Molded articles for use with terpene-containing oils

Abstract

A shaped article comprising a molded component configured to receive a terpene-containing oil composition, the molded component formed from a copolyester composition having high chemical resistance to terpene oils and a Tg of at least 95°C.

Description

Technical Field

[0001] This invention belongs to the field of polymer-based resins, which can be used to form articles or components thereof intended to come into contact with terpene-containing oils. Plastic articles made using these compositions or components for such articles are also provided, such as vaporizers, sprayers, humidifiers, air purifiers, or handheld steam delivery devices or components thereof. Background Technology

[0002] Plastics are a preferred material for manufacturing small devices that can be based on the relative efficiency of molding parts and articles of various shapes and designs for conveying vapors or suspensions of chemical compositions. For example, devices for conveying / generating vapors or suspensions, such as vaporizers, sprayers, humidifiers, air purifiers, or handheld vapor delivery devices, are typically manufactured by molding plastic parts that form assemblies to produce the device.

[0003] However, when plastics are used in applications involving contact with chemicals, there is a possibility of cracking, fissures, softening, and other damage caused by the chemical environment. One particularly corrosive type of chemical is terpene-containing oils, such as those used in condiments and flavorings. Many plastics are adversely affected by these chemicals. Therefore, there is a need for plastic materials that are resistant to such chemicals, readily form articles, and maintain acceptable physical properties.

[0004] It would be beneficial to be able to provide melt-processable polymer-based resins and articles made from such compositions that do not have this disadvantage. Summary of the Invention

[0005] Surprisingly, articles molded from certain copolyester plastics have been found to exhibit excellent resistance to terpene-containing oils while retaining sufficient physical properties required for their intended use. In examples, such articles can be used as containers and / or other components in vapor conveying devices that will come into significant contact with terpene-containing oils during use. In one aspect, articles configured to receive terpene-containing oil compositions can be made from copolyester compositions that can be prepared to have excellent chemical resistance to terpene-containing oil compositions and a glass transition temperature (Tg) exceeding 95°C or 100°C.

[0006] It has been found that molded articles configured to receive terpene-containing oil compositions can be prepared from copolyester plastic materials that exhibit resistance to terpene-containing oils and possess physical properties similar to or superior to those of molded articles produced from other commonly used oil-based engineering thermoplastics. More specifically, these molded articles are produced from copolyester compositions that retain their physical properties better than other plastics after exposure to terpene-containing oils.

[0007] In one aspect of the invention, the present invention relates to a molded article configured to receive a terpene-containing oil composition and comprising a copolyester composition, wherein the copolyester composition has a Tg of at least 95°C or at least 100°C and has at least one property selected from the group consisting of: a tensile modulus greater than 1400 MPa, measured according to ASTM D638 using 3.2 mm thick rods subjected to 50% relative humidity for 40 hours at 23°C; a cantilever beam notched impact strength greater than 1000 J / m, measured according to ASTM D256 using 3.2 mm thick rods subjected to 50% relative humidity for 40 hours at 23°C; a yield tensile stress of at least 40 MPa, measured according to ASTM D638; a transmittance of at least 70, measured according to ASTM D1003 using 3.2 mm thick plates after injection molding at a barrel setpoint of 249°C and a mold temperature of 80°C; or an L* color of at least 85, measured according to ASTM D1003. E1348 was measured using a 3.2 mm sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C. In the examples, the copolyester composition has at least two or at least three of the listed properties.

[0008] In embodiments of the present invention, the molded article or its components may be selected from injection molded articles, extruded articles, rotationally molded articles, compression molded articles, blow molded articles, injection blow molded articles, injection stretch blow molded articles, extruded blow molded articles, sheet or film extruded articles, profile extruded articles, gas-assisted molding articles, structural foam molding articles, or thermoformed articles.

[0009] In embodiments of the invention, the molded article is selected from opaque articles, transparent articles, transparent articles, thin-walled articles, technical articles (e.g., articles with complex designs), articles with high design specifications, complex design articles, containers for containing terpene-containing oil compositions, or other molded articles configured to receive (or contact) terpene-containing oil compositions.

[0010] In the embodiments, technical articles, articles with high design specifications, and articles with complex designs may be selected from articles including electrical / electronic components, perfume or cosmetic containers, vapor delivery devices, or components thereof.

[0011] In one embodiment of the injection-molded article, the copolyester composition further includes at least one property selected from the following: a tensile modulus greater than 1400 MPa, measured according to ASTM D638 using 3.2 mm thick rods subjected to 50% relative humidity at 23°C for 40 hours; a cantilever beam notched impact strength greater than 1000 J / m, measured according to ASTM D256 using 3.2 mm thick rods subjected to 50% relative humidity at 23°C for 40 hours; a yield tensile stress of at least 40 MPa, measured according to ASTM D638; a transmittance of at least 70, measured according to ASTM D1003 using 3.2 mm sheets after injection molding at a barrel set point of 249°C and a mold temperature of 80°C; a ΔE value less than 25, using 3.2 mm sheets after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C; or an L* color of at least 85, as per ASTM D1003. E1348 was measured using a 3.2 mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C. In the embodiments, the polymer-based resin contains at least two or at least three of the listed properties.

[0012] In embodiments according to various aspects of the invention disclosed herein, the copolyester composition comprises at least one copolyester, said copolyester comprising:

[0013] (a) A dicarboxylic acid component, comprising:

[0014] i) 70 mol%-100 mol% of terephthalic acid residues;

[0015] (b) A diol component comprising:

[0016] i) 5 mol%–15 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0017] ii) 85 mol%–95 mol% of 1,4-cyclohexanediethanol residues,

[0018] The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; and the specific logarithmic viscosity is 0.60 to 1.2 dL / g, determined at 25°C in 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane; and the Tg of the polyester is 95°C to 115°C.

[0019] In embodiments according to various aspects of the invention disclosed herein, the copolyester composition comprises at least one copolyester, said copolyester comprising:

[0020] (a) A dicarboxylic acid component, comprising:

[0021] i) 70 mol%-100 mol% of terephthalic acid residues;

[0022] (b) A diol component comprising:

[0023] i) 5 mol%–15 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0024] ii) 85 mol%–95 mol% of 1,4-cyclohexanediethanol residues,

[0025] The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; and the specific logarithmic viscosity is 0.60 to 1.0 dL / g, determined at 25°C in 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane; and the Tg of the polyester is 95°C to 115°C.

[0026] In the embodiments, the dicarboxylic acid component comprises:

[0027] i) 95 mol%–100 mol% of terephthalic acid (TPA) residues; and

[0028] ii) 0 mol%-5 mol% of isophthalic acid (IPA) residues.

[0029] In the embodiments, the dicarboxylic acid component comprises the following residues: greater than 95 mol%-100 mol% TPA and 0 mol%-less than 5 mol% IPA; 96 mol%-100 mol% TPA and 0 mol%-4 mol% IPA; 96.5 mol%-100 mol% TPA and 0 mol%-3.5 mol% IPA; 97 mol%-100 mol% TPA and 0 mol%-3 mol% IPA; 98 mol%-100 mol% TPA and 0 mol%-2 mol% IPA; 98.5 mol%-100 mol% TPA and 0 mol%-1.5 mol% IPA; 95 mol%-98.5 mol% TPA and 1.5 mol%-5 mol% IPA; greater than 95 mol%-98.5 mol% TPA and 1.5 mol%-less than 5 mol% IPA; 96 mol%-97 mol%-100 mol% TPA and 0 mol%-3 mol% IPA; 98 mol%-100 mol% TPA and 0 mol%-2 mol% IPA; 98.5 mol%-100 mol% TPA and 0 mol%-1.5 mol% IPA; ... 8.5 mol% TPA and 1.5 mol%-4 mol% IPA; 96.5 mol%-98.5 mol% TPA and 1.5 mol%-3.5 mol% IPA; 97 mol%-98.5 mol% TPA and 1.5 mol%-3 mol% IPA; 97.5 mol%-98.5 mol% TPA and 1.5 mol%-2.5 mol% IPA; 95 mol%-98 mol% TPA and 2 mol%-5 mol% IPA; greater than 95 mol%-98 mol% TPA and 2 mol%-less than 5 mol% IPA; 96 mol%-98 mol% TPA and 2 mol%-4 mol% IPA; 96.5 mol%-98 mol% TPA and 2 mol%-3.5 mol% IPA; or 97 mol%-98 mol% TPA and 2 mol%-3 mol% IPA.

