Modified heat-resistant polyester polycarbonate copolyester as well as preparation method and application thereof

Abstract

The invention provides modified heat-resistant polyester polycarbonate copolyester with excellent impact strength and high transparency and a preparation method of the modified heat-resistant polyester polycarbonate copolyester. According to the invention, 1, 4; the rigid structure of 1, 4, 5, 6-diglycidyl hexanehexol overcomes the problem of insufficient heat resistance of PET, and the method of introducing a polycarbonate unit overcomes the defect of poor heat resistance of 1, 4, 5, 6-diglycidyl hexanehexol. The invention solves the problem of insufficient impact strength of the 1, 3, 6-diglycidyl hexanehexol copolyester in the prior art, and the polymerization method is simple and convenient and is beneficial to subsequent industrial amplification.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials, and in particular relates to a modified heat-resistant polyester polycarbonate copolyester with high impact strength and high transparency and a preparation method thereof. Background Art

[0002] Polyethylene terephthalate (PET) is one of the most widely used engineering plastics and is widely used in many fields such as fiber, film, packaging, etc. At present, my country's PET production capacity has reached 54 million tons / year, but PET has a low glass transition temperature. At higher temperatures, PET will experience serious deformation and a significant drop in performance. Therefore, the development of heat-resistant modified PET copolyester has become an urgent problem to be solved.

[0003] 1,4:3,6-dihexanedol is a polysaccharide produced by enzymatic decomposition of starch in cereals. The polysaccharide is hydrogenated to obtain hexahydric alcohol, and then further loses two molecules of water to obtain 1,4:3,6-dihexanedol. This bio-based raw material has three isomers, namely isosorbide, isomannide and isoidide. Among them, only isosorbide has achieved large-scale industrial production. Isosorbide is non-toxic and has the advantages of being green and environmentally friendly. It is also a chiral molecule with a rigid structure, which can effectively improve the heat resistance and mechanical properties of polymers. Therefore, it is widely used in the synthesis of condensation polymers such as polyester, polyurethane, polyamide, and polycarbonate. However, the rigid structure of isosorbide also causes the impact strength of copolymer polymers to decrease. If inorganic or organic reinforcing materials such as glass fiber or rubber particles are added, the impact strength can be effectively improved, but the transparency of the material will be greatly lost. Therefore, while improving the heat resistance and impact strength, maintaining the high transparency of the material is also a problem that is of high concern and needs to be solved urgently.

[0004] In summary, in view of the problems that PET has a low glass transition temperature and is not heat-resistant, the addition of isosorbide causes the polymer to have poor impact resistance, and the doped reinforcing materials cause the material to be opaque, how to prepare a new 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] In order to overcome the shortcomings of the prior art, the present invention provides a modified heat-resistant polyester polycarbonate copolyester and a preparation method thereof. The present invention adopts the rigid structure of 1,4;3,6-dihydrohexanedol to overcome the problem of insufficient heat resistance of traditional polyester PET, and introduces polycarbonate segments without affecting the heat resistance of the copolyester to overcome the problem of insufficient impact strength of 1,4;3,6-dihydrohexanedol modified PET copolyester. The polymerization method is simple and convenient, which is conducive to subsequent industrial amplification.

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

[0007] A modified polyester polycarbonate copolyester is prepared by copolymerization of a polyester prepolymer 1 and a polycarbonate prepolymer represented by formula II.

[0008]

[0009] The polyester prepolymer 1 is prepared by esterification reaction and / or transesterification reaction of the compound represented by formula A, ethylene glycol, 1,4;3,6-dihydrohexanedol, 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 same or different, independently selected from H, unsubstituted or optionally substituted by one, two or more Ra: C 1-12 Alkyl or C 6-20 Aryl;

[0013] L is selected from C which is unsubstituted or optionally substituted with 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 are the same or different and are independently selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy;

[0016] The 1,4;3,6-dihydrohexanedol is selected from at least one of isosorbide, isomannide and isoidide,

[0017]

[0018] T is selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rc: 3-12 Alkyl, C 3-20 Cycloalkyl, -C 1-6 Alkyl-C 3-20 Cycloalkyl-C 1-6 Alkyl-, 3-12 membered heterocyclyl or 3-12 membered heterocyclyl and 3-12 membered heterocyclyl;

[0019] Rc is selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy.

