A modified heat-resistant polyester-polycarbonate copolyester, and a preparation method and application thereof

Abstract

The application provides a modified heat-resistant polyester polycarbonate copolymer with excellent impact strength and high transparency and a preparation method thereof. The rigid structure of 1,4; 3,6-diepihexitol is used to overcome the problem of insufficient heat resistance of PET, and the method of introducing polycarbonate units is used to overcome the problem of insufficient impact strength of 1,4; 3,6-diepihexitol copolymer, and the polymerization method is simple, which is beneficial to subsequent industrial amplification.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to a modified heat-resistant polyester polycarbonate copolyester with high impact strength and high transparency and its preparation method. Background Technology

[0002] Polyethylene terephthalate (PET) is one of the most widely used engineering plastics, with extensive applications in many fields such as fibers, films, and packaging. Currently, my country's PET production capacity has reached 54 million tons per year. However, PET has a low glass transition temperature, and at higher temperatures, it will suffer severe deformation and a significant decline in performance. Therefore, developing heat-resistant modified PET copolyesters has become an urgent problem to be solved.

[0003] 1,4:3,6-Diglyhexanediol is produced by enzymatically decomposing starch from cereals into polysaccharides, followed by hydrogenation of the polysaccharides to obtain a hexahydrol, which is then further dehydrated by two molecules to yield 1,4:3,6-diglyhexanediol. This bio-based raw material exists in three isomers: isosorbide, isomannitol, and isoisosorbide. Currently, only isosorbide is produced on a large industrial scale. Isosorbide is non-toxic and environmentally friendly, and its rigid chiral structure effectively improves the heat resistance and mechanical properties of polymers, making it widely used in the synthesis of condensation polymers such as polyesters, polyurethanes, polyamides, and polycarbonates. However, the rigid structure of isosorbide also reduces the impact strength of copolymers. Adding inorganic or organic reinforcing materials such as glass fibers or rubber particles can effectively improve impact strength, but this significantly reduces the material's transparency. Therefore, maintaining high transparency while improving heat resistance and impact strength is a critical and urgent issue that needs to be addressed.

[0004] In summary, given the low glass transition temperature and poor heat resistance of PET, the poor impact resistance of the polymer due to the addition of isosorbide, and the opacity caused by the doping of reinforcing materials, how to prepare a novel copolyester with high heat resistance, impact resistance, and high transparency through a simple method to improve its added value and expand its application range is an urgent problem to be solved. Summary of the Invention

[0005] To overcome the shortcomings of existing technologies, this invention provides a modified heat-resistant polyester polycarbonate copolyester and its preparation method. This invention utilizes the rigid structure of 1,4;3,6-diglychalcogenide hexahydride to overcome the insufficient heat resistance of traditional polyester PET. Furthermore, without affecting the heat resistance of the copolyester, the introduction of polycarbonate segments overcomes the problem of insufficient impact strength in 1,4;3,6-diglychalcogenide hexahydride-modified PET copolyester. This polymerization method is simple and beneficial for subsequent industrial scale-up.

[0006] The technical solution of the present invention is as follows:

[0007] A modified polyester-polycarbonate copolyester is prepared by copolymerization of polyester prepolymer 1 and polycarbonate prepolymer of Formula II.

[0008]

[0009] Polyester prepolymer 1 is prepared by esterification and / or transesterification of the compound represented by Formula A, ethylene glycol, 1,4;3,6-diglihexanediol, and the diol represented by Formula B.

[0010] Formula A: R 1 OOC-L-COOR 1

[0011] Formula B: HO-R-OH

[0012] R 1 The following groups, which may be identical or different and independently selected from H, are unsubstituted or optionally substituted by one, two or more Ra groups: C 1-12 Alkyl or C 6-20 Aryl;

[0013] L is selected from C that is unsubstituted or optionally substituted by one, two or more Rb. 6-20 Aryl;

[0014] R is selected from C 3-12 Alkyl, -C 1-6 Alkyl-C 3-20 cycloalkyl-C 1-6 Alkyl- or C 3-20 cycloalkyl;

[0015] Ra and Rb may be the same or different, and they are independently selected from halogens. 1-12 Alkyl, Halogenated C 1-12 Alkyl or C 1-12 Alkoxy;

[0016] The 1,4;3,6-diglycidol is selected from at least one of isosorbide, isomannitol, and isoidulol.

[0017]

[0018] T is selected from unsubstituted groups, or optionally substituted by one, two or more Rc groups, of the following groups: C 3-12 Alkyl, C 3-20 cycloalkyl, -C 1-6 Alkyl-C 3-20 cycloalkyl-C 1-6 Alkyl-, 3-12-membered heterocyclic or 3-12-membered heterocyclic with 3-12-membered heterocyclic;

[0019] Rc is selected from halogens, C 1-12 Alkyl, Halogenated C 1-12 Alkyl or C 1-12 Alkyl group.

[0020] According to an embodiment of the present invention, the prepolymer 1 has the structure shown in Formula I:

[0021]

[0022] Wherein, L is selected from C 6-14 Aryl groups, such as phenyl or naphthyl groups;

[0023] R is selected from C 3-10 Alkyl, -C 1-3 Alkyl-C 3-12 cycloalkyl-C 1-3 Alkyl- or C 3-12 Cycloalkyl groups, such as propyl, butyl, pentyl, hexyl, cyclohexyl, or -methyl-cyclohexyl-methyl-.

[0024] According to an embodiment of the present invention, compound R of formula A 1 OOC-L-COOR 1 This represents a diacid and / or diester. For example, the compound shown in Formula A represents one diacid, one diester, two or more diacids, two or more diesters, or a mixture of one or more diacids and one or more diesters. Similarly, the diol HO-R-OH shown in Formula B can be a mixture of one or more diols.

