENTION

[0009] In the case of semi-crystalline PET, foaming must occur above the crystallization temperature of PET (approximately 150°C), where the polymer has very low melt strength and can only minimally expand before vitrification begins. As disclosed herein, PET (virgin or recycled) is rendered amorphous. Eliminating crystallization allows the polymer to be processed below 150°C, where melt strength is inherently high. This facilitates cell expansion and results in a low-density product. However, while eliminating crystallinity in the neat form of the polymer is necessary, it is not sufficient for foamability. The addition of one or more soluble blowing agents increases the crystallization rate. Therefore, a further challenge is to avoid polymer crystallization under certain pressures. Further disclosed herein is the specific reduction in polymer block structure required to sufficiently reduce the crystallization rate in the presence of such blowing agents (e.g., CO2). This is because the polymer foams adequately at temperatures below 150°C and achieves a foam density of 0.1 g / cm. 3 These are attributes required to achieve a density of less than

[0010] Unlike semi-crystalline PET, which is known to have low solubility in typical blowing agents, the process of the present invention modifies PET to produce an amorphous polymer that has higher solubility in typical blowing agents, allowing for the production of low-density foams. Preventing the formation of crystalline structures also increases gas permeation rates, which favors cell growth during the foaming process.

[0011] Recycled PET becomes useful for foaming by reducing or eliminating its ability to crystallize in the presence of heat and / or dissolved gases. This is achieved by directly transesterifying molten PET with one or more other polymers in the presence of a catalyst to promote rearrangement and transformation of the repeat units contained within the polymer, forming a new copolyester (such as a copolyester polycarbonate or copolyester polyether). The non-PET polymer component does not necessarily have to be polyester, and it does not necessarily have to be amorphous. The deliberate elimination of carbonyl and ethylene glycol species produces a copolyester or copolyester polyether backbone structure with an increased Tg. With appropriate catalyst selection, temperature, and reaction time, the crystallization rate of the resulting polymer is sufficiently slow. This reduction or elimination of crystallization allows processing at temperatures below 150°C (the crystallization temperature of the starting PET material). The final copolyester (or copolyester polycarbonate or copolyester polyether) can be melt-blended with a physical blowing agent, expanded by extrusion foaming, or rapidly cooled for expansion in a separate process (expandable beads).

[0012] The present invention may be more readily understood by reference to the following detailed description, examples, drawings, and claims, as well as their preceding and following explanations. It should be understood, however, that the present invention is not limited to the specific compositions, articles, devices, systems, and / or methods disclosed, unless expressly stated otherwise, and as such may, of course, vary. Although aspects of the invention may be described and claimed in particular statutory classes, such as composition statutory classes, this is for convenience only, and one of ordinary skill in the art will understand that each aspect of the invention may be described and claimed in any statutory class.

[0013] The following detailed description of the present invention is also provided as an enabling teaching of the best, currently known mode of the present invention. To this end, those skilled in the art will recognize and appreciate that changes and modifications may be made to the various aspects of the present invention described herein and still obtain the beneficial results of the present invention. It will also be appreciated that some of the benefits of the present invention can be obtained by selecting some of the features of the present invention without using other features. Thus, those skilled in the art will recognize that many modifications and adaptations to the present invention are possible and may even be desirable in certain circumstances, and therefore are also a part of the present invention.

[0014] While the present invention may be embodied in various forms, the following description of some embodiments is made with the understanding that the present disclosure is to be considered as an example of the present invention and is not intended to limit the present invention to the specific embodiments illustrated. Headings are provided for convenience only and should not be construed as limiting the present invention in any way. An embodiment illustrated under any heading or in any portion of this disclosure may be combined with an embodiment illustrated under the same or any other heading or portion of this disclosure.

[0015] Any combination of the elements described herein in all possible variations thereof is encompassed by the invention unless otherwise indicated herein or otherwise clearly contradicted by context.

[0016] Unless expressly stated otherwise, it is in no way intended that any method or aspect described herein be construed as requiring that its steps be performed in a particular order. Thus, if a method claim does not specifically recite in the claim or description that the steps are limited to a particular order, no order is intended to be inferred in any sense. This applies to all possible non-expressive bases for interpretation, including logical considerations regarding the arrangement or operational flow of steps, simple meaning derived from grammatical construction or punctuation, or the number or type of embodiments described herein. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only, and not restrictive.

[0017] All publications mentioned herein are incorporated herein by reference to disclose and describe the methods and / or materials in connection with which the publications are cited.

[0018] It should be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In this specification and in the claims that follow, reference will be made to a number of terms defined herein.

[0019] As used in this specification and the appended claims, the singular forms "a," "an," and "the" include plural referents unless the context clearly dictates otherwise.

[0020] As used herein, the term "and / or" means "and, or alternatively."

[0021] As used herein, the term "optional" or "optionally" means that a described event, condition, ingredient, or circumstance may or may not occur, and that the description includes instances in which said event, condition, ingredient, or circumstance occurs and instances in which said event, condition, ingredient, or circumstance does not occur.

[0022] As used herein, the phrase "sufficient for" (e.g., "conditions sufficient for") means a value or condition sufficient to perform the function or property for which such value or condition is manifested. As noted below, the exact values ​​or specific conditions required may vary from embodiment to embodiment, depending on recognized variables such as the materials used and / or processing conditions.

[0023] The term "by weight," when used in connection with an ingredient, is based on the total weight of the formulation or composition in which the ingredient is included, unless otherwise specified. For example, if a particular element or ingredient in a composition or article is said to be present in an amount of 8% by weight, it is understood that this percentage is relative to a total composition percentage of 100% (and thus may be expressed as 8% by weight). In some cases, the weight percentage of an ingredient is based on the total weight of the composition "on a dry basis," which refers to the weight of the composition without water (e.g., less than about 1%, less than about 0.5%, less than about 0.1%, less than about 0.05%, or about 0% water by weight, based on the total weight of the composition).

[0024] When a numerical value, e.g., 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, etc., is disclosed herein, the following sentence typically follows such a numerical value: "Each of the foregoing numerical values ​​can be used in conjunction with the terms "about," "at least about," or "less than about," and any of the foregoing numerical values ​​can be used alone to describe an open-ended range or in combination to describe a limited range." This sentence means that each of the foregoing numerical values ​​can be used alone (e.g., 4), preceded by the word "about" (e.g., about 8), preceded by the phrase "at least about" (e.g., at least about 2), preceded by the phrase "less than about" (e.g., less than about 7), or used in any combination with or without any of the preceding words or phrases used to define the range (e.g., 2 to 9, about 1 to 4, 8 to about 9, about 1 to about 10, etc.). Furthermore, when a range is described as "less than or equal to about X," this phrase is equivalent to the range that is instead a combination of "about X" and "less than about X." For example, "about 10 or less" is the same as "about 10, or less than about 10." Such interchangeable range descriptions are contemplated herein. While other range formats are disclosed herein, differences in format should not be construed to imply differences in substance.

[0025] The use of numerical values ​​in the various quantitative values ​​set forth in this application, unless expressly indicated otherwise, is expressed as approximations, as if both the minimum and maximum values ​​within the stated range were preceded by the word "about." In this manner, slight variations from the stated value may be used to achieve substantially the same results as the stated value. The disclosure of ranges also contemplates continuous ranges, including every value between the recited minimum and maximum values, and any ranges that may be formed by such values. Also disclosed herein are any and all ratios (and any such ratio ranges) that may be formed by dividing a recited numerical value into any other recited numerical value. Accordingly, those skilled in the art will appreciate that many such ratios, ranges, and ratio ranges may be explicitly derived from the numerical values ​​presented herein, and that in all instances, such ratios, ranges, and ratio ranges represent various embodiments of the present invention.

[0026] As used herein, the term "substantially free" means a composition having less than about 1 wt. % of the indicated substance, e.g., less than about 0.5 wt. %, less than about 0.1 wt. %, less than about 0.05 wt. %, or less than about 0.01 wt. %, based on the total weight of the composition.

[0027] As used herein, the term "substantially," when used in reference to a composition, means at least about 60% by weight, e.g., at least about 70% by weight, at least about 80% by weight, at least about 90% by weight, at least about 95% by weight, at least about 98% by weight, at least about 99% by weight, or about 100% by weight of a particular feature or component, based on the total weight of the composition.

[0028] The term "polyester" as used herein refers to a polymer whose repeating units are characterized by ester groups. Thus, the term includes not only homopolymers, i.e., polyesters composed of one acid component and one alcohol component, or one hydroxycarboxylic acid component, or one lactone component, but also copolymers, i.e., polyesters composed of at least two acid and / or alcohol components, and / or hydroxycarboxylic acid and / or lactone components ("copolyesters"). The term "copolyester" is a subset of polyester. When a copolymer results from the transesterification of two different polyester polymers, the resulting copolymer is referred to herein as a "copolyester" copolymer or "mixed copolyester," to distinguish it from the general term copolyester, which also refers to copolyester polycarbonates or copolyester polyethers. When a copolymer results from the transesterification of a polyester polymer and a polycarbonate polymer, the resulting copolymer (copolyester) is referred to herein as a "copolyester polycarbonate" copolymer. The term "copolyester polycarbonate" is a subset of copolyester. It should be understood that under some reaction conditions, such polymers may undergo loss of CO units, so that the resulting functionality is an ether unit (resulting from the loss of CO in carbonate units). If 100% (or nearly 100%, e.g., 99.5%, or 99%, or 95%) of the possible carbonate functional groups are converted to ether functional groups, the resulting polymer is referred to herein as a "copolyester polyether" (the term "copolyester polyether" is a subset of copolyester). Otherwise (i.e., if less than 95%, or less than 99%, or less than 99.5% of the possible carbonate functional groups are converted to ether functional groups), the copolymer is still referred to as a copolyester polycarbonate.