[0030] In the embodiments, the diol component comprises:

[0031] i) 7 mol%–15 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol (TMCD) residues; and

[0032] ii) 85 mol%-93 mol% of 1,4-cyclohexanediethanol (CHDM) residues.

[0033] In the examples, the diol component comprises the following residues: 8 mol%-15 mol% TMCD and 85 mol%-92 mol% CHDM; 8 mol%-14 mol% TMCD and 86 mol%-92 mol% CHDM; 8 mol%-13 mol% TMCD and 87 mol%-92 mol% CHDM; 8 mol%-12 mol% TMCD and 88 mol%-92 mol% CHDM; 9 mol%-15 mol% TMCD and 85 mol%-91 mol% CHDM; 9 mol%-14 mol% TMCD and 86 mol%-91 mol% CHDM; 9 mol%-13 mol% TMCD and 87 mol%-91 mol% CHDM; 9 mol%-12 mol% TMCD and 88 mol%-91 mol% CHDM; 10 mol%-15 mol% TMCD and 85 mol%-90 mol% CHDM; 10 mol%-14 mol% TMCD and 86 mol%-90 mol% CHDM; 10 mol%-13 mol% TMCD and 87 mol%-90 mol% CHDM; or 10 mol%-12 mol% TMCD and 88 mol%-90 mol% CHDM.

[0034] In the embodiments, the copolyester composition comprises at least one copolyester, said copolyester comprising:

[0035] (a) A dicarboxylic acid component, comprising:

[0036] i) 98 mol%-100 mol%, or 100 mol% of terephthalic acid residues;

[0037] (b) A diol component comprising:

[0038] i) 10 mol%–14 mol%, or 11 mol%–13 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0039] ii) 88 mol%-90 mol%, or 87 mol%-89 mol% of 1,4-cyclohexanediethanol residues.

[0040] The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; and the specific logarithmic viscosity is 0.70 to 1.0 dL / g, or 0.75 to 0.95 dL / g, determined at 25°C in 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane; and the Tg of the polyester is 100°C to 115°C.

[0041] In the embodiments, the copolyester composition comprises at least one copolyester, said copolyester comprising:

[0042] (a) A dicarboxylic acid component, comprising:

[0043] i) 97.1 mol%–98.5 mol%, or 97.3 mol%–98.3 mol% of terephthalic acid residues; and

[0044] ii) 1.5 mol%–2.9 mol%, or 1.7 mol%–2.7 mol% of isophthalic acid residues;

[0045] (b) A diol component comprising:

[0046] i) 10 mol%–12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0047] ii) 88 mol%-90 mol% of 1,4-cyclohexanediethanol residues,

[0048] The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; and the specific logarithmic viscosity is 0.70 to 1.0 dL / g, or 0.75 to 0.95 dL / g, determined at 25°C in a 0.5 g / 100 ml concentration of 60 / 40 (wt / wt) phenol / tetrachloroethane; and the Tg of the polyester is 100°C to 115°C. In an example, the at least one copolyester is a melt-blended copolyester with an IV of 0.70 to 0.90 dL / g, or 0.75 to 0.85 dL / g, or 0.79 to 0.82 dL / g. In an example, the melt-blended copolyester is solid to increase the IV. In the examples, the IV of the solid copolyester is 0.80 to 1.0 dL / g, or 0.85 to 1.0 dL / g, or 0.87 to 0.97 dL / g, or 0.90 to 0.95 dL / g.

[0049] In the embodiments, the copolyester composition is amorphous. In other embodiments, the copolyester composition is semi-crystalline.

[0050] In an embodiment, the at least one copolyester is a reactor-grade polyester prepared by a transesterification reaction comprising a reaction mixture including all monomers for the desired (monomer) residues to be included in the copolyester. For example, a copolyester intended to include residues of TPA, CHDM, and TMCD is prepared by a transesterification reaction comprising each of these monomers. In one embodiment, the reactor-grade polyester is amorphous.

[0051] In embodiments, the at least one copolyester is a melt-blended polyester prepared by a method comprising: melt-blending at least two different starting polyesters to provide a final copolyester comprising monomer residues contained in the starting polyesters. For example, a PCTA copolyester containing TPA, IPA, and CHDM residues is melt-blended with a PCTM copolyester containing TPA, CHDM, and TMCD residues to provide a final copolyester having TPA, IPA, CHDM, and TMCD residues. In embodiments, the melt-blended copolyester has a (net) amount of residues according to any embodiment of the copolyester as described herein.

[0052] In embodiments, the melt-blended copolyester undergoes solidification to increase the copolyester's intrinsic viscosity (IV). In embodiments, the solidified copolyester has an IV according to any embodiment of the copolyester (as described herein).

[0053] In an embodiment, a system for vapor-transferring a terpene-containing oil composition is provided, comprising a molded article configured to receive the terpene-containing oil composition and the terpene-containing oil composition, wherein the molded article includes one or more surfaces that contact the terpene-containing oil composition and / or are configured to contact the terpene-containing oil composition when the system is used for its intended purpose, and wherein the one or more surfaces are formed of a copolyester composition (as described herein). In an embodiment, the majority of the surfaces that contact the terpene-containing oil composition and / or are configured to contact the terpene-containing oil composition when the system is used for its intended purpose are formed of a copolyester composition.

[0054] In one embodiment, the terpene-containing oil composition is in liquid and / or vapor form. In another embodiment, the system includes a molded article comprising one or more liquid contact surfaces that contact the liquid terpene-containing oil composition and one or more vapor contact surfaces configured to contact the vaporized terpene-containing oil composition when the system is used for its intended purpose. In one embodiment, the one or more liquid contact surfaces and the one or more vapor contact surfaces are in fluid communication, and the vaporized terpene-containing oil composition is prepared by evaporating the liquid terpene-containing oil composition. In another embodiment, the system includes a molded article comprising one or more surfaces that contact both the liquid and vaporized terpene-containing oil composition.

[0055] In one embodiment, the system includes a molded article comprising one or more liquid contact surfaces that are in contact with a liquid terpene-containing oil composition for at least 5 minutes. In another embodiment, the system includes a molded article comprising one or more vapor contact surfaces that are repeatedly contacted with a vaporized terpene-containing oil composition for a total contact time of at least 5 minutes.

[0056] In the embodiments, based on the total weight of the terpene-containing oil composition, the terpene-containing oil composition comprises at least 25 wt% of terpene-containing oil. Detailed Implementation

[0057] In one aspect of the invention, the present invention relates to a molded article configured to receive a terpene-containing oil composition and comprising a copolyester composition, wherein the copolyester composition has a Tg of at least 95°C or at least 100°C, comprises a copolyester (as described herein), and has at least one property selected from the following: a tensile modulus greater than 1400 MPa, measured according to ASTM D638 using 3.2 mm thick rods subjected to 50% relative humidity for 40 hours at 23°C; a cantilever beam notched impact strength greater than 1000 J / m, measured according to ASTM D256 using 3.2 mm thick rods subjected to 50% relative humidity for 40 hours at 23°C; a yield tensile stress of at least 40 MPa, measured according to ASTM D638; and a transmittance of at least 70, according to ASTM D256. D1003 is measured using a 3.2mm thick sheet after injection molding at a barrel setpoint of 249°C and a mold temperature of 80°C; ΔE value less than 25, using a 3.2mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C; or L* color of at least 85, measured according to ASTM E1348 using a 3.2mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C. In the examples, the polymer-based resin has at least two or at least three of the listed properties.

[0058] The term “polyester” as used herein is intended to include “copolyester” and should be understood as referring to a synthetic polymer prepared by reacting one or more difunctional and / or polyfunctional carboxylic acids with one or more difunctional and / or polyfunctional hydroxy compounds. Typically, the difunctional carboxylic acid can be a dicarboxylic acid, and the difunctional hydroxy compound can be a dihydric alcohol, such as glycols and diols. The term “diol” as used herein includes, but is not limited to, diols, glycols, and / or polyfunctional hydroxy compounds, such as branching agents. Alternatively, the difunctional carboxylic acid can be a hydroxycarboxylic acid, such as p-hydroxybenzoic acid, and the difunctional hydroxy compound can be an aromatic ring with two hydroxyl substituents, such as hydroquinone. The term “residue” as used herein refers to any organic structure introduced into the polymer by the corresponding monomer through polycondensation and / or esterification reactions. As used herein, the term “repeating unit” refers to an organic structure having dicarboxylic acid residues and diol residues bonded by carbonyl groups. Therefore, for example, dicarboxylic acid residues can be derived from dicarboxylic acid monomers or their associated acyl halides, esters, salts, anhydrides, or mixtures thereof. Thus, as used herein, the term dicarboxylic acid is intended to include dicarboxylic acids and any derivatives thereof, including their associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, which can be used in reaction processes with diols to prepare polyesters. Furthermore, as used herein, the term "diacid" includes polyfunctional acids, such as branching agents. As used herein, the term "terephthalic acid" is intended to include terephthalic acid itself and its residues, as well as any derivatives thereof, including their associated acyl halides, esters, half-esters, salts, half-salts, anhydrides, mixed anhydrides, or mixtures thereof, or residues thereof, which can be used in reaction processes with diols to prepare polyesters.