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

[0021]

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

[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, for example propyl, butyl, pentyl, hexyl, cyclohexyl or -methyl-cyclohexyl-methyl-.

[0024] According to an embodiment of the present invention, the compound R 1 OOC-L-COOR 1 represents dibasic acids and / or dibasic esters, for example, the compound represented by formula A represents one dibasic acid, one dibasic ester, two or more dibasic acids, two or more dibasic esters, or a mixture of one or more dibasic acids and one or more dibasic esters. Similarly, the diol HO-R-OH represented by 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, such as R 1 is 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 heterocyclyl and 3-6 membered heterocyclyl, 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, calculated based on the total molar amount of the copolyester diol, the molar percentage of the 1,4;3,6-dihexanedol unit is 10-90%, the molar percentage of the ethylene glycol unit is 1-90%, and the molar percentage of the diol unit represented by formula B is 1-90%; preferably, in the polyester prepolymer 1, the molar percentage of the 1,4;3,6-dihexanedol unit is 10-50%, the molar percentage of the ethylene glycol unit is 20-70%, and the molar percentage of the diol unit represented by formula B is 10-60%.

[0028] According to the embodiment of the present invention, in the polyester prepolymer 1, the molar percentage of the terephthalic acid unit in the formula I is 70-100% based on the total molar amount of the dibasic acid. If other aromatic dibasic acids are contained, the molar percentage of other dibasic acid units is 0-30%.

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

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

[0034] (1) Esterification / transesterification reaction of polyester: the compound represented by formula A, ethylene glycol, 1,4;3,6-dihydrohexanedol, and the diol represented by formula B are mixed and subjected to esterification reaction and / or transesterification reaction to obtain a polyester prepolymer 1;

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

[0036] Formula B: HO-R-OH

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

[0038] (2) Transesterification reaction of polycarbonate: a carbonic acid diester represented by formula C and a diol represented by formula D are mixed and subjected to transesterification reaction to obtain a polycarbonate prepolymer represented by formula II;

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

[0040] Formula D: HO-T-OH

[0041] Wherein, T has the above meaning;

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

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

[0044] (3) Melt polycondensation reaction: The polyester prepolymer 1 and the polycarbonate prepolymer represented by formula II are mixed and subjected to polycondensation reaction to prepare a modified polyester-polycarbonate copolyester.

[0045] According to an embodiment of the present invention, the carbonic acid diester represented by formula C may be a mixture of one or more dibasic esters.

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

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

[0048] According to an embodiment of the present invention, the compound shown in formula A is selected from terephthalic acid, dimethyl terephthalate, isophthalic acid, phthalic acid, 1,4-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, diphenyl terephthalate, dimethyl isophthalate, dipropyl isophthalate, dibutyl isophthalate, dioctyl isophthalate, diphenyl isophthalate, dimethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, 1,4-naphthalene dicarboxylic acid, diethyl terephthalate, dipropyl terephthalate, dibutyl terephthalate, dioctyl terephthalate, diphenyl tere ... At least one of dimethyl formate, diethyl 1,4-naphthalene dicarboxylate, dipropyl 1,4-naphthalene dicarboxylate, dibutyl 1,4-naphthalene dicarboxylate, dioctyl 1,4-naphthalene dicarboxylate, diphenyl 1,4-naphthalene dicarboxylate, dimethyl 2,6-naphthalene dicarboxylate, diethyl 2,6-naphthalene dicarboxylate, dipropyl 2,6-naphthalene dicarboxylate, dibutyl 2,6-naphthalene dicarboxylate, dioctyl 2,6-naphthalene dicarboxylate, and diphenyl 2,6-naphthalene dicarboxylate, and preferably at least one of terephthalic acid, dimethyl terephthalate, phthalic acid, isophthalic acid, 1,4-naphthalene dicarboxylic acid, diethyl terephthalate, and dimethyl isophthalate.