[0029] Polyesters can be obtained by conventional synthesis using dicarboxylic acids and difunctional alcohols. Aromatic dicarboxylic acids are preferred. Examples of suitable dicarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, and 2,5-furandicarboxylic acid (FDCA). Examples of suitable difunctional alcohols (diols) that can be combined with any of these dicarboxylic acids include ethylene glycol, propanediol (including propylene glycol), butanediol (butylene glycol), cyclohexanedimethanol, isosorbide, and spiroglycol. For example, poly(ethylene terephthalate), PET, can be synthesized using ethylene glycol and terephthalic acid, and poly(ethylene furanoate), PEF, can be synthesized using ethylene glycol and 2,5-furandicarboxylic acid.

[0030] Copolyesters can be obtained, for example, by the transesterification of two or more different polyester polymers, as discussed further herein.

[0031] Polycarbonate polymers include those obtainable from the reaction of polyfunctional alcohols (e.g., diols, including those disclosed above, as well as bisphenol A, BPA) with carbon acid derivatives such as diphenyl carbonate, dimethyl carbonate, ethylene carbonate, or phosgene. For example, the polymer most commonly referred to as polycarbonate can be synthesized by the reaction of phosgene (or dimethyl carbonate) with BPA.

[0032] Copolyester polycarbonates and copolyester polyethers (at least formally derived from copolyester polycarbonate) can be obtained, for example, by transesterification of one or more polyester polymers with one or more polycarbonate polymers, as discussed further herein. As discussed above, removal of CO from a copolyester polycarbonate copolymer can form a copolyester polyether copolymer. Such side reactions may or may not occur at all possible structural unit units along the polymer chain.

[0033] As used herein, the term "structural unit" is used in its usual sense in the art. In polymer chemistry, a structural unit is a building block of a polymer chain. This is the result of monomers polymerized into long chains (polymers). There may be one or more structural units in a repeat unit. When different monomers are polymerized, a copolymer is formed. In the case of polyethylene terephthalate (PET), the monomers typically used to make this polymer are ethylene glycol (HO-CH-CH-OH) and terephthalic acid (HOOC-CH-COOH). The polymer has two structural units: -O-CH-CH-O- and -OC-CH-CO-. The repeat unit is -CH-CH-O-CO-CH-CO-O-. Additionally, as used herein, the term "structural unit" can refer to a repeating segment containing two monomer units in polymerized form, which is the repeat unit within a polymer. For example, in the transesterification of a polyester such as PET with a polycarbonate (PC), some repeating units of the product may be two-monomer segments resulting from the original constituent polymer, such as the repeating unit -CH-CH-O-CO-CH-CO-O- of the polyester, as well as other repeating segments, which can be considered structural units where the distinction between a monomeric structural unit and a two-monomer structural unit is clearly defined or clear from the context. For example, a two-monomer segment of a polyester is a structural unit, and a two-monomer segment of a polycarbonate is a structural unit. Structural units can be identified and quantified by techniques such as nuclear magnetic resonance spectroscopy (NMR), as discussed further herein.

[0034] Certain polymerization reactions, or certain polymers undergoing a reaction, may involve side reactions that alter structural units (X) compared to those expected from the monomer or polymerized monomer units. When the altered unit loses a CO molecule from part of its structure, e.g., a polycarbonate unit, the remaining portion is referred to as a residual fragment or residue (X'). Such species can still be identified by NMR and quantitatively included in the number of structural units in the polymer by considering all units derived from the expected structural unit X to now be present in the polymer as a combination of X and X' (i.e., X + X'). Thus, [X + X'] is the mole fraction of structural unit X and its residue X'.

[0035] The glass transition temperature, Tg, of the polymer was measured using differential scanning calorimetry (DSC) and was determined as the inflection point of the baseline step transition on the second heating of the sample (10°C / min heating / cooling rate) and is reported in degrees Celsius (see Example 4).

[0036] The enthalpy of melting or crystallization, ΔHm, was measured by DSC using a linear baseline estimation of the peak area and reported as J / g (measured as the linear integral of the peak area as a deviation from the baseline, starting at 125°C and ending at 250°C). Analysis of the sample before exposure to the hydrostatic pressure of CO2 was performed at a second temperature ramp. When this is performed on a copolyester copolymer before exposure to a blowing agent such as CO2, it is referred to herein as the "pre-foam ΔHm." Considering that the enthalpy of crystallization of crystalline PET is 140 J / g, it can be estimated that an enthalpy of crystallization of less than 10 J / g represents approximately 7% or less crystallinity, and an enthalpy of crystallization of less than 5 J / g represents less than 4% crystallinity.

[0037] ΔH after exposure to the hydrostatic pressure of CO2, referred to herein as "ΔHm after foaming" mTo evaluate ΔHm, samples were compression molded into 1.3 mm thick films (25 tons of pressure at 180°C for 5 minutes) and placed in a pressure vessel. The vessel was heated to 135°C, and the headspace was filled with approximately 1000 psi of carbon dioxide blowing agent, in which the samples were immersed for 4 hours. The pressure was then rapidly released to induce foaming in the samples. Differential scanning calorimetry was then used to obtain the enthalpy of melting or crystallization, "ΔHm after foaming," (as described above and in Example 4), except that analysis of the samples after exposure to CO hydrostatic pressure was performed at the first temperature ramp.

[0038] As used herein, the term "foam" refers to a lightweight, multicellular, fine-bubble mass formed in or on the surface of a liquid, or derived from a liquid. Depending on the context, the term "foam" may refer to the wet foam before drying, or may be used to describe the dried foam. To determine whether a sample can be successfully foamed ("foamable resin" or "foamable copolymer"), the molten sample must be foamed and capable of forming a stable foam. Generally, and for the end uses considered herein, a marginally adequate foam results from a volume expansion of at least 3.5 times, and up to 8 times. A "good" foam results from a volume expansion of 8 to 11.5 times. Preferred foams have a volume expansion of at least 11.5 times, and more preferably at least 16 times. The volume expansion is determined by the density of the solid polymer (e.g., 1.27 g / cm for PET). 3 ) divided by the density of the foam. The density of the foam is measured using the buoyancy method: weigh the sample in air (grams of foam sample) and weigh the buoyancy of the sample in water at room temperature (density of water is 1 g / cm 3 , the weight of water displaced is equal to the volume of water displaced - consequently, this is the mass of the foamed sample in cm of water, assuming no water is absorbed. 3 Then the density of the foam, g / cm 3 (where the volume expansion is calculated as the weight of the foamed sample in air divided by the volume of the foamed sample.) The foams described herein meet these targets for volume expansion.

[0039] As used herein, "stable foam" refers to a foam that is stable with respect to observable shrinkage or collapse during and thereafter the drying process in the absence of external forces other than the surrounding atmosphere.

[0040] As used herein, the term "rigid foam" refers to a dry foam having a cell structure with a compressive strength greater than 5 psi.

[0041] As used herein, "ambient cure conditions" refers to the range of conditions typically experienced in unconditioned outdoor spaces under which a sprayed or aerosol-dispensed foam product may be dispensed and dried. "Ambient cure conditions" excludes environments that include any form of forced convection and / or forced heating.

[0042] All molecular weights and other values ​​related to molecular weight disclosed herein are determined by GPC.

[0043] As used herein, gel permeation chromatography (GPC) refers to a chromatographic separation method in which molecules in a solution are separated by their size. Separation is achieved by the differential exclusion of sample molecules as they pass through a bed of porous particles known as a separation column. GPC can be used to determine substantially accurate molar mass distributions of polymer molecules. For example, a constant volume of the liquid fraction (eluent) that passes through the column is collected. As the polymer elutes through the column, molecules too large to pass through the pores of the column are excluded from the packed pore volume and elute at earlier retention times, while smaller molecules enter the pores and elute at later retention times. The concentration of the eluted polymer can be measured by spectroscopic techniques, such as refractive index (RI) and ultraviolet (UV). The eluent stream can also be continuously analyzed by RI, low-angle laser light scattering (LALLS), multi-angle laser light scattering (MALLS), UV, and / or viscosity measurements.

[0044] As used herein, the terms "molar mass distribution," "MMD," and "molecular weight distribution" are used interchangeably and refer to the number of moles of each polymer species or number of polymer chains (N i ), and the molar mass of the species (M i ) or describes the relationship between polymer chains. The molar mass distribution of a polymer may vary depending on the polymer fraction. Depending on the statistical method applied, different mean values ​​may be defined and are described herein.

[0045] As used herein, the term "number average molecular weight" (M n , or

number

number

[0046] As used herein, the term "weight average molecular weight" (M w , or

number

number

[0047] Because copolymers consist of at least two types of structural (or monomer / monomer residue) units, copolymers can be classified based on the way in which these units are randomly arranged along the chain. One index characterizing the monomer distribution along the copolymer chain is the "König B value" (B), which is defined by the formula for binary copolymers (see, for example, L. Tau et al., EP 2,736,930 B1):

number

[0048] NMR-based methods can be used to determine copolymer composition and the exact monomer sequence in a copolymer, and to calculate a measure of blockiness (B), which accounts for the blockiness (or, in fact, the reduction in the level of blockiness) of copolymers produced by catalytic transesterification processes. This B value has been shown to vary with processing conditions, such as temperature, time, and catalyst type, as well as the level of comonomers, such as polycarbonate, in the blend. For example, Figure 1 shows the variation in the Konig B value (monomer distribution or blockiness breakdown) of a copolymer as a function of reaction time for the catalytic transesterification reaction of polyethylene terephthalate (PET, monomer structural unit, Y) with polycarbonate (PC, monomer structural unit, X) carried out at 275°C. The B value was obtained using the method described herein. Additionally, this method can be used to distinguish the foamable copolymer compositions described herein from those of the prior art.