[0059] In one embodiment, terephthalic acid can be used as a starting material. In another embodiment, dimethyl terephthalate can be used as a starting material. In yet another embodiment, a mixture of terephthalic acid and dimethyl terephthalate can be used as a starting material and / or an intermediate material. In embodiments, at least a portion of the terephthalic acid or dimethyl terephthalate used as a raw material has recycled components directly or indirectly derived from recycled waste. In embodiments, the recycled components can be obtained from waste plastics containing terephthalic acid residues, such as recycled monomers obtained by solvent decomposition (e.g., methanol decomposition) methods. In embodiments, the terephthalic acid residues present in the polyester (according to any embodiment herein) contain at least 50 mol%, or at least 75 mol%, or 100 mol% of recycled components. In embodiments, the dicarboxylic acid component of the polyester contains monomer residues having at least 50 mol% recycled components, or at least 75 mol% recycled components, or 100 mol% recycled components.

[0060] The polyesters used in this invention are generally prepared from dicarboxylic acids and diols, which react in substantially equal proportions and are introduced into the polyester polymer as their respective residues. Therefore, the polyesters of this invention may contain substantially equal molar proportions of acid residues (100 mol%) and diol (and / or polyfunctional hydroxyl compound) residues (100 mol%), such that the total molar number of repeating units is equal to 100 mol%. Therefore, the molar percentages provided in this disclosure may be based on the total molar number of acid residues, the total molar number of diol residues, or the total molar number of repeating units. For example, based on total acid residues, a polyester containing 4 mol% isophthalic acid means that the polyester contains 4 mol% isophthalic acid residues out of a total of 100 mol% acid residues. Therefore, there are 4 moles of isophthalic acid residues per 100 moles of acid residues. In another example, based on total glycol residues, a polyester containing 15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol refers to a polyester containing 15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues out of a total of 100 mol% glycol residues. Therefore, there are 15 moles of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues per 100 moles of glycol residues.

[0061] In other aspects of the invention, the Tg of the polyester used in the invention may be at least one of the following ranges: 95 to 115°C; 95 to 110°C; 95 to 105°C; 95 to 100°C; 100 to 115°C; 100 to 110°C; 100 to 105°C; 105 to 115°C; 105 to 110°C; and 110 to 115°C.

[0062] In other aspects of the invention, the diol components that can be used in the polyesters of the invention include, but are not limited to, at least one of the following ranges: 5 mol%-15 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 85 mol%-95 mol% 1,4-cyclohexanediethanol; 5 mol%-14 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 86 mol%-95 mol% 1,4-cyclohexanediethanol; 5 mol%-13 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 87 mol%-95 mol% 1,4-cyclohexanediethanol; 5 mol%-12 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 88 mol%-95 mol% 1,4-cyclohexanediethanol; 5 mol%-11 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 89 mol%-95 mol% 1,4-cyclohexanediol; 6 mol%-15 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 85 mol%-94 mol% 1,4-cyclohexanediol; 6 mol%-14 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 86 mol%-94 mol% 1,4-cyclohexanediol; 6 mol%-13 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 87 mol%-94 mol% 1,4-cyclohexanediol; 6 mol%-12 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 88 mol%-94 mol% 1,4-cyclohexanediol; 6 mol%-11 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 89 mol%-94 mol% 1,4-cyclohexanediol; 7 mol%-15 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 85 mol%-93 mol% 1,4-cyclohexanediol; 7 mol%-14 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 86 mol%-93 mol% 1,4-cyclohexanediol; 7 mol%-13 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 87 mol%-93 mol% 1,4-cyclohexanediol; 7 mol%-12 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 88 mol%-93 mol% 1,4-cyclohexanediol; 7 mol%-11 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 89 mol%-93 mol% 1,4-cyclohexanediol; 8 mol%-15 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 85 mol%-92 mol% 1,4-cyclohexanediol;8 mol%-14 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 86 mol%-92 mol% 1,4-cyclohexanediol; 8 mol%-13 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 87 mol%-92 mol% 1,4-cyclohexanediol; 8 mol%-12 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 88 mol%-92 mol% 1,4-cyclohexanediol; 8 mol%-11 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 89 mol%-92 mol% 1,4-cyclohexanediol; 9 mol%-15 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 85 mol%-91 mol% 1,4-Cyclohexanediethanol; 9 mol%-14 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 86 mol%-91 mol% 1,4-Cyclohexanediethanol; 9 mol%-13 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 87 mol%-91 mol% 1,4-Cyclohexanediethanol; 9 mol%-12 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 88 mol%-91 mol% 1,4-Cyclohexanediethanol; 9 mol%-11 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 89 mol%-91 mol% 1,4-Cyclohexanediethanol; 10 mol%-15 mol% 2,2,4,4-Tetramethyl-1,3-cyclobutanediol and 85 mol%-90 mol% 1,4-Cyclohexanediethanol; 10 mol%-14 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 86 mol%-90 mol% 1,4-cyclohexanediethanol; 10 mol%-13 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 87 mol%-90 mol% 1,4-cyclohexanediethanol; 10 mol%-12 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 88 mol%-90 mol% 1,4-cyclohexanediethanol; and 10 mol%-11 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 89 mol%-90 mol% 1,4-cyclohexanediethanol.

[0063] For certain embodiments of the present invention, the polyesters used in the present invention may exhibit at least one of the following specific logarithmic viscosities, determined at 25°C in a 0.5 g / 100 ml concentration of 60 / 40 (wt / wt) phenol / tetrachloroethane: 0.60 to 1.2 dL / g; 0.60 to 1.1 dL / g; 0.60 to 1 dL / g; 0.60 to less than 1 dL / g; 0.60 to 0.98 dL / g; 0.60 to 0.95 dL / g; 0.60 to 0.90 dL / g; 0.60 to 0.85 dL / g; 0.60 to 0.80 dL / g; 0.60 to 0.75 dL / g; 0.60 to less than 0.75 dL / g; 0.60 to 0.72 dL / g; 0 0.60 to 0.70 dL / g; 0.60 to less than 0.70 dL / g; 0.60 to 0.68 dL / g; 0.60 to less than 0.68 dL / g; 0.60 to 0.65 dL / g; 0.65 to 1.2 dL / g; 0.65 to 1.1 dL / g; 0.65 to 1 dL / g; 0.65 to less than 1 dL / g; 0 0.65 to 0.98 dL / g; 0.65 to 0.95 dL / g; 0.65 to 0.90 dL / g; 0.65 to 0.85 dL / g; 0.65 to 0.80 dL / g; 0.65 to 0.75 dL / g; 0.65 to less than 0.75 dL / g; 0.65 to 0.72 dL / g; 0.65 to 0.70 dL / g g; or 0.65 to less than 0.70 dL / g; 0.70 to 1.2 dL / g; 0.70 to 1.1 dL / g; 0.70 to 1 dL / g; 0.70 to less than 1 dL / g; 0.70 to 0.98 dL / g; 0.70 to 0.95 dL / g; 0.70 to 0.90 dL / g; 0.70 to 0.85 dL / g; 0.70 to 0.80 dL / g; 0.70 to 0.75 dL / g; 0.70 to less than 0.75 dL / g; 0.75 to 1.2 dL / g; 0.75 to 1.1 dL / g; 0.75 to 1 dL / g; 0.75 to less than 1 dL / g; 0.75 to 0.98 dL / g; 0.75 to 0.95 dL / g; 0. 75 to 0.90 dL / g; 0.75 to 0.85 dL / g; 0.75 to 0.80 dL / g; 0.75 to less than 0.80 dL / g; 0.80 to 1.2 dL / g; 0.80 to 1.1 dL / g; 0.80 to 1 dL / g; 0.80 to less than 1 dL / g; 0.80 to 0.98 dL / g; 0.80 Up to 0.95 dL / g; 0.80 to 0.90 dL / g; 0.80 to 0.85 dL / g; 0.80 to less than 0.85 dL / g; 0.85 to 1.2 dL / g; 0.85 to 1.1 dL / g; 0.85 to 1 dL / g; 0.85 to less than 1 dL / g; 0.85 to 0.98 dL / g; 0.85 to 0.95 dL / g.95 dL / g; 0.85 to 0.90 dL / g; 0.85 to less than 0.90 dL / g; 0.90 to 1.2 dL / g; 0.90 to 1.1 dL / g; 0.90 to 1 dL / g; 0.90 to less than 1 dL / g; 0.90 to 0.98 dL / g; 0.90 to 0.95 dL / g; or 0.90 to less than 0.95 dL / g. Unless otherwise stated, the polyester compositions of the present invention are expected to have at least one specific logarithmic viscosity range and at least one monomer range of the compositions described herein. Unless otherwise stated, the polyester compositions of the present invention are also expected to have at least one Tg range and at least one monomer range of the compositions described herein. Unless otherwise stated, the polyester compositions of the present invention are also expected to have at least one Tg range, at least one specific logarithmic viscosity range and at least one monomer range of the compositions described herein.