[0049] According to an embodiment of the present invention, step (1) is performed under 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-dihydrohexanedol 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-dihydrohexanedol 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 200-400KPa, preferably 200-330KPa; 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 to 260°C, preferably 200 to 240°C; the total time of the transesterification reaction is 2 to 20 hours, preferably 3 to 10 hours.

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

[0055] According to an embodiment of the present invention, step (1) is carried out in the presence of an ester exchange catalyst 1, and the added ester exchange catalyst 1 is at least one of 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 acetylacetonate, manganese sulfate, manganese acetate, manganese chloride, aluminum oxide, aluminum hydroxide, aluminum phosphate, aluminum sulfate, aluminum acetate, cobalt oxide, cobalt acetylacetonate, cobalt acetate, cobalt acetate tetrahydrate, dibutyltin oxide, dibutyltin dichloride, tributyltin acetate, tributyltin chloride, and trimethyltin chloride.

[0057] According to an embodiment of the present invention, step (1) further comprises a post-treatment step, wherein the post-treatment step comprises: removing by-products in the reaction to obtain a polyester prepolymer 1.

[0058] According to an embodiment of the present invention, the carbonic acid diester shown in formula C is selected from any one of dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, ditolyl carbonate, and dinaphthyl carbonate, or a mixture of several thereof; preferably at least one of dimethyl carbonate, diethyl carbonate, and diphenyl carbonate.

[0059] According to an embodiment of the present invention, the diol shown in formula D is selected from at least one of 1,2-propylene glycol, 1,3-propylene glycol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,6-hexanediol, 1,2-cyclohexanediol, 1,4-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-cyclohexanedimethanol, 1,4-cyclohexanedimethanol, and 1,4;3,6-diglycol hexapol, preferably 1,4;3,6-diglycol hexapol and 1,4-cyclohexanedimethanol.

[0060] According to an embodiment of the present invention, in step (2), the molar ratio of the carbonic acid 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 performed under 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 to 180°C, preferably 100 to 160°C; the total time of the transesterification reaction is 2 to 20 hours, preferably 3 to 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, and the ester exchange catalyst 2 is selected from at least one of metal hydrides, hydroxides, metal oxides, metal acetylacetone complexes, titanium organic compounds, tin organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates and metal halides.

[0064] Preferred 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 comprises a post-treatment step, wherein the post-treatment step comprises: removing by-products in the reaction to obtain a polycarbonate prepolymer represented by formula II.

[0066] According to an embodiment of the present invention, the reaction of step (3) is carried out in the presence of a condensation polymerization catalyst, and the condensation polymerization catalyst is at least one of an organic metal compound or oxide or complex containing titanium, antimony, silicon, germanium or zirconium; preferably at least one of titanium dioxide, silicon dioxide / titanium dioxide composite, zirconium dioxide / titanium dioxide composite, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, ethylene glycol antimony, 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, and 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 200Pa, for example 30-190Pa, preferably not more than 110Pa.

[0069] The present invention also provides the use of the modified polyester polycarbonate copolyester as engineering plastics in the fields of fiber, film and packaging.

[0070] Beneficial effects of the present invention

[0071] The present invention provides a modified heat-resistant polyester polycarbonate copolyester having excellent impact strength and high transparency and a preparation method thereof. The present invention overcomes the problem of insufficient heat resistance of PET by utilizing the rigid structure of 1,4;3,6-dihydrohexanedol, overcomes the problem of insufficient impact strength of 1,4;3,6-dihydrohexanedol copolyester by introducing a polycarbonate unit, and the polymerization method is simple, which is conducive to subsequent industrial amplification.