[0049] The Konig B value for the monomer distribution in a polymer can be described as X representing the repeating units of the comonomer (such as polycarbonate) and Y representing the repeating units of the polyester monomer (such as PET): A minimum value of B=0 (close to) means that the copolymer composition exists as a diblock polymer arrangement (non-zero because a diblock must have one XY or YX dimolecule): XXXXXXXYYYYYYYYYYYYYYYYYYYYYYYYYYY. A value of B=1 indicates a random copolymer (or "statistical copolymer") such as, for example: XYYYYYYYYXXXYYYYYYYYYYYYYXXYYY. Maximum value of B, B 最大 = 1 / [Y] represents a perfectly alternating copolymer (every X (minor component) is surrounded by Y (major component), there are no X blocks or XX dyads in the polymer chain); XYYYYYYXYYYXYYYYYYYXYYXYYYYYXYYYXYY In this case, [Y] is the mole fraction of polyester monomer units (e.g., when X:Y=1:4 or 20:80, B 最大 = 1.25. That is, the mole fraction of X is 0.2 and the mole fraction of Y is 0.8 (1 / 0.8 = 1.25).

[0050] Highest possible B 最大 occurs in a 50 / 50 molar ratio binary copolymer containing two perfectly alternating monomers, X and Y ([X] = [Y] = 0.5), so that there are two molecules of XY and YX (in equal amounts), and therefore [XY] = [YX] = 0.5, XYXYXYXYXYXYXYXYXYXYXYXYXYXYXYXYXYXYXYX. Formula 1: B=([XY]+[YX]) / (2[X][Y])=(0.5+0.5) / (2×[0.5]×[0.5])=1 / 0.5=2, and: B 最大 =1 / [Y]=1 / 0.5=2.

[0051] In the case of copolyester polycarbonates made from the transesterification of polyester polymers (PET) and polycarbonate polymers (PC), the resulting copolymer (PC / PET) is not an ideal binary copolymer due to side reactions (such as loss of CO2 from the polycarbonate units). The definition of indicator B is modified to accommodate the side reactions while retaining the same physical meaning as above. The new definition is illustrated using the example of PC / PET transesterification (Figure 2).

number

[0052] Figure 3 shows a representative quantitative analysis of PC / PET copolymers. 13 The C NMR spectrum and detailed peak assignments are shown. Due to the quantitative nature of NMR spectra, the peak intensity (I) is strictly proportional to the number of structural units or bimolecules observed.

[0053] Considering the comonomer units derived from PC units X and X', the total amount of PC comonomer units is N X+X’ In Figure 3, carbon assignments 8, 8', 16, 17, 18, and 19 are unique to the PC fragment (either X or X') and account for the eight carbons of the core PC fragment (eight carbons from the two phenyl rings; in this case, these eight carbons are only bonded to two other phenyl ring carbon atoms and one phenyl ring hydrogen atom). All of these carbons are labeled D, E, and F in Figure 3. 13 C NMR peaks are assigned to 13 The C NMR peaks are expressed as peak intensities and I D、 I E and I F Therefore, the total amount of PC comonomer units N X+X’ =(I D +I E +I F ) / 8.

[0054] Similarly, considering the comonomer units derived from the PET unit Y, the total amount of PET units is N YIn Figure 3, carbon assignments 1 (or 1' or 11), 2 (or 2' or 2''), and 3 (or 3' or 3'') are unique to PET fragment Y and account for the eight carbons of the core PET fragment (the six phenyl carbons and the two carbonyl carbons attached to the phenyl ring). All of these carbons are labeled A, B, and C in Figure 3. 13 C NMR peaks are assigned to 13 The C NMR peaks are expressed as peak intensities and I A、 I B and I C Therefore, the total amount of PET monomer units N Y =(I A +I B +I C ) / 8.

[0055] N X+X’ and N Y From the expression in, the mole fractions of PC and PET can be calculated:

number

number

[0056] For copolyesters containing 75 wt. % PET, resins with B values ​​above 0.88, preferably above 0.90, will produce foamed articles when CO2 is absorbed as a blowing agent. Using batch Haake mixing bowl experiments and continuous Pilot Line runs, several transesterified PET / PC resin samples were produced, with B values ​​of approximately 0.36 for the 75 wt. % PET copolyester without a catalyst (see, for example, Table 3), ranging from 0.51 to 1.25 for the same system with a catalyst (Table 3).

[0057] The B value simply characterizes how randomly (or block-wise) the comonomers are distributed along the copolymer chain. The block length distribution, which governs the foamability of a copolymer, is influenced by both B and the copolymer composition. Using the definition of B in Equation (2), B[X+X'] is a universal indicator for characterizing the foamability of PC / PET copolymers, where [X+X'] is the mole fraction of PC comonomer and residues in the copolymer. Regardless of composition, resins with B[X+X'] greater than 0.18, preferably greater than 0.20, and more preferably greater than 0.22 typically produce foams when absorbed with CO2 as a blowing agent (see Table 1 for examples of copolymers with four different compositions).

[0058] In certain embodiments, the invention described herein comprises: (ii) from 10 mol % to 40 mol % of the sum of polymerized units of ethylene glycol, propylene glycol, butylene glycol, cyclohexanedimethanol, isosorbide, or spiroglycol, or a combination thereof; (iii) a Tg of 85 to 120°C measured from the inflection point of the second heat of the DSC curve using a heating / cooling rate of 10°C / min; and (iv) a heat of fusion, ΔH, of 10 J / g or less after exposure to a hydrostatic pressure of 1000 psi CO2 at 135°C for 4 hours. m The present invention relates to a copolyester, copolyester polycarbonate or copolyester polyether copolymer characterized by having a peak.

[0059] As previously discussed, crystalline and semi-crystalline polyester polymers cannot be easily expanded to produce low-density foams; high temperatures are required to prevent the material from recrystallizing while the gas expands to produce the foam. The approach discussed herein reduces or eliminates the crystallinity of the polymer by breaking down the continuous repeating polyester structural units. Because there is no crystallization to overcome, amorphous copolyesters can be expanded at low temperatures (above the glass transition temperature) where melt strength is reasonable. Disclosed herein are methods for directly converting semi-crystalline PET (optionally, some or all of which may be recycled PET) into amorphous copolyesters, such as blended polyester copolyesters, copolyester polycarbonates, or copolyester polyethylenes, and compositions for producing expandable copolyester polymers.

[0060] Disclosed herein is a method for forming the expandable copolyesters, copolyester polycarbonates, or copolyester polyethers described herein, comprising: (i) melting a blend of at least two polymers selected from a first polyester polymer, one or more other polymers selected from one or more polycarbonate polymers and one or more other polyester polymers, or combinations thereof, in the presence of a transesterification catalyst, and optionally a chain linking agent; (ii) maintaining a temperature above 200°C for at least 3 minutes, optionally with mixing; (iii) optionally collecting at least a portion of the ethylene carbonate produced; and (iv) cooling to form a solid copolymer.

[0061] The starting polyester, or one of the starting polyesters, can be polyethylene terephthalate (PET). The starting polyethylene terephthalate (PET) can be commercially available, for example, as Certene® 8080 from Muehlstein (a subsidiary of Ravago, Arendon, Belgium), or can be supplied as solid recycled polyester, such as recycled PET, from, for example, Reterra Plastics (Reterra Corporation, Houston, TX, USA), PolyQuest Inc. (Darlington, SC, USA), Circular Polymers (Lincoln, CA, USA), or Evergreen Plastics (Clyde, OH, USA). Alternatively, the starting polyester can be synthesized by methods well known in the art (see above). Glycol-modified polyester (PETG) or other polyesters, such as polypropylene terephthalate (commonly called PTT or polytrimethylene terephthalate), polybutylene terephthalate, polycyclohexanedimethanol terephthalate, polyspiroglycol terephthalate, polyisosorbide terephthalate, polyethylene furanoate (PEF), polytrimethylene furanoate (PTF), or other furanoate-based polyesters, can be used as partial or complete replacements for semi-crystalline PET. Similarly, polycarbonate polymers may be commercially available, for example, as Makrolon® 3158 from Covestro AG (Leverkusen, Germany), or as CALIBRE® 1060DVD or CALIBRE® 1080DVD, or 17-22MF (Premier Plastic Resins) from Trinseo, LLC (Berwyn, PA, USA), or may be supplied as solid recycled polycarbonate, for example, as Opticarb PC from Star Plastics, Inc. (Ravenswood, WV, USA) or The Materials Group (Rockford, MI, USA), or may otherwise be synthesized by known methods.High Tg polyesters (such as Tritan® GX100 or FX200 from Eastman Chemical, Kingsport, TN) can be used as a partial or complete replacement for polycarbonate.

[0062] A polyester such as poly(ethylene terephthalate) is melted above its crystalline melt temperature and blended with a polycarbonate (preferably, for example, an aromatic polycarbonate such as bisphenol A polycarbonate) or other polyester, and an optional third polymer (which may be a polyester or polycarbonate-type polymer). Optionally, a chain linker, such as pyromellitic dianhydride, 3-(trimethoxysilyl)propyl methacrylate, or others known in the art, can be added. A transesterification catalyst is added to the melt blend either as a physical blend with the solid or molten polymer, or as a concentrate in one of the polymers. As described herein, the polymers are conveniently mixed and reacted in the melt phase, which also lends itself to extrusion processes already common in the art (e.g., in making foam insulation boards). Mixing and reaction can alternatively occur in solution, but few solvents form suitable solutions for these polymers, and most are considered environmentally unacceptable. Such solvents (and partial solvents) may include, but are not limited to, a 60 / 40 blend of phenol / 1,1,2,2-tetrachloroethane, fluorinated alcohols such as hexafluoroisopropanol, trifluoroacetic acid, orthochlorophenol, meta-cresol, chloroform, and methylene chloride.