[0025] According to an embodiment of the present invention, R 1 Selected from H, C 1-10 Alkyl or C 6-14 Aryl, for example R 1 Selected from H, ethyl, propyl, butyl, pentyl, hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, 1,2-dimethylbutyl, or phenyl.

[0026] According to an embodiment of the present invention, T is selected from C. 3-10 Alkyl, C 3-6 cycloalkyl, C 1-3 Alkyl-C 3-6 cycloalkyl-C 1-3Alkyl, 3-6 membered heterocyclic group, for example, T is selected from propyl, butyl, pentyl, hexyl, cyclohexyl, -methyl-cyclohexyl-methyl- or

[0027] According to an embodiment of the present invention, in the polyester prepolymer 1, the molar percentage of 1,4;3,6-diglycidylhexanediol units is 10-90%, the molar percentage of ethylene glycol units is 1-90%, and the molar percentage of diol units represented by formula B is 1-90% based on the total molar amount of copolyester diols; preferably, in the polyester prepolymer 1, the molar percentage of 1,4;3,6-diglycidylhexanediol units is 10-50%, the molar percentage of ethylene glycol units is 20-70%, and the molar percentage of diol units represented by formula B is 10-60%.

[0028] According to an embodiment of the present invention, in polyester prepolymer 1, the molar percentage of terephthalic acid unit in Formula I is 70-100% based on the total molar amount of diacids, and if other aromatic diacids are contained, the molar percentage of other diacid units is 0-30%.

[0029] According to an embodiment of the present invention, the mass fraction of the polyester prepolymer of Formula I is 70-95% based on the total mass of the modified polyester polycarbonate copolyester, and the mass fraction of the polycarbonate prepolymer of Formula ⅠⅠ is 5-30%.

[0030] According to an embodiment of the present invention, the modified polyester polycarbonate copolyester has an intrinsic viscosity of 0.5 to 1.2 dL / g and a glass transition temperature of 70 to 130°C; preferably, the intrinsic viscosity is 0.5 to 0.9 dL / g and the glass transition temperature is 88 to 125°C.

[0031] According to an embodiment of the present invention, the impact strength of the modified polyester polycarbonate copolyester is 240-550 J / m, preferably 270-480 J / m.

[0032] According to an embodiment of the present invention, the light transmittance of the modified polyester polycarbonate copolyester is not less than 82%, for example, 82%-99%.

[0033] The present invention also provides a method for preparing the above-mentioned modified polyester polycarbonate copolyester, comprising the following steps:

[0034] (1) Esterification / transesterification reaction of polyester: The compound shown in Formula A, ethylene glycol, 1,4;3,6-diglihexanediol and the diol shown in Formula B are mixed and esterified and / or transesterified to obtain polyester prepolymer 1.

[0035] Formula A: R 1 OOC-L-COOR1

[0036] Formula B: HO-R-OH

[0037] Among them, L, R, R 1 It has the above meaning;

[0038] (2) Transesterification reaction of polycarbonate: The carbonate diester shown in formula C and the diol shown in formula D are mixed and subjected to transesterification reaction to obtain the polycarbonate prepolymer shown in formula II.

[0039] Formula C: R 2 O-CO-OR 2

[0040] Formula D: HO-T-OH

[0041] Wherein, T has the meanings described above;

[0042] R 2 The same or different, independently selected from the following groups that are unsubstituted or optionally substituted by one, two or more Rf groups: C 1-12 Alkyl or C 6-20 Aryl;

[0043] Rf is selected from halogens, C 1-12 Alkyl, Halogenated C 1-12 Alkyl or C 1-12 Alkoxy;

[0044] (3) Melt polycondensation reaction: Polyester prepolymer 1 and polycarbonate prepolymer shown in Formula II are mixed and polycondensed to prepare modified polyester polycarbonate copolyester.

[0045] According to an embodiment of the present invention, the diester represented by formula C can be a mixture of one or more diesters.

[0046] According to an embodiment of the present invention, the diol represented by formula D can be a mixture of one or more diesters.

[0047] According to an embodiment of the present invention, R 2 Selected from C 1-10 Alkyl or C 6-14 Aryl. According to an embodiment of the present invention, the diol represented by formula B is selected from at least one of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, and 1,4-cyclohexanediethanol, preferably 1,3-cyclohexanediethanol and 1,4-cyclohexanediethanol.

[0048] According to an embodiment of the present invention, the compound represented by Formula A is selected from terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, diphenyl terephthalate, dimethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, diphenyl terephthalate, dimethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, diphenyl terephthalate, 1,4-naphthalenedicarboxylic acid ... diphenyl terephthalate, diethyl terephthalate, dipropyl terephthalate, di At least one of dimethyl formate, diethyl 1,4-naphthalenedicarboxylate, dipropyl 1,4-naphthalenedicarboxylate, dibutyl 1,4-naphthalenedicarboxylate, dioctyl 1,4-naphthalenedicarboxylate, diphenyl 1,4-naphthalenedicarboxylate, dimethyl 2,6-naphthalenedicarboxylate, diethyl 2,6-naphthalenedicarboxylate, dipropyl 2,6-naphthalenedicarboxylate, dibutyl 2,6-naphthalenedicarboxylate, dioctyl 2,6-naphthalenedicarboxylate, and diphenyl 2,6-naphthalenedicarboxylate, preferably at least one of terephthalic acid, dimethyl terephthalate, phthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylate, diethyl terephthalate, and dimethyl isophthalate.

[0049] According to an embodiment of the present invention, step (1) is carried out in an inert gas atmosphere, such as a nitrogen atmosphere.

[0050] According to an embodiment of the present invention, in step (1), the molar ratio of the compound represented by formula A to the diol (including ethylene glycol, 1,4;3,6-diglycidol and the diol represented by formula B) is 1:1 to 3, preferably 1:1.1 to 2.