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

[0073] Definition and explanation of terms

[0074] The term "halogen" means fluorine, chlorine, bromine and / or iodine. Accordingly, the term "halo" refers to fluoro, chloro, bromo and / or iodo. Within the scope of this document, when an atom, residue, group or moiety is halogenated, the atom at the halogenated position may be monosubstituted, disubstituted or polysubstituted up to full substitution by halogen atoms, for example, "halo C 1-12 Alkyl" etc.

[0075] In the present application, some substituents marked with "*" represent the connection site.

[0076] The term "C 1-12 "Alkyl" is understood to mean a straight-chain or branched saturated monovalent hydrocarbon group having 1 to 12 carbon atoms. For example, "C 1-10"Alkyl" means straight chain and branched chain alkyl groups having 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms. 1-6 The term "alkyl" refers to straight-chain and branched alkyl groups 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 the like or isomers thereof.

[0077] The term "C 3-12 The term “alkyl” refers to straight-chain and branched alkyl groups having 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, for example, 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] The term "C 3-20 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or bridged cycloalkane having 3 to 20 carbon atoms, preferably "C 3-12 The term "Cycloalkyl" 3-12 "Cycloalkyl" is understood to mean a saturated monovalent monocyclic, bicyclic hydrocarbon ring or a bridged cycloalkane having 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms. 3-12 The cycloalkyl group may be a monocyclic hydrocarbon group, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl or cyclodecyl, or a bicyclic hydrocarbon group such as decalin. The cycloalkyl group may be a spiro ring, such as spiro [3,3] ring, spiro [3,4] ring, spiro [3,5] ring, spiro [4,4] ring, spiro [4,5] ring, spiro [5,5] ring.

[0079] The term "3-12 membered heterocyclyl" means a saturated or partially unsaturated monovalent monocyclic or bicyclic non-aromatic hydrocarbon ring, which contains 1-5 heteroatoms independently selected from N, O and S and has a total of 3-12 ring atoms; the term "3-10 membered heterocyclyl" means a saturated or partially unsaturated monovalent monocyclic or bicyclic hydrocarbon ring, which contains 1-5, optionally 1-3 heteroatoms selected from N, O and S, and is also exemplified by "3-6 membered heterocyclyl", "4-6 membered heterocyclyl", "5-6 membered heterocyclyl". When the ring atoms in the heterocyclyl are all bonded by saturated bonds, it is called a saturated heterocyclyl. When there are 1, 2, 3 or more olefin bonds or acetylenic bonds, but the heterocyclyl does not form an aromatic ring, it is called a heterocycloalkenyl or heterocycloalkynyl. The heterocyclyl can be connected to the rest of the molecule through any carbon or nitrogen atom (if present) among the carbon atoms that do not form an acetylenic bond. For example, "3-6 membered heterocyclyl" is further divided into "3-6 membered saturated heterocyclyl", and "3-6 membered heterocycloalkenyl", "3-6 membered heterocycloalkynyl". In particular, the heterocyclyl may include, but is not limited to: a 4-membered ring, such as azetidinyl, azetidinyl, oxetanyl or oxetanyl; a 5-membered ring, such as tetrahydrofuranyl, dihydrofuranyl, dioxolyl, pyrrolidinyl, dihydroimidazolyl, imidazolidinyl, dihydropyrazolyl, pyrazolidinyl, pyrrolinyl, oxazolinyl, oxazolidinyl, thiazolinyl or thiazolidinyl; or a 6-membered ring, such as pyranyl, tetrahydropyranyl, thiopyranyl, dihydropyrimidinyl, piperidinyl, morpholinyl, dithianyl, thiomorpholinyl, piperazinyl or trithianyl; or a 7-membered ring, such as diazepanyl or diazepanyl. Optionally, the heterocyclic group can be a fused ring, a bridged ring or a spiro ring. The heterocyclic group can be bicyclic, such as but not limited to hexahydropyrrolo[1,2-a]pyrazine-2(1H)-yl. The heterocyclic group can be partially unsaturated, that is, it can contain one, two or more double bonds, such as but not limited to 2,5-dihydro-1H-pyrrolyl, 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 may be fused with the above 4-membered, 5-membered, 6-membered, or 7-membered ring, such as 2,3-dihydrobenzofuran, benzopyran, 1,2-dihydroquinazoline, 3,4-dihydroquinazoline, and the like.