[0064] For the desired polyester, the molar ratio of cis / trans 2,2,4,4-tetramethyl-1,3-cyclobutanediol can differ from their respective pure forms or mixtures thereof. In some embodiments, the molar percentage of cis- and / or trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol is greater than 50 mol% cis and less than 50 mol% trans; or greater than 55 mol% cis and less than 45 mol% trans; or 30 mol%-70 mol% cis and 70 mol%-30% trans; or 40 mol%-60 mol% cis and 60 mol%-40 mol% trans; or 50 to 70 mol% trans and 50 mol%-30 mol% cis; or 50 mol%-70 mol% cis and 50 mol%-30 mol% trans; or 60 mol%-70 mol% cis and 30 mol%-40 mol% trans; or greater than 70 mol% cis and less than 30 mol% trans; wherein the total molar percentage of cis- and trans-2,2,4,4-tetramethyl-1,3-cyclobutanediol equals 100 mol. The molar ratio of cis / trans-1,4-cyclohexanediethanol can vary from 50 / 50 to 0 / 100, for example, from 40 / 60 to 20 / 80. The cis / trans ratio of the composition can be determined by proton nuclear magnetic resonance (NMR) spectroscopy.

[0065] In some embodiments, terephthalic acid or its esters, such as dimethyl terephthalate, or mixtures of terephthalic acid and its esters, constitute the majority or all of the dicarboxylic acid component for forming the polyesters usable in this invention. In some embodiments, terephthalic acid residues may constitute part or all of the dicarboxylic acid component for forming the polyesters of this invention, at a concentration of at least 70 mol%, for example at least 80 mol%, at least 90 mol%, at least 95 mol%, at least 99 mol%, or 100 mol% in a preferred embodiment (e.g., reactor-grade). In some embodiments, polyesters having a higher amount of terephthalic acid may be used to produce higher impact strength properties. For the purposes of this disclosure, the terms "terephthalic acid" and "dimethyl terephthalate" are used interchangeably herein. In one embodiment, dimethyl terephthalate is part or all of the dicarboxylic acid component used to prepare the polyester that can be used in the present invention; in all embodiments, 70 mol%-100 mol%; or 80 mol%-100 mol%; or 90 mol%-100 mol%; or 99 mol%-100 mol%; or 100 mol% of terephthalic acid and / or dimethyl terephthalate and / or mixtures thereof may be used.

[0066] In some embodiments, in addition to terephthalic acid residues, the dicarboxylic acid component of the polyester used in the present invention may comprise up to 30 mol%, up to 20 mol%, up to 10 mol%, up to 5 mol%, or less than 5 mol%, or up to 3 mol%, or up to 1 mol% of one or more modified aromatic dicarboxylic acids. In a preferred embodiment, the polyester contains 0 mol% of modified aromatic dicarboxylic acids. Therefore, if present, the amount of one or more modified aromatic dicarboxylic acids is contemplated to be within any of these foregoing endpoint values, including, for example, 0.01 mol%-30 mol%, 0.01 mol%-20 mol%, 0.01 mol%-10 mol%, 0.01 mol%-5 mol%, 0.01 mol%-less than 5 mol%, 0.01 mol%-4 mol%, 0.01 mol%-3 mol%, 0.01 mol%-2 mol%, or 0.01 mol%-1 mol% of one or more modified aromatic dicarboxylic acids. In some embodiments, the amount of one or more modified aromatic dicarboxylic acids may be one or more modified aromatic dicarboxylic acids within the following ranges: 1 mol%-5 mol%, 1 mol%-less than 5 mol%, 1 mol%-4 mol%, 1 mol%-3 mol%, 1 mol%-2 mol%, or 1.5 mol%-5 mol%, 1.5 mol%-less than 5 mol%, 1.5 mol%-4 mol%, 1.5 mol%-3.5 mol%, 1.5 mol%-3 mol%, 1.5 mol%-2.5 mol%, 1.5 mol%-2 mol%, or 2 mol%-5 mol%, 2 mol%-less than 5 mol%, 2 mol%-4 mol%. mol%, 2mol%-3.5mol%, 2mol%-3mol%, 2mol%-2.5mol%, or 2.5mol%-5mol%, 2.5mol%-less than 5mol%, 2.5mol%-4mol%, 2.5mol%-3.5mol%, 2.5mol%-3mol%, or 3mol%-5mol%, 3mol%-less than 5mol%, 3mol%-4mol%, 3mol%-3.5mol%, or 3.5mol%-5mol%, 3.5mol%-less than 5mol%, 3.5mol%-4mol%, 4mol%-5mol%, 4mol%-less than 5mol.

[0067] In one embodiment, the modified aromatic dicarboxylic acids used in this invention include, but are not limited to, those having up to 20 carbon atoms, and may be linear, para-oriented, or symmetrical. Examples of modified aromatic dicarboxylic acids used in this invention include, but are not limited to, isophthalic acid, 4,4'-biphenyl dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and trans-4,4'-stilbene dicarboxylic acid and their esters. In one embodiment, the modified aromatic dicarboxylic acid is isophthalic acid. A preferred embodiment of this invention is based on a 100% dicarboxylic acid composition of terephthalic acid residues.

[0068] The carboxylic acid component of the polyester used in this invention can be further modified with up to 10 mol%, for example up to 5 mol% or up to 1 mol%, of one or more aliphatic dicarboxylic acids containing 2-16 carbon atoms, such as malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, octanoic acid, azelaic acid, and dodecanedicarboxylic acid. Some embodiments may also contain 0.01 mol% or more, for example 0.1 mol% or more, 1 mol% or more, 5 mol% or more, or 10 mol% or more of one or more modified aliphatic dicarboxylic acids. In a preferred embodiment, the polyester contains 0 mol% of modified aliphatic dicarboxylic acid. Therefore, if present, the amount of one or more modified aliphatic dicarboxylic acids is expected to be within any of these foregoing endpoint values, including, for example, 0.01 mol%-10 mol% and 0.1 mol%-10 mol%. The total mol% of the dicarboxylic acid component is 100 mol%.

[0069] Esters of terephthalic acid and other modified dicarboxylic acids, or their corresponding esters and / or salts, may be used in place of dicarboxylic acids. Suitable examples of dicarboxylic acid esters include, but are not limited to, dimethyl ester, diethyl ester, dipropyl ester, diisopropyl ester, dibutyl ester, and diphenyl ester. In one embodiment, the ester is selected from at least one of the following: methyl ester, ethyl ester, propyl ester, isopropyl ester, and phenyl ester.

[0070] 1,4-Cyclohexanediethanol can be cis, trans, or a mixture thereof, for example, in a cis / trans ratio of 60:40 to 40:60. In another embodiment, trans-1,4-cyclohexanediethanol can be present in an amount of 60 mol% to 80 mol%.

[0071] The polyester portion of the polyester composition usable in the present invention may contain 14 mol% or less of one or more modified diols, which are not 2,2,4,4-tetramethyl-1,3-cyclobutanediol or 1,4-cyclohexanediol; in another embodiment, the polyester usable in the present invention may contain 10 mol% or less of one or more modified diols. In another embodiment, the polyester usable in the present invention may contain 5 mol% or less of one or more modified diols. In another embodiment, the polyester usable in the present invention may contain 3 mol% or less of one or more modified diols. In a preferred embodiment, the polyester usable in the present invention may contain 0 mol% of modified diols. Some embodiments may also contain 0.01 or more mol%, for example 0.1 or more mol%, 1 or more mol%, 5 or more mol%, or 10 or more mol% of one or more modified diols. Thus, if present, the amount of one or more modified diols is expected to be within any of these foregoing endpoint values, including, for example, 0.1 mol% to 10 mol%.