[0063] The inventors have found that in the absence of a catalyst, the polymer does not transesterify sufficiently to produce a new copolymer that does not crystallize when a blowing agent is dissolved therein. Thus, when polyester polymers (or polyester and polycarbonate polymers) are simply blended in the absence of a catalyst (a "polymer mix," "polymer blend," or "mixed composition"), the result is either a blend of the starting polymers or a polymer that has significant "blockiness" and cannot be used to produce stable foams.

[0064] Suitable catalysts for the transesterification reaction include those known in the art, in particular, for example, titanium(IV) tetrabutoxide, Ti(OBu)4, titanium(IV) tetraisopropoxide, Ti(O i Organometallic complexes such as calcium(II) acetate in combination with cerium(III) acetate, Ce(OAc)3, ytterbium(III) acetoacetonate, Yb(acac)3, and antimony(III) oxide, Ca(OAc)2 / Sb2O3, as well as tin organometallic complexes such as monobutyltin oxide (MBTO), dibutyltin oxide (DBTO), and dioctyltin oxide (DOTO), some of which are available under the trade name FASCAT® catalyst (PMC Organometallix, Mount Laurel, NJ, USA). Suitable use levels may vary from catalyst to catalyst, but are generally in the range of 50 ppm to 10,000 ppm, 1,000 ppm to 5,000 ppm, or 1,500 ppm to 3,000 ppm (parts by weight of catalyst, parts by million by weight of total polymer present in the reaction).

[0065] In certain embodiments, as will be readily understood by those skilled in the art, the processes described herein can be carried out in any reactor known in the art that can withstand the process conditions. For example, without limitation, the reactor can include one vessel or two or more vessels. The polymer components are mixed to significantly disperse the minor phase and promote transesterification. In one embodiment, the components are mixed in the melt phase in a Haake blender (e.g., a Thermo-Scientific Haake Melt Rheometer), as described in Example 1. In another embodiment, the components are mixed in the melt phase in an extruder device, such as a twin-screw extruder, as described in Example 2. Optionally, other desired additives can be added to the Haake blend or extruder blend and mixed with the melt-phase polymer, or preferably, they are added later. Such other additives can include, for example, pigments, clays, colorants, lubricants, acid scavengers, infrared attenuators, nucleating agents, flame retardants, and / or fillers / agents for increasing gas permeability, in any combination. The polymer blend (with any additives) is heated to 200-280°C for approximately 1-5 minutes before quench cooling and pelletization.

[0066] The transesterification reaction can proceed without the use of high pressure, although high pressure can also be used (with a similar effect as increasing the temperature). Practical considerations can influence the specific selection of time and temperature conditions for the transesterification reaction, with lower temperatures requiring a longer time frame to affect the extent of reaction required to sufficiently minimize the degree of "blockiness" in the resulting copolyester and allow foaming of the copolyester product (see, e.g., Figure 1). In certain embodiments, the transesterification reaction can be carried out at a temperature (°C) of 150, 160, 170, 180, 190, 200, 205, 210, 215, 220, 225, 230, 235, 240, 245, 250, 255, 260, 265, 270, 275, 280, 285, 290, 295, 300, 310, 320, 330, or 350. The time (minutes) can be 0.5, 1, 2, 3, 4, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, or 150 or more. Each of the foregoing numbers (temperature or time) can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a limited range. Suitable reaction temperatures and times can be 200°C to 300°C and 5 to 60 minutes. Preferred reaction conditions (using a catalyst) are 230°C to 275°C and 5 to 30 minutes (using an initial time of about 2 minutes at 275°C to ensure the PET is in the molten phase).

[0067] While the by-product chemicals (CO2, ethylene glycol, and ethylene carbonate) have been discussed in the open literature, most prior art has focused on methods to avoid the by-chemicals altogether. As disclosed herein, certain side reactions can be selectively promoted through the selection of catalysts and reaction temperatures to preferentially promote the loss of ethylene glycol and increase the Tg of the final polymer. Thus, higher loadings of PET can be used in the blend without the expected limitation of Tg. Preferred catalysts for specifically promoting the loss of ethylene glycol to increase the Tg of the final polymer are DBTO, DOTO, Ti(OBu)4, and Ti(Oi Pr)4.

[0068] In one embodiment, a foamable composition is provided comprising the copolyester, copolyester polycarbonate, or copolyester polyether disclosed herein and a blowing agent. In certain embodiments, the blowing agent is selected from one or more physical blowing agents, such as pentane hydrocarbons, hydrofluoroolefins, carbon dioxide, nitrogen, oxygen, water, alcohols such as methanol and ethanol, ketones including acetone, ethers such as dimethyl ether and diethyl ether, halogenated hydrocarbons such as ethylene chloride and methylene chloride, or olefins such as pentene, or combinations thereof. Examples of suitable chemical blowing agents are azides such as azodicarbonamide (AZNP), 5-phenyltetrazole (5PT), or a mixture of citric acid and bicarbonate.

[0069] In another embodiment of the present invention, there are provided solid expandable beads made from any of the expandable compositions disclosed herein.

[0070] Additionally, the present invention provides foamed articles made by either: (a) extrusion foaming of any of the foamable compositions disclosed herein, or (b) expansion of the aforementioned solid foamable beads.

[0071] In certain embodiments, a method of forming a copolyester, copolyester polycarbonate, or copolyester polyether copolymer disclosed herein is disclosed, the method comprising: (i) melting a blend of at least two polymers selected from a first polyester polymer, one or more other polymers selected from one or more polycarbonate polymers and one or more other polyester polymers, or combinations thereof, in the presence of a transesterification catalyst, and optionally a chain linking agent; (ii) maintaining a temperature of greater than 200°C and less than 330°C for at least 3 minutes and up to 180 minutes, optionally with mixing; (iii) optionally collecting at least a portion of the ethylene carbonate produced; and (iii) cooling to form a solid copolymer.

[0072] In certain embodiments, at least a portion of the polyester units in the copolymer are derived from recycled polyethylene terephthalate.

[0073] In certain embodiments, reduced pressure is used to remove volatile species.

[0074] In certain such embodiments of this method, the weight ratio of the first polyester polymer to the one or more other polymers can be 35:65, 40:60, 42:58, 44:56, 46:54, 48:52, 50:50, 52:48, 54:46, 56:44, 58:42, 60:40, 62:38, 64:36, 66:34, 68:32, 70:30, 72:28, 74:26, 75:25, 76:24, 78:22, 80:20, 82:18, 84:16, 86:14, or 85:15. Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a limited range. For example, the weight ratio of the first polyester polymer to the one or more other polymers can be at least about 50:50, from about 50:50 to about 80:20, or from about 50:50 to about 75:25, or less than about 85:15. As discussed above, one or more other polymers can be present, which can include other polyester polymers. When the other polymer type includes one or more polyester polymers, separate embodiments exist in which the weight ratio of the total of all polyester polymers to polycarbonate polymers can be 35:65, 40:60, 42:58, 44:56, 46:54, 48:52, 50:50, 52:48, 54:46, 56:44, 58:42, 60:40, 62:38, 64:36, 66:34, 68:32, 70:30, 72:28, 74:26, 75:25, 76:24, 78:22, 80:20, 82:18, 84:16, or 85:15. Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a limited range. For example, the weight ratio of the total of all polyester polymers to polycarbonate polymer can be at least about 50:50, from about 50:50 to about 80:20, or from about 50:50 to about 75:25, or less than about 85:15.

[0075] In certain embodiments, disclosed are product copolyester copolymers obtained from the methods disclosed herein.

[0076] As discussed above, some structural units may suffer loss of a fragment of the structural unit, but the remaining fragment (residue) of the structural unit will still be present in the polymer chain. Each structural unit contains its residue in the following ratio: In certain embodiments, the molar ratio of polyester structural monomer units to one or more comonomer structural units (polycarbonate or other polyester structural units) in the copolyester, copolyester polycarbonate, or copolyester polyether is 45:55, 46:54, 48:52, 50:50, 52:48, 54:46, 56:44, 58:42, 60:40, 62:38, 64:36, 66:34, 68:32, 70:30, 72:28, 74:26, 75:25, 76:24, 78:22, 80:20, 82:18, 84:16, 86:14, 88:12, or 90:10. Each of the foregoing numbers may be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a limited range. For example, the molar ratio may be at least about 50:50, from about 50:50 to about 80:20, from about 50:50 to about 75:25, or less than about 85:15. As discussed above, one or more types of comonomer structural units may be present, which may include other polyester structural unit types or polycarbonate structural units. When two or more comonomer structural unit types are present, the ratio of each comonomer structural unit type (comonomer A to comonomer B) is not particularly limited in any way.

[0077] In certain embodiments, the molar ratio of polymerized structural units of polyethylene terephthalate (PET) or PET residues to one or more polycarbonate (PC) structural units or PC residues (in polymerized form) in the copolyester polycarbonate (or copolyester polyether) is 45:55, 46:54, 48:52, 50:50, 52:48, 54:46, 56:44, 58:42, 60:40, 62:38, 64:36, 66:34, 68:32, 70:30, 72:28, 74:26, 75:25, 76:24, 78:22, 80:20, 82:18, 84:16, 86:14, 88:12, 90:10. Each of the foregoing numbers may be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a limited range. For example, the molar ratio may be at least about 50:50, from about 50:50 to about 80:20, from about 50:50 to about 75:25, or less than about 85:15. As discussed above, one or more types of comonomer polycarbonate structural units (or residues thereof) may be present. When two or more comonomer polycarbonate types are present, the ratio of each comonomer polycarbonate unit type (comonomer A or residues thereof to comonomer B or residues thereof) is not particularly limited in any way. In one such embodiment, the copolymer contains only one type of polycarbonate comonomer (in polymerized form), which is a bisphenol A polycarbonate structural unit or residue thereof. Also, as discussed above, the polymerized structural units of polycarbonate (PC) in the polymer may remain intact (as polycarbonate monomers in polymerized form), or some or all of these structural units may be present as residual fragments (residues) remaining after loss of a CO molecule from the polycarbonate functional group.