[0051] According to an embodiment of the present invention, in step (1), the molar ratio of ethylene glycol, 1,4;3,6-diglycidol and the diol represented by formula B is 1:(0.01-1):(0.01-1), for example 1:0.125:0.5, 1:0.25:0.625, 1:0.313:0.438, 1:1:1.67, 1:0.357:0.5.

[0052] According to an embodiment of the present invention, in step (1), the esterification reaction is carried out under high temperature and high pressure, the reaction temperature is 200-260°C, preferably 220-260°C; the reaction pressure is 200-400 kPa, preferably 200-330 kPa; and the total time of the esterification reaction is 2-20 hours, preferably 3-10 hours.

[0053] According to an embodiment of the present invention, in step (1), the transesterification reaction is carried out under normal pressure, the reaction temperature of the transesterification reaction is 180-260°C, preferably 200-240°C, and the total time of the transesterification reaction is 2-20 hours, preferably 3-10 hours.

[0054] According to an embodiment of the present invention, the purity of the 1,4:3,6-diglycidol is 99.0% or higher, preferably 99.5% or higher.

[0055] According to an embodiment of the present invention, step (1) is carried out in the presence of transesterification catalyst 1, which is at least one of the following: metal oxides, metal hydroxides, alkoxy metal compounds, metal phosphates, metal sulfates, metal acetylacetone complexes, metal acetates, and metal halides containing magnesium, zinc, manganese, aluminum, cobalt, and tin.

[0056] Preferably, the transesterification catalyst 1 is at least one of magnesium oxide, magnesium hydroxide, magnesium stearate, magnesium sulfate, magnesium acetate, magnesium chloride hexahydrate, zinc oxide, zinc hydroxide, zinc stearate, zinc phosphate, zinc sulfate, zinc acetate, manganese oxide, manganese acetylacetone, manganese sulfate, manganese acetate, manganese chloride, aluminum oxide, aluminum hydroxide, aluminum phosphate, aluminum sulfate, aluminum acetate, cobalt oxide, cobalt acetylacetone, cobalt acetate, cobalt acetate tetrahydrate, dibutyltin oxide, dibutyltin dichloro, tributyltin acetate, tributyltin chloride, and trimethyltin chloride.

[0057] According to an embodiment of the present invention, step (1) further includes a post-processing step, which includes removing byproducts from the reaction to obtain polyester prepolymer 1.

[0058] According to an embodiment of the present invention, the carbonate diester represented by Formula C is selected from any one or a mixture of several of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, dimethyl carbonate, and dinaphthalene carbonate; preferably at least one of dimethyl carbonate, diethyl carbonate, and diphenyl carbonate.

[0059] According to an embodiment of the present invention, the diol represented by Formula D is selected from at least one of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, 1,4-cyclohexanediethanol, and 1,4;3,6-diglycidol, preferably 1,4;3,6-diglycidol and 1,4-cyclohexanediethanol.

[0060] According to an embodiment of the present invention, in step (2), the molar ratio of the carbonate diester represented by formula C to the diol represented by formula D is 2:1 to 1:10, preferably 1.5:1 to 1:5.

[0061] According to an embodiment of the present invention, step (2) is carried out in an inert gas atmosphere, such as a nitrogen atmosphere.

[0062] According to an embodiment of the present invention, in step (2), the transesterification reaction is carried out under normal pressure, the reaction temperature of the transesterification reaction is 90-180°C, preferably 100-160°C, and the total time of the transesterification reaction is 2-20 hours, preferably 3-10 hours.

[0063] According to an embodiment of the present invention, step (2) is carried out in the presence of an ester exchange catalyst 2, wherein the ester exchange catalyst 2 is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetone complexes, titanium-based organic compounds, tin-based organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates, and metal halides.

[0064] Preferably, it is at least one of lithium hydride, sodium hydride, potassium hydride, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium oxide, lithium acetylacetonate, sodium acetylacetonate, potassium acetylacetonate, magnesium acetylacetonate, zinc acetylacetonate, calcium acetylacetonate, tetraethoxytitanium, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide, stannous octoate, dibutyltin dilaurate, lithium methoxide, sodium methoxide, potassium methoxide, lithium carbonate, sodium carbonate, potassium carbonate, cesium carbonate, sodium bicarbonate, potassium bicarbonate, sodium phosphite, potassium phosphite, phosphoric acid, acetic acid, p-toluenesulfonic acid, m-toluenesulfonic acid, benzenesulfonic acid, trimethylamine, triethylamine, dimethylaminopyridine, lithium acetate, sodium acetate, potassium acetate, zinc acetate, magnesium acetate, manganese acetate, lithium chloride, sodium chloride, potassium chloride, and cesium chloride.

[0065] According to an embodiment of the present invention, step (2) further includes a post-processing step, which includes removing byproducts from the reaction to obtain the polycarbonate prepolymer represented by formula II.

[0066] According to an embodiment of the present invention, the reaction in step (3) is carried out in the presence of a polycondensation catalyst, which is at least one of an organometallic compound or oxide or complex containing titanium, antimony, silicon, germanium or zirconium; preferably at least one of titanium dioxide, silicon dioxide / titanium dioxide complex, zirconium dioxide / titanium dioxide complex, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycolate, antimony acetate, germanium dioxide, and germanium acetate.

[0067] According to an embodiment of the present invention, in step (3), the amount of the polycondensation catalyst added is 0.001 wt.% to 0.05 wt.% of the theoretical yield of the polyester polycarbonate copolyester, preferably 0.001 wt.% to 0.04 wt.%.