[0072] The modified diols that can be used in the polyesters of this invention refer to diols other than 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanediol, and may contain 2-16 carbon atoms. Suitable examples of modified diols include, but are not limited to, ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, neopentyl glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, p-xylenediol, or mixtures thereof. In one embodiment, the modified diol is ethylene glycol. In another embodiment, the modified diol includes, but is not limited to, 1,3-propanediol and / or 1,4-butanediol. In another embodiment, ethylene glycol is excluded as a modified diol. In another embodiment, 1,3-propanediol and 1,4-butanediol are excluded as modified diols. In another embodiment, 2,2-dimethyl-1,3-propanediol is excluded as a modified diol. The polyesters usable in this invention may each comprise 0 to 10 mol% of the total molar percentage of diol or diacid residues, for example 0.01 mol%-5 mol%, 0.01 mol%-1 mol%, 0.05 mol%-5 mol%, 0.05 mol%-1 mol%, or 0.1 mol%-0.7 mol%, or 0.1 mol%-0.5 mol% of one or more residues of a branched monomer (also referred to herein as a branching agent) having three or more carboxyl substituents, hydroxyl substituents, or combinations thereof. In some embodiments, the branched monomer or agent may be added before and / or during and / or after the polyester polymerization. Therefore, the polyesters usable in this invention may be linear or branched. In some embodiments, the branched monomer or agent may be added before and / or during and / or after polymerization.

[0073] Examples of branched monomers include, but are not limited to, polyfunctional acids or alcohols, such as trimellitic acid, trimellitic anhydride, pyromellitic dianhydride, trimethylolpropane, glycerol, pentaerythritol, citric acid, tartaric acid, 3-hydroxyglutaric acid, etc. In one embodiment, the branched monomer residues may comprise 0.1 mol% to 0.7 mol% of one or more residues selected from: trimellitic anhydride, pyromellitic dianhydride, glycerol, sorbitol, 1,2,6-hexanetriol, pentaerythritol, trimethylolethane, and / or pyromellitic acid. Branched monomers may be added to a polyester reaction mixture or blended with polyesters in the form of concentrates, as described, for example, in U.S. Patent Nos. 5,654,347 and 5,696,176, the disclosures of which regarding branched monomers are incorporated herein by reference.

[0074] Polyesters usable in this invention can be prepared by methods known in the literature, such as methods in a homogeneous solution, transesterification methods in a melt, and methods at a two-phase interface. Suitable methods include, but are not limited to, reacting one or more dicarboxylic acids with one or more diols at a temperature of 100°C to 315°C and a pressure of 0.1 to 760 mmHg for a time sufficient to form a polyester. See U.S. Patent No. 3,772,405 concerning a method for producing polyesters, the disclosure of which is incorporated herein by reference.

[0075] The polyesters that can be used in this invention can also be prepared by reactive melt blending and extrusion of two polyesters. For example, a polyester containing 100% terephthalic acid residues, 10 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues, and 90 mol% 1,4-cyclohexanediol can be prepared by reactive melt blending and extrusion of an equal amount of a polyester containing 100 mol% terephthalic acid residues and 100% 1,4-cyclohexanediol residues with another polyester containing 100 mol% terephthalic acid residues, 80 mol% 1,4-cyclohexanediol residues, and 20 mol% 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues.

[0076] In the embodiments, the polyester of the present invention, prepared in a reactor or by melt blending / extrusion, may subsequently be crystallized and solidified by techniques known in the art to further improve IV if desired.

[0077] In embodiments, articles made from the copolyester composition may be amorphous. For the purposes of this disclosure, amorphous means crystallinity of 1% or less. In other embodiments, articles made from the copolyester composition may be semi-crystalline, for example, by heat crystallization. In embodiments, the articles of the present invention have a crystallinity of 1% to 40%, or 1% to 35%, or 1% to 30%, or 5% to 40%, or 5% to 35%, or 5% to 30%, or 10% to 40%, or 10% to 35%, or 10% to 30%.

[0078] In other embodiments, articles made from copolyester compositions may exhibit strain-induced crystallinity. Strain-induced crystallinity refers to the phenomenon in which initially amorphous solid material undergoes a phase transition, in which some amorphous domains are transformed into crystalline domains due to the application of strain. This phenomenon has a significant impact on strength and fatigue properties.

[0079] In embodiments, when stretched at temperatures above the polyester Tg, such as during molding or forming processes (e.g., stretch blow molding), the articles of the present invention have a strain-induced crystallinity of 1% to 40%, or 1% to 35%, or 1% to 30%, or 5% to 40%, or 5% to 35%, or 5% to 30%, or 10% to 40%, or 10% to 35%, or 10% to 30%.

[0080] In the embodiments, the article is a transparent semi-crystalline article comprising a copolyester with a crystallization half-life of less than 10 minutes but greater than about 30 seconds. In the embodiments, the crystallization half-life of the copolyester is 30 seconds to 5 minutes, or 30 seconds to 3 minutes, or 30 seconds to 2 minutes, or 30 seconds to 1.5 minutes.

[0081] In embodiments, the articles of the present invention may include the polyester of the present invention having a melt temperature (Tm) of 260°C to 300°C.

[0082] Furthermore, the polyesters used in this invention may also contain 0.01wt%-25wt%, 0.01wt%-20wt%, 0.01wt%-15wt%, 0.01wt%-10wt%, or 0.01 to 5wt% of commonly used additives, such as colorants, dyes, release agents, reheat additives, flame retardants, plasticizers, stabilizers, including but not limited to UV stabilizers, heat stabilizers and / or their reaction products, fillers, and impact modifiers, by weight of 0.01wt%-25wt%, 0.01wt%-20wt%, 0.01wt%-15wt%, 0.01wt%-10wt%, or 0.01 to 5wt% of the total weight of the polyester composition. Examples of typical commercially available impact modifiers known in the art and usable in this invention include, but are not limited to, ethylene / propylene terpolymers; functionalized polyolefins, such as those containing methyl acrylate and / or glycidyl methacrylate; styrene-based block copolymer impact modifiers; and various acrylic core / shell impact modifiers. For example, UV additives can be introduced into manufactured articles by adding to the bulk, by applying a hard coating, or by co-extruding a capping layer. Residues of these additives are also considered as part of the polyester composition.

[0083] The polyesters used in this invention may contain at least one chain extender. Suitable chain extenders include, but are not limited to, polyfunctional (including but not limited to difunctional) isocyanates, polyfunctional epoxides, including, for example, epoxidized phenolic varnishes and phenoxy resins. In some embodiments, the chain extender may be added at the end of the polymerization process or after the polymerization process. If added after the polymerization process, the chain extender may be introduced by compounding or by adding it during a conversion process such as injection molding or extrusion. The amount of chain extender used may vary depending on the specific monomer composition used and the desired physical properties, but is typically from about 0.1 wt% to about 10 wt% based on the total weight of the polyester, preferably from about 0.1 wt% to about 5 wt%.

[0084] Heat stabilizers are compounds that stabilize polyesters during polyester manufacturing and / or post-polymerization, including but not limited to phosphorus compounds, including but not limited to phosphoric acid, phosphorous acid, phosphonic acid, hypophosphonic acid, phosphonous acid, and their various esters and salts. These may be present in polyester compositions that can be used in the present invention. Esters may be alkyl, branched alkyl, substituted alkyl, difunctional alkyl, alkyl ether, aryl, and substituted aryl. In one embodiment, the number of ester groups present in a particular phosphorus compound may vary from zero to a maximum allowed based on the number of hydroxyl groups present on the heat stabilizer used. The term "heat stabilizer" is intended to include its reaction products. The term "reaction product" used in conjunction with the heat stabilizers of the present invention refers to any product of a polycondensation or esterification reaction between the heat stabilizer and any monomer used to prepare the polyester, as well as the product of a polycondensation or esterification reaction between a catalyst and any other type of additive.

[0085] Reinforcing materials can be used in the compositions of the present invention. Reinforcing materials may include, but are not limited to, carbon filaments, silicates, mica, clay, talc, titanium dioxide, wollastonite, glass sheets, glass beads and fibers, and polymer fibers and combinations thereof. In one embodiment, the reinforcing material is glass, such as fiber glass filaments, mixtures of glass and talc, glass and mica, and glass and polymer fibers.