[0078] In certain embodiments, the expandable copolyester, copolyester polycarbonate, or copolyester polyether copolymer has 10 mol % to 40 mol % of total polymerized structural units of one or more aliphatic diols, where mol % is the total moles of polymerized structural units of one or more aliphatic diols in the copolymer, expressed as a percentage of the total moles of polymerized structural units comprising the copolymer. The mol % of aliphatic diols can be determined by NMR of the product of the transesterification reaction. In certain embodiments, the expandable copolyester, copolyester polycarbonate, or copolyester polyether copolymer has 10, 15, 20, 22, 24, 26, 28, 30, 32, 34, 36, 38, 39, or 40 total polymerized structural units of one or more aliphatic diols (mol %). Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a limited range. Suitable mole percent of polymerized structural units of one or more aliphatic diols in the foamable copolyesters can be 15 mole percent to 40 mole percent, or 20 mole percent to 40 mole percent, or 20 mole percent to 39 mole percent, or 20 mole percent to 38 mole percent. In one embodiment, the mole percent of the aliphatic diol is 25 mole percent to 38 mole percent.

[0079] In certain embodiments, the expandable copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a glass transition temperature, Tg (°C), of 80, 85, 90, 95, 98, 100, 102, 105, 110, 115, 120, 125, or 130°C. Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range, or in combination to describe a limited range. Suitable Tg values ​​for expandable copolyesters can be 80°C to 125°C, or 85°C to 125°C, or 85°C to 120°C, or 90°C to 115°C. In one embodiment, the Tg is 95°C to 110°C.

[0080] In certain embodiments, the foamable copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a melting enthalpy, "ΔHm before foaming," (J / g), of 0, 0.1, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range, or in combination to describe a limited range. Suitable ΔHm values ​​before foaming for the foamable copolyester can be 15 J / g or less, or 10 J / g or less, or 0 J / g to 15 J / g, or 0 J / g to 10 J / g, or 0.1 J / g to 15 J / g, or 0.1 J / g to 10 J / g. Preferably, the ΔHm is 0 J / g or 5 J / g or less.

[0081] In certain embodiments, the foamable copolyester, copolyester polycarbonate, or copolyester polyether copolymer has an enthalpy of melting or crystallization, "post-foam ΔHm," (J / g), of 0, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15. Each of the foregoing numbers may be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers may be used alone to describe an open-ended range or in combination to describe a limited range. Post-foam ΔHm means that the ΔHm measurement is performed after exposure to the hydrostatic pressure of CO2. A suitable ΔHm after foaming of the foamable copolyester may be 15 J / g or less, or 12 J / g or less, or 10 J / g or less, or 0 J / g to 15 J / g, or 0 J / g to 12 J / g, or 0 J / g to 10 J / g, or 0.1 J / g to 15 J / g, or 0.1 J / g to 10 J / g, and preferably 0 J / g, or 10 J / g or less, or 5 J / g or less.

[0082] In certain embodiments, the copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a dimensionless Konig B value of greater than 0.90 for copolymers having a molar ratio of polyester:polycarbonate structural units in the copolymer, or a molar ratio of polyester:(polycarbonate + polyether) structural units in the copolymer, of 65:35 to 85:15. Within the recited range of molar ratios, the copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a dimensionless Konig B value of 0.8, 0.9, 1.0, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, or 2.0. Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range, or can be used in combination to describe a limited range. For example, the B value may be greater than 1.0, or may be between 0.9 and 2.0, or between 1.0 and 2.0, or between 1.1 and 1.7.

[0083] In certain embodiments, the copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a B[X] value or B[X+X'] greater than 0.20, where B is the Konig B value for randomness of the copolymer, [X] is the mole fraction of comonomer polycarbonate and / or polyether structural units in the copolymer, and [X+X'] is the mole fraction of comonomer polycarbonate and / or polyether structural units in the copolymer, including any units containing residue fragments thereof. The copolyester, copolyester polycarbonate, or copolyester polyether copolymer has a B[X] or B[X+X'] value (dimensionless) of 0.18, 0.20, 0.22, 0.24, 0.26, 0.28, 0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70, 0.75, or 0.80. Each of the foregoing numbers can be preceded by the words "about," "at least about," or "less than about," and any of the foregoing numbers can be used alone to describe an open-ended range or in combination to describe a limited range. For example, the B[X] or B[X+X'] value may be greater than 0.22, or may be 0.18 to 0.80, or 0.20 to 0.75, or 0.22 to 0.75, or 0.25 to 0.70.

[0084] The present invention relates to copolyester polymers prepared from one or more virgin or recycled polyesters, such as PET and / or PETG, and one or more virgin or recycled polycarbonate polymers, such as bisphenol A, where the resulting copolyesters have several surprising attributes. For example, foamable polyester (e.g., PET)-based copolymers have a foaming density of 0.1 g / cm. 3 This is in stark contrast to other current technologies or commercial products based on PET (virgin or recycled), allowing these starting materials, particularly PET, to be used in a variety of product areas and applications (discussed below) that were previously unavailable to PET or PETG (virgin or recycled).

[0085] Due to its chemical structure, PET is less flammable than polystyrene (the primary polymer used in thermoplastic insulation foams). Therefore, foams based on the amorphous form of polyester, either virgin or recycled, derived from PET / PC or PETG / PC, are less flammable and do not require additional flame retardants to meet U.S. Limiting Oxygen Index (LOI) requirements. The flame retardant performance of such foams is sufficient to pass building and construction code requirements without the need for flame retardant additives in the foam formulation. Furthermore, it is expected that they will be able to pass the German B2 test without the need for flame retardant additives. Even in the case of more stringent building codes, using PET as the base resin for the copolyester polymer in the insulation foam eliminates the need for halogenated flame retardants, and in certain cases, non-halogenated flame retardants can be added instead to meet stringent building codes.

[0086] The copolyesters of the present invention have increased blowing agent solubility (for many blowing agents, including CO, 1-chloro-3,3,3-trifluoropropene (HFO 1233zd), cyclopentane, acetone, and methanol) allowing a wide range of extrusion or expansion processes to be used to produce foamed articles.

[0087] The products of the present invention can be used in multiple fields and applications, such as, but not limited to, as packaging materials or construction materials, such as, for example, building insulation or air sealant applications, cushion packaging, 3D printing, thermoforming, and many others.

[0088] Some embodiments disclosed herein are described in the following clauses, and any combination of these clauses (or portions thereof) may be taken to define an embodiment.

[0089] Clause 1: Copolyester, copolyester polycarbonate or copolyester polyether copolymers comprising different polyester units, or comprising polyester units and polycarbonate or polyether units or both, and optionally further comprising one or more binders; and (i) polymerized units of one or more aromatic diacid monomers; (ii) 10 mol % to 40 mol % of the sum of polymerized units of one or more aliphatic diols (mol % is the sum of the moles of polymerized units of one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized units comprising the copolymer); (iii) a primary Tg between 85°C and 125°C measured from the second heat inflection point of the DSC curve using a heating / cooling rate of 10°C / min; and (iv) a heat of fusion ΔH of less than 10 J / g after exposure to a hydrostatic pressure of 1000 psi CO2 at 135°C for 4 hours m A copolyester, copolyester polycarbonate or copolyester polyether copolymer characterized by having a peak.

[0090] Clause 2: The copolyester, copolyester polycarbonate, or copolyester polyether copolymer of Clause 1 having a B[X] or B[X+X'] value of 0.20 or greater, where B is the Konig B value for randomness of the copolymer, [X] is the mole fraction of comonomer polyester structural units, or the mole fraction of comonomer polycarbonate and / or polyether structural units, and [X+X'] is the mole fraction of comonomer polyester structural units, or the mole fraction of comonomer polycarbonate and / or polyether structural units, in the copolymer, including any units containing residue fragments thereof. In one embodiment, the copolymer has a B[X] or B[X+X'] value greater than 0.22.

[0091] Clause 3: The copolyester, copolyesterpolycarbonate or copolyesterpolyether copolymer of clause 1, having a Konig B value of greater than 0.90 for copolymers having a ratio of polyester:polycarbonate structural units in the copolymer, or polyester:(polycarbonate+polyether) structural units in the copolymer, in a molar ratio of 65:35 to 85:15.

[0092] Clause 4: The copolyester, copolyester polycarbonate, or copolyester polyether copolymer of any one of clauses 1 to 3, wherein the one or more aromatic diacid monomers are selected from phthalic acid, terephthalic acid, isophthalic acid, or 2,5-furandicarboxylic acid.

[0093] Clause 5: The copolyester, copolyester polycarbonate, or copolyester polyether, or copolymer of any one of clauses 1 to 4, further comprising one or more binders. In one embodiment, the one or more binders is pyromellitic dianhydride.

[0094] Clause 6: The copolyester, copolyester polycarbonate or copolyester polyether or copolymer of any one of clauses 1 to 5, wherein at least a portion of the polyester units in the copolymer are derived from recycled polyethylene terephthalate.

[0095] Clause 7: The copolyester, copolyester polycarbonate, or copolyester polyether copolymer of any one of clauses 1 to 6, wherein the one or more diols are selected from ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, butylene glycol, cyclohexanedimethanol, isosorbide, and spiroglycol. In one embodiment, the one or more diols are ethylene glycol.