[0068] According to an embodiment of the present invention, in step (3), the temperature of the polycondensation reaction is 200–300°C, preferably 240–280°C; the time of the polycondensation reaction is 1–48 hours, preferably 3–12 hours. The pressure of the reaction system during the polycondensation reaction is less than 200 Pa, for example 30–190 Pa, preferably not greater than 110 Pa.

[0069] The present invention also provides the application of the modified polyester polycarbonate copolyester as described above as an engineering plastic in the fields of fiber, film and packaging.

[0070] Beneficial effects of the present invention

[0071] This invention provides a modified heat-resistant polyester polycarbonate copolyester with excellent impact strength and high transparency, and its preparation method. This invention overcomes the problem of insufficient heat resistance of PET by utilizing the rigid structure of 1,4;3,6-diglihexyl alcohol. By introducing polycarbonate units, it overcomes the problem of insufficient impact strength in 1,4;3,6-diglihexyl alcohol copolyester. Furthermore, the polymerization method is simple and facilitates subsequent industrial scale-up.

[0072] The polyester polycarbonate copolyester prepared by this invention is a transparent and colorless solid with an intrinsic viscosity of 0.5 to 1.2 dL / g and high impact strength. It can be used directly as a plastic. Furthermore, the copolyester main chain contains a high and controllable content of 1,4;3,6-diglycidol or its mixture, which greatly improves the heat resistance and mechanical properties of PET.

[0073] Terminology Definitions and Explanations

[0074] The term "halogen" refers to fluorine, chlorine, bromine, and / or iodine. Correspondingly, the term "halogenated" refers to fluorination, chlorination, bromination, and / or iodination. Within the scope of this document, when an atom, residue, group, or part is halogenated, the atom at the halogenated position can be monosubstituted, disubstituted, or polysubstituted up to fully substituted by the halogen atom, for example, "halogenated C..." 1-12 Alkyl groups, etc.

[0075] In this application, some substituents marked with an asterisk (*) indicate connection sites.

[0076] Term "C" 1-12 "Alkyl" should be understood as representing a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms. For example, "C 1-10"Alkyl" refers to straight-chain and branched alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms. 1-6 "Alkyl" means a straight-chain or branched alkyl group having 1, 2, 3, 4, 5, or 6 carbon atoms. The alkyl group is, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, or their isomers.

[0077] Term "C" 3-12 "Alkyl" refers to straight-chain and branched alkyl groups having 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms, such as propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, 2-methylbutyl, 1-methylbutyl, 1-ethylpropyl, 1,2-dimethylpropyl, neopentyl, 1,1-dimethylpropyl, 4-methylpentyl, 3-methylpentyl, 2-methylpentyl, 1-methylpentyl, 2-ethylbutyl, 1-ethylbutyl, 3,3-dimethylbutyl, 2,2-dimethylbutyl, 1,1-dimethylbutyl, 2,3-dimethylbutyl, 1,3-dimethylbutyl, or 1,2-dimethylbutyl, etc.

[0078] Term "C" 3-20 "Cycloalkyl" should be understood to refer to saturated monovalent monocyclic, bicyclic, or bridged cycloalkanes having 3 to 20 carbon atoms, preferably "C". 3-12 cycloalkyl. The term "C" 3-12 "Cycloalkyl" should be understood to refer to saturated monovalent monocyclic, bicyclic, or bridged cycloalkanes having 3, 4, 5, 6, 7, 8, 9, 10, 11, or 12 carbon atoms. The C 3-12 The cycloalkyl group can be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, or cyclodecyl, or a bicyclic hydrocarbon group, such as decahydronaphthalene. The cycloalkyl group can be a spirocyclic group, such as spiro[3,3] ring, spiro[3,4] ring, spiro[3,5] ring, spiro[4,4] ring, spiro[4,5] ring, or spiro[5,5] ring.

[0079] The term "3-12 membered heterocyclic group" refers to a saturated or partially unsaturated monovalent monocyclic or bicyclic non-aromatic hydrocarbon ring containing 1-5 heteroatoms independently selected from N, O, and S, and having a total of 3-12 ring atoms. The term "3-10 membered heterocyclic group" refers to a saturated or partially unsaturated monovalent monocyclic or bicyclic hydrocarbon ring containing 1-5, optionally 1-3, heteroatoms selected from N, O, and S, and also, for example, "3-6 membered heterocyclic group," "4-6 membered heterocyclic group," and "5-6 membered heterocyclic group." When all ring atoms in the heterocyclic group are connected by saturated bonds, it is called a saturated heterocyclic group. When it has 1, 2, 3, or more alkene or alkyne bonds, but does not cause the heterocyclic group to form an aromatic ring, it is called a heterocyclic alkenyl or heterocyclic alkyne group. The heterocyclic group can be connected to the rest of the molecule through any one of the un-alkyne bonded carbon atoms (if present). For example, "3-6 membered heterocyclic group" is further divided into "3-6 membered saturated heterocyclic group", "3-6 membered heterocyclic alkenyl group", and "3-6 membered heterocyclic alkynyl group". In particular, the heterocyclic group may include, but is not limited to: 4-membered ring, such as azirmonobutyl, azirmonobutylenyl, oxacyclobutyl or oxacyclobutylenyl; 5-membered ring, such as tetrahydrofuranyl, dihydrofuranyl, dioxacyclopentenyl, pyrrolyl, dihydroimidazolyl, imidazolyl, dihydropyrazolyl, pyrazolyl, pyrrolinyl, oxazolinyl, oxazolinyl, thiazolinyl or thiazolyl; or 6-membered ring, such as pyranyl, tetrahydropyranyl, thiaranyl, dihydropyrimidinyl, piperidinyl, morpholinyl, dithiaalkyl, thiomorpholinyl, piperazine or trithiaalkyl; or 7-membered ring, such as diazacycloheptyl or diazacycloheptenyl. Optionally, the heterocyclic group can be a fused ring, a bridged ring, or a spirocyclic ring. The heterocyclic group can be bicyclic, for example, but not limited to, hexahydropyrrolo[1,2-a]pyrazin-2(1H)-yl. The heterocyclic group can be partially unsaturated, i.e., it can contain one, two, or more double bonds, for example, but not limited to, 2,5-dihydro-1H-pyrroloyl, 3,6-dihydro-2H-pyranyl, 1,2,3,6-tetrahydropyridyl, 4H-[1,3,4]thiadiazinyl, 4,5-dihydrooxazolyl, or 4H-[1,4]thiazinyl, 5H,6H,8H-[1,2,4]triazolo[4,3-a]pyrazinyl. The heterocyclic group can be fused with the above-mentioned 4-, 5-, 6-, or 7-membered ring benzo[a], such as 2,3-dihydrobenzofuran, benzopyran, 1,2-dihydroquinazoline, 3,4-dihydroquinazoline, etc.