[0086] In the embodiments, the articles (configured to receive the terpene-containing oil composition) may include, but are not limited to, injection blow-molded articles, injection stretch blow-molded articles, extrusion blow-molded articles, extrusion stretch blow-molded articles, calendered articles, compression molded articles, and solution cast articles. Methods of manufacturing the articles include, but are not limited to, extrusion blow molding, extrusion stretch blow molding, injection blow molding, injection stretch blow molding, calendering, compression molding, and solution casting.

[0087] In embodiments, the article (configured to receive a terpene-containing oil composition) may comprise a film and / or sheet comprising a polyester composition forming the article of the present invention. Methods for forming polyester films and / or sheets are well known in the art. Examples of films and / or sheets of the present invention include, but are not limited to, extruded films and / or sheets, calendered films and / or sheets, compression-molded films and / or sheets, and solution-cast films and / or sheets. Methods for preparing films and / or sheets include, but are not limited to, extrusion, calendering, compression molding, and solution casting.

[0088] In embodiments of the invention, the notched cantilever impact strength of the copolyester composition is at least 800 J / m or at least 900 J / m, measured according to ASTM D256 using 3.2 mm thick rods subjected to 50% relative humidity at 23°C for 48 hours. In some embodiments, the notched cantilever impact strength of the polymer-based resin is at least 1000 J / m or at least 1050 J / m, measured according to ASTM D256 using 3.2 mm thick rods subjected to 50% relative humidity at 23°C for 48 hours.

[0089] In embodiments of the present invention, using 3.2mm thick plates injection molded at a barrel temperature of 249°C and a mold temperature of 80°C, the ΔE value of the polymer-based resin is less than 25, or less than 20, or less than 15, or less than 14, or less than 13, or less than 12, or less than 11, or less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, wherein ΔE is determined by the following equation ((L*-100)). 2 + (a*-0) 2 + (b*-0) 2 ) 1 / 2Wherein, the color components L*, a*, and b* are measured according to ASTM E1348. In some embodiments, using 3.2 mm thick sheets after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C, the ΔE value of the polymer-based resin is in the range of 2 to 25, or 2 to 20, or 2 to 15, or 2 to 14, or 2 to 13, or 2 to 12, or 2 to 11, or 2 to 10, or 2 to 9, or 2 to 8, or 2 to 7, or 2 to 6, or 2 to 5, wherein ΔE is determined by the following equation: ((L*-100) 2 + (a*-0) 2 + (b*-0) 2 ) 1 / 2 The L*, a*, and b* color components were measured according to ASTM E1348.

[0090] In embodiments of the invention, the L* color of the polymer-based resin is at least 85, or at least 86, or at least 87, or at least 88, or at least 89, or at least 90, or at least 91, or at least 92, or at least 93, or at least 94, or at least 95, measured according to ASTM E1348 using a 3.2 mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C. In some embodiments, the L* color of the polymer-based resin is in the range of 85 to 98, or 85 to 97, or 85 to 96, or 85 to 95, measured according to ASTM E1348 using a 3.2 mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C.

[0091] In embodiments of the invention, the b* value of the polymer-based resin is less than 15, or less than 12, or less than 10, or less than 9, or less than 8, or less than 7, or less than 6, or less than 5, or less than 4, measured according to ASTM E1348 using a 3.2 mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C. In some embodiments, the b* color of the polymer-based resin is in the range of 0 to 15, or 0 to 10, or 0 to 8, or 0 to 5, measured according to ASTM E1348 using a 3.2 mm thick sheet after injection molding at a barrel temperature of 249°C and a mold temperature of 80°C.

[0092] In this invention, the present invention relates to molded articles. In some embodiments, the molded article is not a continuously extruded film that is infinitely (or continuously) in one direction and has a fixed width and thickness in the other two directions, as is the case in rolled film. In some embodiments, a film or sheet can be converted into a molded article, for example, by thermoforming into a three-dimensional object, such as a cup or bowl. In embodiments of the present invention, the molded article is neither a film nor a sheet. In embodiments of the present invention, the molded article may be selected from injection molded articles, extruded articles, rotationally molded articles, compression molded articles, blow molded articles, injection blow molded articles, injection stretch blow molded articles, extruded blow molded articles, sheet or film extruded articles, profile extruded articles, gas-assisted molding articles, structural foam molding articles, or thermoformed articles.

[0093] Molded articles made from the polyester compositions of the present invention can be molded or extruded for use in steam conveying applications. In embodiments of the invention, the molded articles are selected from transparent articles, see-through articles, thin-walled articles, technical articles (e.g., articles with complex designs), articles with high design specifications, complex design articles, containers, food contact articles, household articles, general consumer goods, packaging articles, medical articles, or components thereof, wherein the articles are configured to receive a terpene-containing oil composition.

[0094] In some embodiments, the polyester composition can be molded in one step into, for example, pellets, sheets or preforms, and then can be molded a second time into articles, such as conduits, tubes, thin-walled containers or thick-walled containers, configured to receive terpene-containing oil compositions.

[0095] Methods for forming polyester compositions into films, molded articles, and sheets may be based on methods known in the art. In embodiments, the polyester composition may be overmolded onto itself or onto different polyester compositions, and when the article (having such an overmolded interface) is used for its intended purpose, it maintains interfacial bond (or weld line) strength that does not separate (or delaminate). In embodiments, transparent polyesters and translucent (or opaque) polyesters may be overmolded onto each other. In embodiments, the different polyesters all belong to one or more embodiments of the invention (as discussed herein).

[0096] In one aspect, an article is provided comprising a molding assembly configured to receive a terpene-containing oil composition, wherein the molding assembly is formed of a copolyester composition comprising a copolyester and having a Tg of at least 95°C.

[0097] The terpene-containing oil composition contains a terpene-containing oil in an amount of at least 1 wt%, or at least 5 wt%, or at least 10 wt%, or at least 15 wt%, or at least 20 wt%, or at least 25 wt%. A terpene-containing oil refers to an oil containing at least one terpene compound, wherein the amount of the terpene compound is at least 0.1 wt% based on the weight of the oil. In embodiments, the terpene-containing oil composition comprises at least 0.01 wt%, or at least 0.05 wt%, or at least 0.1 wt%, or at least 0.5 wt%, or at least 1 wt%, or at least 5 wt%, or at least 10 wt% of total terpene compounds.

[0098] In the embodiments, the terpene-containing oil is a terpene-containing plant-based oil. A terpene-containing plant-based oil refers to an oil that can be found in or obtained from a plant and contains at least one terpene. The definition of a plant is not limited and can include any type or classification of plant, including vascular plants, non-vascular plants, seed plants, spore plants, angiosperms, and gymnosperms. Plants can include small plants, shrubs, or trees. In the embodiments, the terpene-containing plant-based oil can be synthesized or prepared without actually being derived from a plant, as long as the oil is of a type that can be found in or obtained from a plant.

[0099] In the embodiments, the terpene-containing plant-based oil is of the type found primarily in the leaves or flowers of a plant. In the embodiments, the terpene-containing plant-based oil is of the type found primarily in the seeds or fruits of a plant. In the embodiments, the terpene-containing oil composition may be a combination of different plant-based oils (e.g., a mixture or blend), provided that the composition contains at least one terpene-containing plant-based oil.

[0100] In the embodiments, the terpene-containing oil composition comprises a plant-based oil. In the embodiments, the plant-based oil is a vegetable oil. A vegetable oil refers to a fatty, dense, and non-volatile type of oil obtained from a plant. In the embodiments, the vegetable oil is extracted from the roots, stems / bark, leaves, flowers, seeds, or fruits of a plant, tree, or shrub. In the embodiments, the vegetable oil is cold-pressed or extracted by heat. Examples of vegetable oils may include rosehip oil (Rosa dogbane), evening primrose oil (evening primrose), almond oil (sweet almond), calendula oil (calendula), MCT oil, olive oil, canola oil, corn oil, vegetable oil, cottonseed oil, safflower oil, sunflower seed oil, soapberry oil; and extracts, isolates, or derivatives of the foregoing substances; and any combination of the foregoing substances.