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

[0081] The term "C 6-20 "Aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring having 6 to 20 carbon atoms, preferably "C 6-14 The term "C6-14 The term "aryl" is understood to mean preferably a monovalent aromatic or partially aromatic monocyclic, bicyclic or tricyclic hydrocarbon ring ("C 6-14 Aryl), especially a ring having 6 carbon atoms ("C 6 aryl), such as phenyl; or biphenyl, or a ring having 9 carbon atoms ("C 9 aryl), such as indanyl or indenyl, or a ring having 10 carbon atoms ("C 10 aryl), such as tetrahydronaphthyl, dihydronaphthyl or naphthyl, or a ring having 13 carbon atoms ("C 13 aryl), such as fluorenyl, or a ring having 14 carbon atoms ("C 14 aryl”), such as anthracenyl. When the C 6-20 When the aryl group is substituted, it may be monosubstituted or polysubstituted. Also, there is no limitation on the substitution position, for example, it may be substituted at the ortho position, para position or meta position.

[0082] The term "halogenated C 1-12 "Alkyl" means C 1-12 In the case where the H on the alkyl group is optionally substituted by 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 halogens, the term “halo” and “C 1-12 "Alkyl" has the above definition. The substitution is on the same carbon atom or on different carbon atoms. 1-6 Alkyl". The "halogenated C 1-12 "Alkyl" is, for example, trifluoromethyl.

[0083] The term "C 1-12 "Alkoxy" means C 1-12 In the case where 1, 2 or 3 carbon atoms in the alkyl group are replaced by O, the above and "C 1-12 "Alkyl" has the above definition. Optionally "C 1-6 Alkoxy". The "C 1-12 "Alkoxy" is, for example, methoxy, ethoxy or propoxy. DETAILED DESCRIPTION

[0084] The technical scheme of the present invention will be further described in detail below in conjunction with specific embodiments. It should be understood that the following embodiments are only exemplary descriptions and explanations 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 included in the scope that the present invention is intended to protect.

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

[0086] The performance parameters in the following examples are measured according to the following methods.

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

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

[0089] Impact strength: The Izod impact strength of a copolyester sample with a notch prepared with a thickness of 4 mm was measured at 23° C. using an Izod impact strength tester according to GB-T1843-2008.

[0090] Light transmittance: Use a light transmittance meter to measure the light transmittance of a 50 mm round copolyester sample at 23°C according to GB / T2410-2008.

[0091] Example 1

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

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

[0094] (3) 70 g of prepolymer I-1 and 30 g of prepolymer II-1 were added to a 250 mL glass flask, 0.013 wt % of polycondensation catalyst tetrabutyl titanate was added, vacuum was gradually established to 100 Pa, and the mixture was reacted at 280° C. for 4 hours to obtain polyester polycarbonate copolyester.

[0095] According to tests, the intrinsic viscosity of the copolyester is 0.66 g / dL, the glass transition temperature is 85°C, the impact strength is 456 J / m, and the light transmittance is 87%.

[0096] Example 2

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

[0098] (2) At room temperature, in a 250 mL glass flask, 43.2 g (0.3 mol) of 1,4-cyclohexanedimethanol, 18.0 g (0.2 mol) of dimethyl carbonate and 0.0018 g of ester exchange catalyst lithium acetylacetonate (the molar ratio of 1,4-cyclohexanedimethanol to dimethyl carbonate is 1.5:1) were added under nitrogen atmosphere, and the mixture was stirred at 80°C, then gradually heated to 180°C, reacted for 3.2 hours, and the by-product methanol produced by the reaction was completely evaporated to obtain prepolymer II-2.