[0080] The term "3-12-membered heterocyclic group with 3-12-membered heterocyclic group" means that two of the above-mentioned 3-12-membered heterocyclic groups are linked together to form a ring structure.

[0081] Term "C" 6-20 "Aryl" should be understood to preferably represent a monocyclic, bicyclic, or tricyclic hydrocarbon ring having 6 to 20 carbon atoms and possessing monovalent aromaticity or partial aromaticity, preferably "C". 6-14 Aryl. The term "C"6-14 "Aryl" should be understood to preferably represent a monovalent aromatic or partially aromatic monocyclic, bicyclic, or tricyclic hydrocarbon ring ("C") having 6, 7, 8, 9, 10, 11, 12, 13, or 14 carbon atoms. 6-14 Aryl), particularly a ring with 6 carbon atoms (“C6 aryl”), such as phenyl; or biphenyl, or a ring with 9 carbon atoms (“C9 aryl”), such as indenyl or indenyl, or a ring with 10 carbon atoms (“C9 aryl”). 10 Aryl groups, such as tetrahydronaphthyl, dihydronaphthyl, or naphthyl, or rings with 13 carbon atoms (“C”). 13 Aryl groups, such as fluorene groups, or rings with 14 carbon atoms (“C”). 14 Aryl), for example, anthracene. When the C 6-20 When the aryl group is substituted, it can be monosubstituted or polysubstituted. Furthermore, there are no restrictions on the substitution site; for example, it can be ortho, para, or meta substituted.

[0082] The term "halogenated C" 1-12 "alkyl" indicates C 1-12 The H on the alkyl group is optionally replaced by 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10 halogens, as indicated by "halogenated" and "C". 1-12 "Alkyl" has the definition as described above. The substitution refers to substitution on the same carbon atom or on different carbon atoms. Optional "halogenated C" 1-6 Alkyl group. The "halogenated C" 1-12 "Alkyl" is, for example, trifluoromethyl.

[0083] Term "C" 1-12 "Alkoxy" indicates C 1-12 When one, two, or three carbons in an alkyl group are replaced by O, the case described with "C" 1-12 "alkyl" has the definition as described above. Optionally, "C" 1-6 "alkoxy". The "C" 1-12 "Alkoxy" can be, for example, methoxy, ethoxy, or propoxy. Detailed Implementation

[0084] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. It should be understood that the following embodiments are merely illustrative and explanatory of the present invention, and should not be construed as limiting the scope of protection of the present invention. All technologies implemented based on the above content of the present invention are covered within the scope of protection intended by the present invention.

[0085] Unless otherwise stated, the raw materials and reagents used in the following examples are commercially available products or can be prepared by known methods.

[0086] The performance parameters in the following examples were all measured using the following methods.

[0087] Intrinsic viscosity: 0.125 g of copolyester was dissolved in 25 mL of phenol tetrachloroethane solution, and the intrinsic viscosity of the polymer was determined using an Ubbelohde viscometer in a thermostat at 25 °C.

[0088] Glass transition temperature: The copolyester was heated at 300℃ for 5 minutes. After eliminating the thermal history, the furnace temperature was rapidly cooled to room temperature. The glass transition temperature of the copolyester was then determined during a second scan at a heating rate of 10℃ / min.

[0089] Impact strength: The cantilever beam impact strength of copolyester specimens with a 4 mm thickness and a notch was determined at 23 °C using a cantilever beam impact strength tester in accordance with GB-T1843-2008.

[0090] Transmittance: The transmittance of a 50mm circular copolyester sample was measured at 23℃ using a transmittance meter according to GB / T2410-2008.

[0091] Example 1

[0092] (1) In a 500 mL glass flask, under a nitrogen atmosphere, add 83.0 g (0.5 mol) terephthalic acid, 24.8 g (0.4 mol) ethylene glycol, 7.3 g (0.05 mol) isosorbide, and 28.8 g (0.2 mol) 1,4-cyclohexanediethanol (the molar ratio of dicarboxylic acid to diol is 1:1.3). Under a pressure of 280 kPa, gradually raise the temperature of the system to 245 °C and react for 3.5 hours. The water byproduct generated by the reaction is completely evaporated to obtain prepolymer I-1.

[0093] (2) At room temperature, 116.8 g (0.8 mol) isosorbide, 36.0 g (0.4 mol) dimethyl carbonate and 0.0026 g potassium methoxide as a transesterification catalyst were added to a 250 mL glass flask under a nitrogen atmosphere (the molar ratio of isosorbide to dimethyl carbonate was 2:1). The mixture was stirred at 60 °C and then gradually heated to 160 °C. The reaction was carried out for 3 hours, and the methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer II-1.