[0096] Item 8: A copolyester, copolyester polycarbonate, or copolyester polyether copolymer according to any one of items 1 to 7, wherein the copolyester, copolyester polycarbonate, or copolyester polyether contains at least 7 mol% of polymerized units of bisphenol A.

[0097] Clause 9: The copolyester, copolyester polycarbonate, or copolyester polyether copolymer of any one of clauses 1 to 8, wherein the molar ratio of polyester polymer structural units to the sum of polycarbonate polymer structural units and polyether polymer structural units is 40:60 to 85:15, or 50:50 to 80:20.

[0098] Clause 10: A foamable composition comprising the copolyester, copolyester polycarbonate, or copolyester polyether copolymer of any one of clauses 1-9 and one or more blowing agents.

[0099] Clause 11: The foamable composition of clause 10, wherein the blowing agent is selected from one or more pentane hydrocarbons, one or more hydrofluoroolefins, carbon dioxide, nitrogen, oxygen, water, alcohols, ketones, ethers, halogenated hydrocarbons, or olefins, or combinations thereof.

[0100] Clause 12: The foamable composition of clause 10, wherein the blowing agent is selected from one or more chemical blowing agents.

[0101] Clause 13: The foamable composition of any one of clauses 10-12, further comprising one or more of an immiscible polyolefin, a colorant, a pigment, a filler, a clay, a flame retardant, an infrared attenuator, a nucleating agent, a lubricant, an acid scavenger, an antistatic agent, or an antioxidant, or a combination thereof.

[0102] Clause 14: A solid expandable bead made from the composition of any one of clauses 10-13.

[0103] Clause 15: A foam or foamed article obtained from the composition of any one of clauses 10 to 13.

[0104] Article 16: A foam or foamed article made by (a) extrusion foaming of the foamable composition of any one of clauses 10 to 13, or (b) expansion of the solid foamable beads of clause 14.

[0105] Clause 17: The foam has a density of 0.01 to 0.1 g / cm 3 15. A foam or foamed article according to clause 15 or 16 having a density of

[0106] Article 18: (i) melting a blend of at least two polymers selected from a first polyester polymer, one or more other polymers selected from one or more polycarbonate polymers and one or more other polyester polymers, or combinations thereof, in the presence of a transesterification catalyst, and optionally, a chain linking agent; (ii) maintaining the temperature above 200°C and below 330°C for at least 3 minutes and up to 180 minutes, optionally with mixing; (iii) optionally collecting at least a portion of the ethylene carbonate produced; and (iv) cooling to form a solid copolymer.

[0107] Clause 19: The method of Clause 18, wherein the weight ratio of the first polyester polymer to the one or more other polymers is 40:60 to 85:15.

[0108] Clause 20: The method of clause 18, wherein the weight ratio of the sum of all polyester polymers to polycarbonate polymer is 40:60 to 85:15.

[0109] Clause 21: The method of any one of clauses 18 to 20, wherein reduced pressure is used to remove volatile species.

[0110] Clause 22: The method of any one of clauses 18-21, further comprising collecting at least a portion of the ethylene carbonate produced.

[0111] Clause 23: The method of any one of clauses 18 to 22, wherein the one or more polyester polymers is recycled polyethylene terephthalate.

[0112] Clause 24: The copolyester, copolyester polycarbonate, or copolyester polyether copolymer of any one of clauses 1 to 9 or 25, wherein at least a portion of the polyester structural units in the copolymer are derived from recycled polyethylene terephthalate.

[0113] Article 25: a) one or more aliphatic diols; b) one or more aromatic diacids; c) one or more aromatic diols; d) copolyesters, copolyester polycarbonates or copolyester polyether copolymers comprising polymerized structural units selected from one or more organic carbonates, The copolyester copolymer comprises polymerized structural units a+b, The copolyester polycarbonate copolymer comprises polymerized structural units a+b+c+d, Copolyester polyether copolymers comprise polymerized structural units a+b+c+optionally d, and further comprise ether functional groups in the polymer backbone; The aforementioned copolymers are i) the polymerized structural units (a) of one or more aliphatic diols are present in an amount of 15 mol % to 40 mol % in total, where mol % is the sum of the moles of polymerized structural units of one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized structural units a+b+c+d comprising the copolymer; ii) a primary Tg between 85°C and 125°C measured from the inflection point of the second heat of the DSC curve using a heating / cooling rate of 10°C / min; and iii) A heat of fusion ΔH of less than 10 J / g after exposure to 1000 psi CO2 hydrostatic pressure at 135°C for 4 hours m A copolyester, copolyester polycarbonate or copolyester polyether copolymer characterized by having a peak.

[0114] As described in the embodiments of clauses 1-24, similar embodiments exist for the copolyester, copolyester polycarbonate or copolyester polyether copolymer of clause 25.

[0115] The present invention is further defined in the following examples, in which all parts and percentages are by weight unless otherwise specified. It should be understood that these examples, while indicating preferred embodiments of the present invention, are given by way of illustration only and should not be construed as limiting in any way. From the foregoing discussion and these examples, one skilled in the art will be able to ascertain the essential characteristics of the present invention and will be able to make various changes and modifications to the present invention to adapt it to various uses and conditions without departing from the spirit and scope thereof. [Example]

[0116] Example 1 Haake blend process for melt transesterification. In this example, the bulk polymer resin was dried in either a forced-air convection oven or a vacuum oven, according to the manufacturer's recommendations. The moisture content was tested using an Omnimark Mark2 high-performance moisture meter and confirmed to be 0.005% or less. The bulk polymer resin and additives were then physically mixed together and slowly added to a Thermo-Scientific Haake melt rheometer preheated to at least 10°C above the highest peak softening temperature of the added components. The polymer resin addition was carried out at a relatively slow mixer speed (25-50 rpm). Once the resin was fully melted, catalyst and / or additional additives were added, and the mixer speed was then increased to 200 rpm, and blending continued at a time and temperature profile set according to the experimental conditions. All blending was carried out under a strong dry nitrogen sweep implemented at the mixer throat. Once the set blend melting and mixing conditions were achieved, the mixed / reacted materials were removed and placed in a Teflon pan, bagged, and stored in a dry box, where they were kept cool until testing or part assembly was to begin. Unless otherwise specified, all percentages are by weight and pph is "parts per hundred" of the total weight of the polymer.

[0117] Example 2 Extruder process for melt transesterification. Example 2a. Twin-Single Screw In-Line Extrusion System Continuous melt transesterification was carried out by feeding the material into a co-rotating twin-screw extruder (40 mm shaft diameter and length-to-diameter ratio, L / D = 45.5:1) at rates of 75-150 lb / h. The molten polymer mixture exiting the twin-screw extruder was fed directly into a side-feed single-screw extruder (90 mm shaft diameter, 30:1 L / D) and subsequently into an annealing tube / static mixer. The annealing section was 2.25 inches in diameter and 24 inches long, and the static mixer section was 12 inches long and contained four SMX static mixers, each 3 inches long. The extrudate was collected by underwater pelletization using a die face cutter. Pellets ranged in size from 3 to 5 mm in diameter (nominal spherical).

[0118] Example 2b. Twin-screw in-line extrusion system The transesterification reaction was carried out in a series twin-screw extrusion system consisting of a first co-rotating twin-screw extruder (TEX44αIII, manufactured by Japan Steel Works (JSW)) ("primary extruder") and a second co-rotating twin-screw extruder (TEX28V, also manufactured by JSW) ("secondary extruder"). Specifically, the 44αIII twin-screw extruder had 17 barrels with a shaft diameter of 47 mm and a shaft length-to-diameter ratio of L / D = 59.5, while the TEX28V twin-screw extruder had 12 barrels with a shaft diameter of 28 mm and an L / D ratio of 42. The transfer pipe connecting the TEX44αIII twin-screw extruder and the TEX28V twin-screw extruder had a diameter of 22 mm and a length of 1592.5 mm. The catalyst was blended with the polyester to obtain catalyst concentrates with concentrations ranging from 2.5 to 7 wt%. The polyesters were dried overnight in an oven and packaged in aluminum foil bags before extrusion for the transesterification reaction. Three weight-loss feeders were used to feed two polyesters / resins (e.g., PET and PC) and catalyst concentrate into the main feed throat of a TEX44αIII twin-screw extruder. All feeders and the main feed throat were purged with a continuous nitrogen flow. The TEX44αIII twin-screw extruder had three vent ports connected to a condensation system with two knockout pots and a vacuum pump. Similarly, the TEX28V twin-screw extruder had a rear vent and two wide vent ports connected to a condensation system with one multitrap pot and the other with a cooling coil and vacuum pump. A high vacuum (at least 28 inches Hg) was applied to the condensation system and extruder to remove volatiles generated by the transesterification reaction. The polymer melt exited a three-hole (4 mm diameter) strand die, was immediately quenched in a water bath, and then pelletized.

[0119] Example 3 NMR methods for determining decomposition and randomness factors. Each sample was weighed in an amount of 0.3 g and dissolved in 3.0 ml of deuterated chloroform (CDCl) with 5 mM chromium(III) acetylacetonate as a relaxation agent. Trifluoroacetic acid (TFA) (0.05–0.2 ml) was also added to aid in the dissolution of polymeric materials in the presence of high crystallinity. One-dimensional (1D) quantitative analysis was performed. 13 C NMR experiments were performed on a 600 MHz Bruker Avance III spectrometer equipped with a 10 mm cryogenic probe. 13 In C NMR spectroscopy, inverse-gated 1 A single-pulse technique with H decoupling was used, with a total repetition time of 10 seconds and an acquisition time of 1.7 seconds. The receiver gain was optimized, and 1024 scans were recorded to generate a spectral sensitivity suitable for quantitative analysis. The spectral width was set to 250 ppm, centered at 100 ppm.