[0101] In this embodiment, the plant-based oil is an essential oil. An essential oil is a concentrated and volatile substance extracted from a plant selected from aromatic herbs or plants, wherein the essential oil refers to an oil that carries the distinctive aroma (or essence) of that plant. Examples of essential oils may include agar oil or oodh, wormwood oil, angelica oil, fennel oil, asafoetida oil, Peruvian balsam, basil oil, laurel oil, bergamot oil, black pepper oil, broomcorn oil, birch oil, camphor oil, calamansi oil, or calamansi essential oil. Oils containing: coriander oil, cardamom seed oil, carrot seed oil, cedarwood oil, chamomile oil, calamus oil, cinnamon oil, rockrose oil, citronella oil, lemongrass oil, sage oil, coconut oil, clove oil, coffee oil, coriander oil, tansy oil, costus root oil, cranberry seed oil, long pepper oil, cumin seed oil or black seed oil, cypress oil, cyperus oil, curry leaf oil, artemisia oil, dill oil, eucalyptus oil, elemi oil, eucalyptus oil, fennel oil. Coriander seed oil, fenugreek oil, fir oil, frankincense oil, galangal oil, white pine resin oil, garlic oil, bay leaf oil, ginger oil, goldenrod oil, grapefruit oil, henna oil, immortelle oil, pecan oil, horseradish oil, hyacinth, Idaho-grown tansy, jasmine oil, juniper berry oil, bay leaf oil, lavender oil, basil oil, lemon oil, lemongrass oil, lime oil, litsea cubeba oil, linalool oil, orange peel oil, oregano oil, bee oil Flower oil or lemon balm, wild peppermint oil or peppermint oil, moringa oil, mountain peppermint oil, artemisia oil, mustard oil, myrrh oil, myrtle oil, neem oil, neroli oil, nutmeg oil, orange oil, oregano oil, iris oil, sage oil, parsley oil, patchouli oil, perilla essential oil, peppermint oil, black peppermint oil, orange leaf oil, pine oil, ravensa leaf oil, red cedarwood oil, Roman chamomile oil, rose oil, rosehip oil Rosemary oil, rosewood oil, sage oil, sandalwood oil, sassafras oil, peppermint oil, schisandra oil, spearmint oil, nard oil, spruce oil, star anise oil, mandarin orange oil, tarragon oil, tea tree oil, thyme oil, hemlock oil, turmeric oil, chamomile oil, vetiver oil, red cedar oil, wintergreen oil, yarrow oil, and orchid oil; as well as extracts, isolates, or derivatives of the foregoing substances; and any combination of the foregoing substances. In embodiments, the extracts, isolates, or derivatives of the essential oils contain terpenes or flavonoids. In embodiments, the terpenes are selected from d-limonene, geraniol, β-pinene, myrcene, terpinene, or mixtures thereof.

[0102] In embodiments, the plant-based oil may be a combination of one or more plant oils and one or more essential oils. In embodiments, the terpene-containing oil composition comprises a terpene-containing plant-based oil component, wherein the terpene-containing plant-based oil component comprises one or more terpene-containing plant-based oils selected from plant oils, essential oils, or combinations of plant oils and essential oils. Examples of terpene-containing plant-based oils include eucalyptus oil, lavender oil, neroli oil, hemp oil, peppermint oil, sweet orange oil, tea tree oil, lemon oil, lime oil, and orange oil; and extracts, isolates, or derivatives of the aforementioned oils and / or their plant-derived forms; and combinations of any of the aforementioned substances.

[0103] In embodiments, the terpene-containing oil composition comprises a terpene-containing plant-based oil component and a terpene-free plant-based oil component, wherein the terpene-containing plant-based oil component comprises one or more terpene-containing plant-based oils, and the terpene-free plant-based oil component comprises one or more terpene-free plant-based oils. In embodiments, the terpene-containing oil composition further comprises one or more additional additives selected from solvents, dispersants, stabilizers, emulsifiers, carriers, solvents, and active ingredients. In embodiments, the additional additives may be selected from glycols (e.g., propylene glycol), glycerin (e.g., vegetable glycerin), polysorbates, plant-based alkaloids (e.g., nicotine), or combinations thereof.

[0104] In the embodiments, the copolyester composition forming the injection-molded article is selected from any copolyester composition discussed herein. In one embodiment, the copolyester composition comprises at least one copolyester, said copolyester comprising:

[0105] (a) A dicarboxylic acid component, comprising:

[0106] i) 96 mol%–100 mol% of terephthalic acid residues; and

[0107] ii) 0 mol%-4 mol% of isophthalic acid residues;

[0108] (b) A diol component comprising:

[0109] i) 10 mol%–15 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and

[0110] ii) 85 mol%-90 mol% of 1,4-cyclohexanediethanol residues,

[0111] The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; and the specific logarithmic viscosity is 0.70 to 1.0 dL / g, or 0.75 to 0.95 dL / g, determined at 25°C in 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane; and the Tg of the polyester is 100°C to 115°C.

[0112] The characteristics of the testing methods disclosed in this article can be determined as follows:

[0113] Test methods

[0114] The properties disclosed throughout this application can be determined according to the test methods described herein. The samples can be evaluated (or may be evaluated) using standard ASTM test methods under any of the following specific conditions.

[0115] Table 1. Test Methods

[0116]

[0117] The specific logarithmic viscosity of the polyester was determined at 25°C in 0.5 g / 100 ml of 60 / 40 (wt / wt) phenol / tetrachloroethane (according to ASTM D4603).

[0118] The diol content was determined by proton nuclear magnetic resonance (NMR) spectroscopy. All NMR spectra were recorded on a JEOL EclipsePlus 600 MHz NMR spectrometer using chloroform-trifluoroacetic acid (70–30 v / v). Peak assignment of the 2,2,4,4-tetramethyl-1,3-cyclobutanediol resonance was performed by comparison with models of its monobenzoic and dibenzoic acid esters. These model compounds closely approximate the resonance positions found in the polymer.

[0119] The crystallization half-life, t, was determined by measuring the transmittance of the sample as a function of time on a temperature-controlled hot stage using a laser and a photodetector. 1 / 2 By exposing the polymer to temperature T max The sample was then cooled to the desired temperature for the measurement. The sample was then held at the desired temperature via a hot stage while transmission measurements were performed as a function of time. Initially, the sample was visually transparent with high transmittance, and became opaque as the sample crystallized. The crystallization half-life was recorded as the time it took for the transmittance to be half between the initial and final transmission values. T max Defined as the temperature required to melt the crystal domains of the sample (if domains exist). T is reported in the following examples. maxThis indicates that each sample was heated to adjust its temperature before measuring the crystallization half-life. T max The temperature depends on the composition and is generally different for each polyester. For example, PCT may require heating to a temperature greater than 290°C to melt the crystalline domains.

[0120] Differential scanning calorimetry (DSC) was performed using a TA Instruments 2920 with a liquid nitrogen cooling attachment. Sample weights ranging from 8 to 12 mg were measured and recorded. The sample was first heated from 0°C to 320°C at 20°C / min (first heating scan), then cooled to 0°C at 20°C / min (cooling scan), and then heated again from 0°C to 320°C at 20°C / min. Various thermal parameters were measured and recorded. ΔH cc (cal / g) is the heat of crystallization measured from a cooling scan. T cc It is the peak crystallization temperature during cooling scanning. T g The glass transition temperature was measured during the second heating scan. T m The melting point was measured during the second heating scan. ΔH ch1 (cal / g) is the heat of crystallization measured during the first heating scan. ΔH m1 (cal / g) is the heat of fusion measured during the first heating scan.

[0121] The percentage of crystallinity formed during cooling was calculated by equation (1), assuming a melting specific heat of 29 cal / g (based on unmodified PCT).

[0122]

[0123] For unmodified PCT, the peak temperature in the exothermic crystallization (TCC) occurs at 227°C.

[0124] The percentage of strain-induced crystallinity (Xc) was determined by the first thermal scan of the film evaluated in DSC using equation (2).

[0125]

[0126] As used in this article, the abbreviation "wt" means "weight".

[0127] The following examples further illustrate how the material compositions of the present invention are prepared and evaluated, and are intended to be merely examples of the invention and not to limit its scope. Unless otherwise stated, parts are parts by weight, temperature is degrees Celsius or room temperature, and pressure is atmospheric pressure or near atmospheric pressure.