[0094] (3) Add 70g of prepolymer I-1 and 30g of prepolymer II-1 to a 250mL glass flask, add 0.013wt% tetrabutyl titanate as a polycondensation catalyst, gradually build up a vacuum to 100Pa, and react at 280℃ for 4 hours to obtain polyester polycarbonate copolyester.

[0095] The copolyester was tested and found to have an intrinsic viscosity of 0.66 g / dL, a glass transition temperature of 85℃, an impact strength of 456 J / m, and a light transmittance of 87%.

[0096] Example 2

[0097] (1) In a 500 mL glass flask, under a nitrogen atmosphere, add 66.4 g (0.4 mol) terephthalic acid, 16.6 g (0.1 mol) phthalic acid, 19.84 g (0.32 mol) ethylene glycol, 11.68 g (0.08 mol) isosorbide, and 28.8 g (0.2 mol) 1,3-cyclohexanediethanol (the molar ratio of dicarboxylic acid to diol is 1:1.2). Under a pressure of 305 kPa, gradually raise the temperature of the system to 247 °C and react for 4 hours. The water byproduct produced by the reaction is completely evaporated to obtain prepolymer I-2.

[0098] (2) At room temperature, 43.2 g (0.3 mol) of 1,4-cyclohexanediethanol, 18.0 g (0.2 mol) of dimethyl carbonate and 0.0018 g of lithium acetylacetone transesterification catalyst were added to a 250 mL glass flask under a nitrogen atmosphere (the molar ratio of 1,4-cyclohexanediethanol to dimethyl carbonate was 1.5:1). The mixture was stirred at 80 °C and then gradually heated to 180 °C. The reaction was carried out for 3.2 hours. The methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer II-2.

[0099] (3) Add 75g of prepolymer I-2 and 25g of prepolymer II-2 into a 250mL glass flask, add 0.03wt% antimony acetate condensation catalyst, gradually build up a vacuum to 80Pa, and react at 273℃ for 4.2 hours to obtain polyester polycarbonate copolyester.

[0100] Tests showed that the copolyester had an intrinsic viscosity of 0.68 g / dL, a glass transition temperature of 91℃, an impact strength of 417 J / m, and a light transmittance of 88%.

[0101] Example 3

[0102] (1) In a 500 mL glass flask, under a nitrogen atmosphere, 97.0 g (0.5 mol) dimethyl terephthalate, 10.66 g (0.175 mol) ethylene glycol, 18.25 g (0.125 mol) isosorbide, 36.0 g (0.25 mol) 1,4-cyclohexanediethanol (the molar ratio of diester to diol is 1:1.1) and 0.022 wt% zinc acetate transesterification catalyst were added. Under a pressure of 295 kPa, the system temperature was gradually increased to 253 °C and the reaction was carried out for 4.5 hours. The methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer I-3.

[0103] (2) At room temperature, 69.12 g (0.48 mol) of 1,3-cyclohexanediethanol, 36.0 g (0.4 mol) of dimethyl carbonate and 0.003 g of tetrabutyl titanate, a transesterification catalyst, were added to a 250 mL glass flask under a nitrogen atmosphere (the molar ratio of 1,3-cyclohexanediethanol to dimethyl carbonate was 1.2:1). The mixture was stirred at 90 °C and then gradually heated to 170 °C. The reaction was carried out for 4 hours, and the methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer II-3.

[0104] (3) 80g of prepolymer I-3 and 20g of prepolymer II-3 were added to a 250mL glass flask, and 0.036wt% antimony trioxide condensation catalyst was added. The vacuum was gradually built up to 90Pa, and the reaction was carried out at 275℃ for 4.9 hours to obtain a polyester polycarbonate copolyester. The intrinsic viscosity of the copolyester was tested to be 0.71g / dL, the glass transition temperature was 101℃, the impact strength was 371J / m, and the light transmittance was 91%.

[0105] Example 4

[0106] (1) In a 1000 mL glass flask, under a nitrogen atmosphere, add 166.0 g (1.0 mol) terephthalic acid, 49.6 g (0.8 mol) ethylene glycol, 36.5 g (0.25 mol) isosorbide, and 50.4 g (0.35 mol) 1,4-cyclohexanediethanol (the molar ratio of dicarboxylic acid to diol is 1:1.4). Under a pressure of 310 kPa, gradually raise the temperature of the system to 250 °C and react for 4 hours. The water byproduct produced by the reaction is completely evaporated to obtain prepolymer I-4.

[0107] (2) At room temperature, 11.7 g (0.3 mol) isosorbide, 32.4 g (0.36 mol) dimethyl carbonate and 0.0015 g lithium methoxide transesterification catalyst were added to a 250 mL glass flask under a nitrogen atmosphere (the molar ratio of isosorbide to dimethyl carbonate was 1:1.2). The mixture was stirred at 60 °C and then gradually heated to 200 °C. The reaction was carried out for 2.8 hours. The methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer II-4.

[0108] (3) 85g of prepolymer I-4 and 15g of prepolymer II-4 were added to a 250mL glass flask, along with 0.013wt.% germanium dioxide as a polycondensation catalyst. A vacuum was gradually established to 80Pa, and the reaction was carried out at 280℃ for 5 hours to obtain a polyester polycarbonate copolyester. The copolyester had an intrinsic viscosity of 0.75g / dL, a glass transition temperature of 109℃, an impact strength of 330J / m, and a light transmittance of 91%.

[0109] Example 5

[0110] (1) In a 1000 mL glass flask, under a nitrogen atmosphere, add 166.0 g (1.0 mol) terephthalic acid, 18.6 g (0.3 mol) ethylene glycol, 43.8 g (0.3 mol) isosorbide, and 72.0 g (0.5 mol) 1,3-cyclohexanediethanol (the molar ratio of dicarboxylic acid to diol is 1:1.1). Under a pressure of 330 kPa, gradually raise the temperature of the system to 255 °C and react for 3.5 hours. The water byproduct generated by the reaction is completely evaporated to obtain prepolymer I-5.