[0120] Example 4 DSC method for quantifying crystallinity The samples were weighed and sealed in aluminum DSC pans. Sample weights were approximately 5–10 mg for each sample. Samples were scanned on a TA Instruments Q2000 DSC (differential scanning calorimeter) equipped with an autosampler, with a 50 ml / min nitrogen purge. The heating rate was 10°C / min, and a temperature profile between 20°C, 280°C, and a return to 20°C was applied twice to each sample. Scans were analyzed using Universal Analysis V4.7A software. The primary output parameters of the DSC test were the glass transition temperature and the temperature and enthalpy of melting and crystallization of the sample. Analysis of the samples before CO2 immersion was performed during the second temperature ramp. Analysis of the samples after exposure to 1000 psi CO2 hydrostatic pressure at 135°C for 4 hours was performed during the first temperature ramp. The glass transition temperature (Tg) was measured as the inflection point of the baseline process transition and is reported in degrees Celsius. The enthalpy of melting or crystallization is measured using a linear baseline estimation of the area of ​​the peak and is reported as J / g. Considering that the crystallization enthalpy of crystalline PET is 140 J / g, it can be estimated that a crystallization enthalpy of less than 10 J / g represents approximately 7% or less crystallinity, and a crystallization enthalpy of less than 5 J / g represents less than 4% crystallinity.

[0121] Example 5 Expandable Bead Extruder Process The transesterified copolyester is melt-blended with one or more physical blowing agents, such as n-pentane, cyclopentane, or 1-chloro-3,3,3-trifluoropropene (HFO 1233zd), at pressures (>1000 psi) using a single-screw extruder, which feeds a mixer into which the blowing agent is introduced. The polymer-blowing-agent blend is then cooled using additional mixing components (or heat exchangers) and then exits through a multi-hole die with the desired diameter to produce cylindrical pellets (or spherical beads) ranging from 0.5 to 1 mm in diameter. The beads can be quenched with water or air.

[0122] Example 6 GPC method Samples were prepared by adding approximately 0.04 g of polymer to 20 mL of chloroform at ambient temperature and placing the solution on a low-tap mechanical shaker overnight. Prior to injection, the solution was filtered through a 0.2 μm PTFE syringe filter. Using a Waters 2690 pump / autosampler set at 1 mL / min with continuous vacuum degassing, 50 microliters of solution was injected onto two Agilent Technology PL gel-mixed C columns (7.5 mm internal diameter, 300 mm length, 5 micron particle size) and held at 40°C. Molecular weight measurements were performed using a Shodex RI-501EX differential refractive index detector set at 40°C. Agilent Laboratories narrow MWD PS standards were used for calibration over the molecular weight range of 3,740–580,000 g / mol. Data were acquired and reduced using Agilent Technology Cirrus SEC / GPC software version 3.3. Air was used.

[0123] Example 7 Foaming evaluation method To evaluate the foaming properties of the comparative and inventive examples, the samples were compression molded into 1.3 mm thick films (25 tons of pressure at 180°C for 5 minutes). A portion of the pressed film (approximately 7 mm x 7 mm in area) was placed in a pressure vessel preheated to 125°C. The vessel was then pressurized to 1000 psi using carbon dioxide, and the sample was immersed for 3-4 hours to allow the gas to dissolve into the polymer. The pressure was then rapidly released to induce foaming in the sample. Successful foaming was determined by visually observing void formation in the polymer sample and a corresponding increase in sample volume of at least 50%.

[0124] Example 8 In this example, copolyester-polycarbonate polymers (PC / PET) were prepared by catalytic transesterification starting with the constituent polyester (PET) and polycarbonate (bisphenol A). To define the range of PC / PET copolyester copolymer compositions and the range of ethylene glycol units encompassed by this invention, a series of blends were produced with increasing levels of PET in the formulation, from which copolyesters were produced by catalytic transesterification. In the table below, B[X] is B[X+X'] (meaning it includes the residue fragment of X). CO2 loss (mol %) is the mole % of total PC monomer units that lost CO2 during the reaction.

[0125] In Table 1, and in the tables that follow, the last column (labeled "Batch Foam CO2") shows foamability screening tests performed on compression molded thick films of the product, where small scale samples of the modified polyester are available (see "Foamability Evaluation Method" above).

[0126] [Table 1]

[0127] Based on the findings of this series, foamable copolyester products may contain up to 40 mole percent ethylene glycol (EG) structural units. A copolyester containing 41 mole percent EG structural units (Example 1) failed to produce foam under the foaming test conditions. Note that the EG structural unit content is defined as the mole percent of EG structural units expressed as a percentage of the sum of all structural units in the backbone (in this case, there are four structural units total, two from each starting polymer, PET and PC), and is calculated taking into account any loss of EG. All Tg values ​​are given in degrees Celsius, measured by the inflection point method (described above).

[0128] Because PET is relatively inexpensive and recycled PET is cheap and abundant, it is desirable to maximize the PET level in the foamable copolymer. In this example, Example 1, an 80 / 20 weight ratio of starting polymer (80 wt. % PET) was not able to foam (higher ΔH after foaming). m showed significant crystallinity, approximately 14% crystallinity, reflecting significant blockiness due to the length of consecutive repeat units in the PET structural bimolecules. Because both samples with a starting weight ratio of 75 / 25 (75 wt% PET) were successfully foamed, some further investigation focused on the starting 75 / 25 weight ratio. All successfully foamed samples had a post-foam ΔH of less than 10 J / g. m had.

[0129] Example 9 In this example, the transesterification reaction (for a 75 / 25 by weight PET / PC blend) was stopped at various reaction times. The degree of blockiness of the copolymer was determined by the method described herein. 13 The König B values ​​for the monomer distribution in the polymer chains were evaluated as determined by C NMR (see Table 2, and also Figure 1).

[0130] [Table 2]

[0131] Based on the series of reactions shown in Table 2, a B value greater than 0.90 is required to sufficiently randomize the original PET repeat units to avoid crystallization during exposure to hydrostatic CO2 pressure. Therefore, polymers with a B value of 0.90 or greater are considered suitable for foaming. All four copolyester copolymer products that are unable to produce stable foams have a ΔH greater than 16 J / g. m (after CO2 exposure), while the two copolyester copolymer products that successfully produced stable foams both had a ΔH of 8.3 J / g or less. m (after CO2 exposure).

[0132] Example 10 In this example, various catalysts promoting transesterification with PET were explored and demonstrated, resulting in various blockiness and final Tg values. The resulting copolyesters were investigated for their ability to produce stable foams under the test conditions described herein (Table 3).

[0133] [Table 3]

[0134] Preferred catalysts produce B values ​​greater than 0.90. More preferred are catalysts that promote EG loss, resulting in higher Tg. Even more preferred are catalysts that promote EG loss with less than 50% CO loss, as evidenced by Samples 11 and 13.

[0135] Example 11 The use of recycled raw materials in formulations inherently introduces small amounts of ternary or quaternary blends due to contamination with other recycled polymers. In this example, small amounts of typical recycled contaminants (at typical contaminant levels, e.g., 0.05 wt. % or 0.15 wt. %) were intentionally added to the reactant blend mixture prior to the catalytic transesterification reaction. The effect of the contaminants on foaming performance was evaluated as described above (Table 4, reaction conditions indicated in the footnotes).

[0136] [Table 4]

[0137] Examples 14-21 (Table 4) demonstrate that small amounts of a third polymer (different from the first two) do not significantly affect the ability of the copolyester to produce stable foams, and that such small amounts of contaminant copolymers are within the scope of the present invention. In all cases, the blends performed similarly to their control examples (Example 11) that did not contain any additives.

[0138] Example 12 In the following samples, the ability to form foamable copolyester copolymers was extended to include terpolymers. Table 5 shows the results for PET / PETG / PC terpolymers, demonstrating that several PET / PETG / PC terpolymer compositions are capable of producing stable foams. (PETG is glycol-modified polyethylene terephthalate.)

[0139] [Table 5]

[0140] Example 13 Table 6 shows the results for PET / PBT / PC ternary copolymers, demonstrating that some PET / PBT / PC ternary copolymer compositions can produce stable foams. (PBT is polybutylene terephthalate.)

[0141] [Table 6]

[0142] Example 14 In this example, Table 7 shows the results for PET / PTF / PC ternary copolymers, demonstrating that some PET / PTF / PC ternary copolymer compositions can produce stable foams. (PTF is polytrimethylene furanoate.)

[0143] [Table 7]

[0144] Example 15 In this example, Table 8 shows the results of ternary copolymers obtained from the transesterification of ternary blends using PET, PC, and Tritan® FX200, demonstrating that some of these ternary copolymer compositions can produce stable foams. (Tritan® FX200 is polyethylene terephthalate modified with 2,2,4,4-tetramethyl-1,3-cyclobutanediol (CBDO), resulting in a copolyester containing a mixture of polymerized units of the diols: ethylene glycol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol.)

[0145] [Table 8]

[0146] Any ternary blend is considered within the scope of the present invention, including partial or complete replacement of the ethylene glycol repeat units (from the PET component) with other repeat units such as butylene glycol (from PBT), cyclohexanedimethanol (from PETG), or cyclobutanediol (from Tritan). All of these ternary blends were able to produce copolyester copolymer compositions that were foamable within the conditions of the foaming test described herein.

[0147] While preferred forms of the invention have been disclosed, it will be apparent to those skilled in the art that various changes and modifications can be made which achieve several advantages of the invention without departing from the spirit and scope of the invention. The scope of the invention should therefore be determined solely by the appended claims.