[0128] Example

[0129] Example 1

[0130] The melt-blended copolyester composition is prepared from the following starting materials:

[0131] 1) PCTA 13319 (from Eastman Chemical Company)

[0132] 2) Copolyester TX1000 (from Eastman Chemical Company)

[0133] 3) Blue toner concentrate

[0134] After drying PCTA 13319 at 120°C and TX1000 at 90°C for 6-8 hours in a desiccant bed drying system, the starting material was melt-blended on a single-screw extruder set to 285°C. Three components were added to the extruder from a loss-in-weight feeder at the following concentrations: 49.26 wt% PCTA, 49.44 wt% TX1000, and 1.30 wt% toner. The resulting (extruded) wire was quenched and cut into cylindrical pellets with a weight of 0.80 g / 50 pellets. The pellets were amorphous with a specific logarithmic viscosity (IV) of 0.79-0.82 (Example 1-A).

[0135] The composition of Example 1-A copolyester has about 97.8 mol% of TPA and 2.2 mol% of IPA diacid residues, and about 88.8 mol% of CHDM and 11.2 mol% of TMCD diol residues. Example 1-A has a Tg of about 102 °C, a Tm of 253 to 259 °C, and a crystallization half-life of about 1 minute at 175 °C.

[0136] Some examples 1-A amorphous granules were crystallized in a rotary reactor at 180°C for about 120-180 minutes, and then the temperature was raised to 225°C and held for a sufficient time to cure the copolyester so that the IV increased to about 0.92 dL / g (Example 1-B).

[0137] Example 2

[0138] Production of test rods

[0139] Granules of each copolyester material from Examples 1 (Examples 1-A and 1-B) were injection molded to form standard test rods measuring 0.5 inches × 5 inches × 0.125 inches (1.27 cm × 12.7 cm × 0.3 cm). The granules were molded in a 110-ton Toyo injection molding machine with a barrel capacity of 3.4 ounces. The copolyester material was injected at an injection speed of 1 inch / second, producing four test rods per injection. The barrel temperature was nominally approximately 249°C (480°F), and the mold temperature was approximately 80°C.

[0140] Test Results

[0141] ESCR - Property Retention in Reverse Impact

[0142] Tests were performed using injection-molded bending bars with lengths of 5.0 inches, widths of 0.5 inches, and thicknesses of 0.125 inches. The bars were placed at 23°C / 50% RH for at least 72 hours. The bars were clamped in a constant strain fixture with 1.5% strain or a 3-point bending fixture, and exposed to the test oil using a cotton pad soaked in the test oil, with the pad placed on the top surface of the bar. After applying the test oil to the side of the bar without pin markings, the strain fixture with the bar attached was sealed in a polyethylene bag at the nominal temperature of 23°C for 24 hours. The bar was then wiped clean and removed from the strain fixture.

[0143] Following exposure, the bars were tested for reverse impact at 23°C. The testing apparatus was a CEAST pendulum impact tester equipped with a 15-joule hammer. The bars were placed in a 2-inch span fixture with the non-chemically exposed side facing the hammer. In addition to the bars exposed to the test oil, control bars (exposed to water) were also subjected to impact testing. The results between the control and chemically exposed bars were used to calculate the percentage of original impact energy retained. The tests were repeated five times, and the results were the average of the five tests. The results are shown in Table 2 below.

[0144] Table 2 - Percentage of Retained Back Impact Strength After Exposure

[0145]

[0146] A review of Table 2 shows that both materials exhibit good resistance to all tested oils, with material 1-A being superior to material 1-B.

[0147] Comparative Example 1

[0148] Test bars made from the following materials were subjected to tests similar to those in Example 2: copolyesters TX1001, GMX201, and DX4001 (from Eastman Chemical Company); cellulose-based engineering bioplastics GC6011 and GC6021 (from Eastman Chemical Company); and polycarbonate products (MAKROLON polycarbonate PC2608 from Covestro). The results are shown in Table 3 below.

[0149] Table 3 - Percentage of Retained Back Impact Strength After Exposure

[0150]

[0151] A review of Table 3 indicates that, for the oils tested, cellulose-based materials outperformed the other materials. However, comparing Table 3 and Table 2, the materials in Examples 1-A and 1-B were superior to those in Table 3, except for β-pinene, where the cellulose-based polymers were superior to the materials in Table 3.

[0152] Example 3 and Comparative Example

[0153] Test bars made from the following materials were subjected to tests similar to those in Example 2: copolyester EX 1-A; copolyesters TX1001, TX1501, and TX2001 (from Eastman Chemical Company); cellulose-based engineering bioplastic GC6021 (Eastman Chemical Company); polycarbonate products (MAKROLON polycarbonate PC2608 from Covestro); polypropylene products (polypropylene homopolymer PAG3Z-039 from Flint Hills Resources); and ABS plastic products (Terluan GP-35 from Ineos). The test solutions used were as follows (in weight %): Solution A (50% limonene / 50% resorcinol); Solution B (80% MCT oil / 20% limonene); Solution C (95% MCT oil / 5% limonene); and Solution D (99% MCT oil / 1% limonene). The MCT oil was a medium-chain triglyceride oil (MCT oil from Now Sports). The results are shown in Table 4 below.

[0154] Table 4 - Percentage of Retained Back Impact Strength After Exposure

[0155]

[0156] *During the testing, most (5 samples) of the test bars were damaged.

[0157] No data was reported due to severe breakage of the bar in the fixture.

[0158] A review of Table 4 shows that, for the tested limonene / resorcinol solutions, cellulose-based, PP, and Example 1-A materials are superior to the other materials; and for the tested limonene / MCT oil solutions, PP and Example 1-A materials are superior to the other materials.

[0159] Other embodiments will be apparent to those skilled in the art upon consideration of the specification and practice with the embodiments disclosed herein. However, it should be understood that variations and modifications may be made within the spirit and scope of the disclosed embodiments. It is further intended that the specification and examples be considered exemplary only, and the true scope and spirit of the disclosed embodiments are indicated by the appended claims.

Claims

1. An article comprising a molding assembly configured to receive a terpene-containing oil composition, said molding assembly being formed of a copolyester composition comprising at least one copolyester, said copolyester comprising: (a) A dicarboxylic acid component, comprising: i) 97.1 mol% - 98.5 mol% of terephthalic acid residues; ii) 1.5 mol%–2.9 mol% of isophthalic acid residues; (b) A diol component comprising: i) 10 mol%–12 mol% of 2,2,4,4-tetramethyl-1,3-cyclobutanediol residues; and ii) 88 mol%-90 mol% of 1,4-cyclohexanediethanol residues, The total mol% of the dicarboxylic acid component is 100 mol%, and the total mol% of the diol component is 100 mol%; the specific logarithmic viscosity of the copolyester composition is 0.70 to 1.0 dL / g, determined at 25°C in a phenol / tetrachloroethane mass ratio of 60 / 40 at a concentration of 0.5 g / 100 ml; and the Tg of the copolyester composition is 100°C to 115°C, determined by differential scanning calorimetry at a scan rate of 20°C / min according to ATSM D3418.

2. The article of claim 1, wherein the copolyester composition has a specific logarithmic viscosity of 0.75 to 0.95 dL / g.

3. The article according to claim 1 or 2, wherein the copolyester composition has a crystallization half-life of 30 seconds to 5 minutes at 175°C.

4. The article of claim 1 or 2, wherein the molding component comprises a container configured to contain a terpene-containing oil composition and selectively release the terpene-containing oil composition.

5. The article of claim 4, wherein the molding component comprises a container configured to contain a terpene-containing oil composition in the form of a pre-vaporized formulation.

6. The article of claim 1 or 2, wherein the molding component comprises a conduit configured to deliver a terpene-containing oil composition.

7. The article of claim 6, wherein the molding component comprises a conduit configured to deliver a terpene-containing oil composition in vapor form.

8. The article of claim 5 or 7, wherein the article comprises one or more molding components, the molding components comprising a container configured to contain a terpene-containing oil composition and a conduit configured to deliver the terpene-containing oil composition, wherein the container and the conduit are in fluid communication.

9. The article of claim 1 or 2, wherein the article is a steam conveying device configured to convey steam, the steam comprising a terpene-containing oil composition.

10. The article of claim 9, wherein the steam conveying device is a vaporizer.

11. The article of claim 1 or 2, wherein the molding component is selected from injection molded articles, extruded articles, rotationally molded articles, compression molded articles or blow molded articles.

12. The article of claim 1 or 2, wherein when tested according to the method disclosed in Example 2, the reverse impact strength of the molded component after exposure to terpene oil is retained to at least 80%.

13. The article of claim 12, wherein when tested according to the method disclosed in Example 2, the reverse impact strength of the molded component after exposure to d-limonene is retained to at least 95%.

14. The article of claim 1 or 2, wherein the dicarboxylic acid component of the polyester comprises monomer residues having at least 50 mol% recycled content.

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