[0111] (2) At room temperature, 116.8 g (0.8 mol) isosorbide, 85.6 g (0.4 mol) diphenyl carbonate and 0.003 g tetraethoxytitanium ester exchange catalyst were added to a 500 mL glass flask under a nitrogen atmosphere (the molar ratio of isosorbide to diphenyl carbonate was 2:1). The mixture was stirred at 60 °C and then gradually heated to 200 °C. The reaction was carried out for 3 hours, and the byproduct toluene produced by the reaction was completely distilled off to obtain prepolymer II-5.

[0112] (3) 90g of prepolymer I-5 and 10g of prepolymer II-5 were added to a 250mL glass flask, along with 0.025wt% of a silica / titanium dioxide composite polycondensation catalyst. A vacuum was gradually established to 110Pa, and the reaction was carried out at 280℃ for 4.8 hours to obtain a copolyester. The copolyester had an intrinsic viscosity of 0.69g / dL, a glass transition temperature of 125℃, an impact strength of 302J / m, and a light transmittance of 92%.

[0113] Example 6

[0114] (1) In a 5L reactor, under a nitrogen atmosphere, add 1660g (10.0mol) terephthalic acid, 434g (7.0mol) ethylene glycol, 365g (2.5mol) isosorbide, and 504g (3.5mol) 1,4-cyclohexanediethanol (the molar ratio of dicarboxylic acid to diol is 1:1.3). Under a pressure of 280kPa, gradually raise the system temperature to 252℃ and react for 3.5 hours. The byproduct water generated by the reaction is completely evaporated to obtain copolyester prepolymer I-6.

[0115] (2) At room temperature, 1440g (10.0mol) of 1,4-cyclohexanediethanol, 180g (2.0mol) of diester and 0.022g of magnesium acetylacetonate transesterification catalyst were added to a 5L reactor under a nitrogen atmosphere (the molar ratio of 1,4-cyclohexanediethanol to dimethyl carbonate was 5:1). The mixture was stirred at 80°C and then gradually heated to 175°C. The reaction was carried out for 4.2 hours. The methanol byproduct produced by the reaction was completely distilled off to obtain prepolymer II-6.

[0116] (3) 850g of prepolymer I-6 and 150g of prepolymer II-6 were added to a 5L reactor, along with 0.017wt.% tetrabutyl titanate as a polycondensation catalyst. A vacuum was gradually established to 80Pa, and the reaction was carried out at 280℃ for 4 hours to obtain a copolyester. The copolyester had an intrinsic viscosity of 0.67g / dL, a glass transition temperature of 112℃, an impact strength of 314J / m, and a light transmittance of 90%.

[0117] Comparative Example 1

[0118] (1) In a 5L reactor, 1660g (10mol) of terephthalic acid and 744g (12mol) of ethylene glycol (the molar ratio of diacid to glycol is 1:1.2) were added under a nitrogen atmosphere. The system temperature was gradually increased to 255℃ under a pressure of 320kPa and the reaction was carried out for 3.5 hours. The water byproduct generated by the reaction was completely evaporated to obtain the copolyester prepolymer.

[0119] (2) 2000g of copolyester prepolymer and 0.023wt.% antimony trioxide polycondensation catalyst were added to a 5L reactor, and a vacuum was gradually built up to 80Pa. The reaction was carried out at 282℃ for 4 hours to obtain the copolyester. The intrinsic viscosity of the copolyester was tested to be 0.68g / dL, the glass transition temperature was 68℃, the impact strength was 61J / m, and the light transmittance was 89%.

[0120] Comparative Example 2

[0121] (1) In a 5L reactor, 1660g (10mol) of terephthalic acid, 589g (9.5mol) of ethylene glycol and 365g (2.5mol) of isosorbide (the molar ratio of diacid to diol is 1:1.2) were added. Under a nitrogen atmosphere, the system temperature was gradually increased to 252℃ and the reaction was carried out for 3.7 hours. The water byproduct generated by the reaction was completely evaporated to obtain the copolyester prepolymer.

[0122] (2) 2000g of copolyester prepolymer and 0.012wt.% tetrabutyl titanate, a polycondensation catalyst, were added to a 5L reactor. A vacuum was gradually established to 90Pa, and the reaction was carried out at 276℃ for 4.2 hours to obtain the copolyester. The intrinsic viscosity of the copolyester was tested to be 0.67g / dL, its glass transition temperature was 110℃, its impact strength was 12J / m, and its light transmittance was 90%.

[0123] The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiments. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A modified polyester polycarbonate copolyester, characterized in that, It is prepared by copolymerization of polyester prepolymer 1 and polycarbonate prepolymer shown in Formula II. Formula II The polyester prepolymer 1 is prepared by esterification and / or transesterification of the compound represented by Formula A, ethylene glycol, 1,4;3,6-diglihexanediol, and the diol represented by Formula B. Formula A: R 1 OOC-L-COOR 1 Formula B: HO-R-OH The compound represented by Formula A is selected from at least one of terephthalic acid, isophthalic acid, and phthalic acid; R is selected from C 3-6 Alkyl, -C 1-3 Alkyl-C 4-6 cycloalkyl-C 1-3 Alkyl- or C 4-6 cycloalkyl; The 1,4;3,6-diglycidol is selected from at least one of isosorbide, isomannitol and isoidol: ； T is selected from the following groups: C 3-6 Alkyl, C 4-6 cycloalkyl or -C 1-3 Alkyl-C 4-6 cycloalkyl-C 1-3 alkyl-; The polyester prepolymer 1 has a mass fraction of 70-95% based on the total mass of the modified polyester polycarbonate copolyester, and the polycarbonate prepolymer represented by Formula ⅠⅠ has a mass fraction of 5-30%.