[0148] When ranges are used herein for physical properties, such as temperature ranges and pressure ranges, or chemical properties, such as chemical formulas, all combinations and sub-combinations of specific embodiments of the ranges within the ranges are intended to be included.

[0149] The disclosures of each patent, patent application, and publication cited or described in this document are incorporated herein by reference in their entirety.

[0150] Those skilled in the art will appreciate that many changes and modifications to the preferred embodiments of the present invention may be made and that such changes and modifications may be made without departing from the spirit of the present invention. It is, therefore, intended by the appended claims to cover all such equivalent variations as fall within the true spirit and scope of the present invention. The embodiments of the present invention are listed below. [Aspect 1] Copolyester, copolyester polycarbonate or copolyester polyether copolymers comprising different polyester units or comprising polyester units and polycarbonate or polyether units or both, and optionally further comprising one or more binders; and polymerized units of one or more aromatic diacid monomers; 10 mol % to 40 mol % of the total of polymerized units of one or more aliphatic diols, said mol % being the total of moles of polymerized units of the one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized units comprising the copolymer; a primary Tg between 85°C and 125°C measured from the inflection point of the second heat of the DSC curve using a heating / cooling rate of 10°C / min; and 135°C for 4 hours, 1000 psi CO 2 Heat of fusion ΔH of less than 10 J / g after exposure to hydrostatic pressure of m A copolyester, copolyester polycarbonate or copolyester polyether copolymer characterized by having a peak. [Aspect 2] 2. The copolyester, copolyester polycarbonate or copolyester polyether copolymer of claim 1 having a B[X] or B[X+X'] value of greater than 0.20, where B is the Konig B value for randomness of the copolymer, [X] is the mole fraction of comonomer polyester structural units or the mole fraction of comonomer polycarbonate and / or polyether structural units, and [X+X'] is the mole fraction of comonomer polyester structural units or the mole fraction of comonomer polycarbonate and / or polyether structural units in the copolymer, including any units containing residue fragments thereof. [Aspect 3] 2. The copolyester, copolyester polycarbonate or copolyester polyether copolymer according to claim 1, having a Konig B value of greater than 0.90 for copolymers having a ratio of polyester:polycarbonate structural units in the copolymer, or polyester:(polycarbonate + polyether) structural units in the copolymer, in a molar ratio of 65:35 to 85:15. [Aspect 4] 2. The copolyester, copolyester polycarbonate, or copolyester polyether copolymer of claim 1, wherein the one or more aromatic diacid monomers are selected from phthalic acid, terephthalic acid, isophthalic acid, or 2,5-furandicarboxylic acid. [Aspect 5] 2. The copolyester, copolyester polycarbonate or copolyester polyether or copolymer according to claim 1, wherein at least a portion of the polyester units in the copolymer are derived from recycled polyethylene terephthalate. [Aspect 6] 2. The copolyester, copolyester polycarbonate, or copolyester polyether copolymer according to claim 1, wherein the copolyester, copolyester polycarbonate, or copolyester polyether contains at least 7 mol % of polymerized units of bisphenol A. [Aspect 7] 2. The copolyester, copolyester polycarbonate, or copolyester polyether copolymer according to claim 1, wherein the molar ratio of polyester polymer structural units to the sum of polycarbonate polymer structural units and polyether polymer structural units is 40:60 to 85:15. [Aspect 8] 10. A foamable composition comprising the copolyester, copolyester polycarbonate, or copolyester polyether copolymer of claim 1 and one or more blowing agents, and optionally further comprising an immiscible polyolefin, a colorant, a filler, a flame retardant, an infrared attenuator, a nucleating agent, a lubricant, an antistatic agent, or an antioxidant, or a combination thereof. [Aspect 9] A foam or foamed article obtainable from the composition of claim 8. [Aspect 10] The foam has a density of 0.01 to 0.1 g / cm 3 10. The foam or foamed article of claim 9, having a density of [Aspect 11] (i) melting a blend of at least two polymers selected from a first polyester polymer, one or more other polymers selected from one or more polycarbonate polymers and one or more other polyester polymers, or combinations thereof, in the presence of a transesterification catalyst, and optionally, a chain linking agent; (ii) maintaining the temperature above 200°C and below 330°C for at least 3 minutes and up to 180 minutes, optionally with mixing; (iii) optionally collecting at least a portion of the ethylene carbonate produced; and (iv) cooling to form a solid copolymer. [Aspect 12] 12. The method of claim 11, wherein the weight ratio of the first polyester polymer to the one or more other polymers is 40:60 to 85:15. [Aspect 13] 12. The method of claim 11, wherein the weight ratio of the total of all polyester polymers to polycarbonate polymer is 40:60 to 85:15. [Aspect 14] 12. The method of claim 11, wherein the one or more polyester polymers is recycled polyethylene terephthalate. [Aspect 15] a) one or more aliphatic diols; b) one or more aromatic diacids; c) one or more aromatic diols; d) copolyesters, copolyester polycarbonates or copolyester polyether copolymers comprising polymerized structural units selected from one or more organic carbonates, The copolyester copolymer comprises polymerized structural units a+b, The copolyester polycarbonate copolymer comprises polymerized structural units a+b+c+d, the copolyester polyether copolymer comprises polymerized structural units a+b+c+optionally d and further comprises ether functional groups in its polymer backbone; The copolymer is i) the polymerized structural units (a) of one or more aliphatic diols are present in an amount of 15 mol % to 40 mol % in total, said mol % being the sum of the moles of polymerized structural units of the one or more aliphatic diols in the copolymer expressed as a percentage of the total moles of polymerized structural units a+b+c+d comprising the copolymer; ii) a primary Tg between 85°C and 125°C measured from the inflection point of the second heat of the DSC curve using a heating / cooling rate of 10°C / min; and iii) 135°C for 4 hours at 1000 psi CO 2 Heat of fusion ΔH of less than 10 J / g after exposure to hydrostatic pressure of m A copolyester, copolyester polycarbonate or copolyester polyether copolymer characterized by having a peak.

Claims

1. a copolyester-polycarbonate copolymer comprising polyester units and polycarbonate units, and optionally further comprising one or more binders; polymerized units of one or more aromatic diacid monomers; 10 mol % to 40 mol % of the sum of polymerized units of one or more aliphatic diols, said mol % being the sum of moles of polymerized units of said one or more aliphatic diols in said copolymer expressed as a percentage of the total moles of polymerized units comprising said copolymer; a primary Tg of 85°C to 125°C measured from the inflection point of the second heat of the DSC curve using a heating / cooling rate of 10°C / min; and 135°C for 4 hours, 1000 psi CO ２ A heat of fusion ΔH of 10 J / g or less after exposure to a hydrostatic pressure of ｍ It has a peak, and A copolyester polycarbonate copolymer characterized by having a B[X] or B[X+X'] value greater than 0.20: where B is the Konig B value for randomness of the copolymer, [X] is the mole fraction of comonomer polyester structural units or the mole fraction of comonomer polycarbonate structural units, and [X+X'] is the mole fraction of comonomer polyester structural units or the mole fraction of comonomer polycarbonate structural units in the copolymer, including any units containing a residue fragment of X, and the molar ratio of polyester:polycarbonate structural units in the copolymer is from 65:35 to 85:

15.

2. 10. The copolyester polycarbonate copolymer of claim 1, wherein at least a portion of the polyester units in the copolymer are derived from recycled polyethylene terephthalate.

3. 10. A foamable composition comprising the copolyester polycarbonate copolymer of claim 1 and one or more blowing agents, and optionally further comprising an immiscible polyolefin, a colorant, a filler, a flame retardant, an infrared attenuator, a nucleating agent, a lubricant, an antistatic agent, or an antioxidant, or a combination thereof.

4. A foam or foamed article obtainable from the composition of claim 3.

5. The foam has a density of 0.01 to 0.1 g / cm ３ 5. The foam or foamed article of claim 4 having a density of

6. (i) melting a blend of at least two polymers selected from a first polyester polymer and one or more polycarbonate polymers in the presence of a transesterification catalyst, and optionally, a chain linking agent; (ii) maintaining the temperature above 200°C and below 330°C for at least 3 minutes and up to 180 minutes, optionally with mixing; (iii) optionally collecting at least a portion of the ethylene carbonate produced; and (iv) cooling to form a solid copolymer.

7. a) one or more aliphatic diols; b) one or more aromatic diacids; c) one or more aromatic diols; d) a copolyester polycarbonate copolymer comprising polymerized structural units selected from one or more organic carbonates, The copolyester polycarbonate copolymer comprises polymerized structural units a+b+c+d, The copolymer is i) the polymerized structural units (a) of one or more aliphatic diols are present in a total amount of 15 mol % to 40 mol %, said mol % being the sum of the moles of polymerized structural units of said one or more aliphatic diols in said copolymer expressed as a percentage of the total moles of polymerized structural units a+b+c+d comprising said copolymer; ii) a primary Tg of 85°C to 125°C measured from the inflection point of the second heat of the DSC curve using a heating / cooling rate of 10°C / min; and iii) 135°C for 4 hours, 1000 psi CO ２ A heat of fusion ΔH of 10 J / g or less after exposure to a hydrostatic pressure of ｍ It has a peak, and A copolyester polycarbonate copolymer characterized by having a B[X] or B[X+X'] value greater than 0.20: where B is the Konig B value for randomness of the copolymer, [X] is the mole fraction of comonomer polyester structural units or the mole fraction of comonomer polycarbonate structural units, and [X+X'] is the mole fraction of comonomer polyester structural units or the mole fraction of comonomer polycarbonate structural units in the copolymer, including any units containing a residue fragment of X, and the molar ratio of polyester:polycarbonate structural units in the copolymer is from 65:35 to 85:15.

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