2. The modified polyester polycarbonate copolyester according to claim 1, characterized in that, The polyester prepolymer 1 has the structure shown in Formula I: Formula I Wherein, L is selected from phenyl; R is selected from C 3-6 Alkyl, -C 1-3 Alkyl-C 4-6 cycloalkyl-C 1-3 Alkyl- or C 4-6 Cycloalkyl.

3. The modified polyester polycarbonate copolyester according to claim 1, characterized in that, R is selected from -C 1-3 Alkyl-C 5-6 cycloalkyl-C 1-3 Alkyl- or C 5-6 Cycloalkyl.

4. The modified polyester polycarbonate copolyester according to claim 1, characterized in that, R is selected from propyl, butyl, pentyl, hexyl, cyclohexyl or -methyl-cyclohexyl-methyl-.

5. The modified polyester polycarbonate copolyester according to claim 1, characterized in that, T is selected from C 3-6 Alkyl, C 5-6 cycloalkyl, C 1-3 Alkyl-C 5-6 cycloalkyl-C 1-3 alkyl.

6. The modified polyester polycarbonate copolyester according to claim 1, characterized in that, T is selected from propyl, butyl, pentyl, hexyl, cyclohexyl, and -methyl-cyclohexyl-methyl-.

7. The modified polyester polycarbonate copolyester according to any one of claims 1-4, characterized in that, The modified polyester polycarbonate copolyester has an intrinsic viscosity of 0.5–1.2 dL / g and a glass transition temperature of 70–130 °C. o C.

8. The modified polyester polycarbonate copolyester according to any one of claims 1-4, characterized in that, The modified polyester polycarbonate copolyester has an impact strength of 240-550 J / m.

9. The modified polyester polycarbonate copolyester according to any one of claims 1-4, characterized in that, The light transmittance of the modified polyester polycarbonate copolyester is not less than 82%.

10. The method for preparing the modified polyester polycarbonate copolyester according to any one of claims 1-9, characterized in that, Includes the following steps: (1) Esterification / transesterification of polyester: The compound shown in Formula A, ethylene glycol, 1,4;3,6-diglihexane and the diol shown in Formula B are mixed and esterified and / or transesterified to obtain polyester prepolymer 1. Formula A: R 1 OOC-L-COOR 1 Formula B: HO-R-OH Among them, the compound represented by formula A, L, R, R 1 It has the meaning as described in any one of claims 1-8; (2) Transesterification reaction of polycarbonate: The carbonate diester shown in formula C and the diol shown in formula D are mixed and transesterified to obtain the polycarbonate prepolymer shown in formula II. Formula C: R 2 O-CO-OR 2 Formula D: HO-T-OH Wherein, T has the meaning as described in any one of claims 1-9; R 2 Selected from C 1-8 Alkyl or C 6-14 Aryl; (3) Melt polycondensation reaction: Polyester prepolymer 1 and polycarbonate prepolymer shown in Formula II are mixed and polycondensed to prepare modified polyester polycarbonate copolyester.

11. The preparation method according to claim 10, characterized in that, R 2 Selected from C 1-6 Alkyl or C 6-14 Aryl.

12. The preparation method according to claim 10, characterized in that, The carbonate diester represented by formula C is a mixture of one or more diesters.

13. The preparation method according to claim 10, characterized in that, The diol represented by formula D is a mixture of one or more diols.

14. The preparation method according to claim 10, characterized in that, The diol represented by Formula B is selected from at least one of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, and 1,4-cyclohexanediethanol.

15. The preparation method according to claim 10, characterized in that, In step (1), the molar ratio of the compound represented by formula A to the diol is 1:1.1 to 3.

16. The preparation method according to claim 10, characterized in that, In step (1), the molar ratio of ethylene glycol, 1,4;3,6-diglycidol and the diol shown in formula B is 1:(0.01-1):(0.01-1).

17. The preparation method according to claim 10, characterized in that, Step (1) is carried out in the presence of transesterification catalyst 1, which is at least one of the following: metal oxides, metal hydroxides, alkoxy metal compounds, metal phosphates, metal sulfates, metal acetylacetone complexes, metal acetates, and metal halides containing magnesium, zinc, manganese, aluminum, cobalt, and tin.

18. The preparation method according to claim 10, characterized in that, The carbonate diester represented by Formula C is selected from any one or a mixture of several of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, dimethyl carbonate, and dinaphthalene carbonate.

19. The preparation method according to claim 10, characterized in that, The diol represented by Formula D is selected from at least one of 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanediethanol, 1,3-cyclohexanediethanol, and 1,4-cyclohexanediethanol.

20. The preparation method according to claim 10, characterized in that, In step (2), the molar ratio of the carbonate diester represented by formula C to the diol represented by formula D is 2:1 to 1:

10.

21. The preparation method according to claim 10, characterized in that, Step (2) is carried out in the presence of transesterification catalyst 2, which is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetone complexes, titanium-based organic compounds, tin-based organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates, and metal halides.

22. The preparation method according to claim 10, characterized in that, The reaction in step (3) is carried out in the presence of a polycondensation catalyst, which is at least one of an organometallic compound or oxide or complex containing titanium, antimony, silicon, germanium or zirconium.

23. The preparation method according to claim 22, characterized in that, The polycondensation catalyst is at least one of titanium dioxide, silicon dioxide / titanium dioxide composite, zirconium dioxide / titanium dioxide composite, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycolate, antimony acetate, germanium dioxide, and germanium acetate.

24. The application of the modified polyester polycarbonate copolyester according to any one of claims 1-9 as an engineering plastic in the fields of fiber, film and packaging.

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