[0099] (3) 75 g of prepolymer I-2 and 25 g of prepolymer II-2 were added to a 250 mL glass flask, 0.03 wt % of polycondensation catalyst antimony acetate was added, vacuum was gradually established to 80 Pa, and the mixture was reacted at 273° C. for 4.2 hours to obtain polyester polycarbonate copolyester.

[0100] According to tests, the intrinsic viscosity of the copolyester is 0.68 g / dL, the glass transition temperature is 91° C., the impact strength is 417 J / m, and the light transmittance is 88%.

[0101] Example 3

[0102] (1) In a 500 mL glass flask, 97.0 g (0.5 mol) of dimethyl terephthalate, 10.66 g (0.175 mol) of ethylene glycol, 18.25 g (0.125 mol) of isosorbide, 36.0 g (0.25 mol) of 1,4-cyclohexanedimethanol (the molar ratio of dibasic acid ester to diol is 1:1.1) and 0.022 wt% of ester exchange catalyst zinc acetate were added under a nitrogen atmosphere. 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 by-product methanol produced by the reaction was completely evaporated to obtain prepolymer Ⅰ-3.

[0103] (2) At room temperature, in a 250 mL glass flask, 69.12 g (0.48 mol) of 1,3-cyclohexanedimethanol, 36.0 g (0.4 mol) of dimethyl carbonate and 0.003 g of ester exchange catalyst tetrabutyl titanate (the molar ratio of 1,3-cyclohexanedimethanol to dimethyl carbonate is 1.2:1) were added under nitrogen atmosphere, and the mixture was stirred at 90°C, then gradually heated to 170°C, reacted for 4 hours, and the by-product methanol produced by the reaction was completely evaporated 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, 0.036wt% of polycondensation catalyst antimony trioxide was added, vacuum was gradually established to 90Pa, and the reaction was carried out at 275°C for 4.9 hours to obtain polyester polycarbonate copolyester. After testing, the intrinsic viscosity of the copolyester was 0.71g / dL, the glass transition temperature was 101°C, the impact strength was 371J / m, and the light transmittance was 91%.

[0105] Example 4

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

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

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

[0109] Example 5

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

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

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

[0113] Example 6

[0114] (1) In a 5L reactor, 1660 g (10.0 mol) of terephthalic acid, 434 g (7.0 mol) of ethylene glycol, 365 g (2.5 mol) of isosorbide, and 504 g (3.5 mol) of 1,4-cyclohexanedimethanol (the molar ratio of dibasic acid to diol is 1:1.3) were added under a nitrogen atmosphere. Under a pressure of 280 kPa, the system temperature was gradually increased to 252°C and the reaction was carried out for 3.5 hours. The by-product water produced by the reaction was completely evaporated to obtain a copolyester prepolymer I-6.

[0115] (2) At room temperature, in a 5L reactor, 1440 g (10.0 mol) of 1,4-cyclohexanedimethanol, 180 g (2.0 mol) of carbonic acid diester and 0.022 g of ester exchange catalyst magnesium acetylacetonate (the molar ratio of 1,4-cyclohexanedimethanol to dimethyl carbonate is 5:1) were added to the reactor under nitrogen atmosphere, and the mixture was stirred at 80°C, and then gradually heated to 175°C and reacted for 4.2 hours. The by-product methanol produced by the reaction was completely evaporated to obtain prepolymer II-6.

[0116] (3) 850 g of prepolymer I-6 and 150 g of prepolymer II-6 were added to a 5 L reactor, 0.017 wt.% of polycondensation catalyst tetrabutyl titanate was added, vacuum was gradually established to 80 Pa, and the reaction was carried out at 280° C. for 4 hours to obtain a copolyester. The copolyester had an intrinsic viscosity of 0.67 g / dL, a glass transition temperature of 112° C., an impact strength of 314 J / 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 dibasic acid to diol is 1:1.2) were added under a nitrogen atmosphere, and the system temperature was gradually increased to 255°C under a pressure of 320kPa. The reaction was carried out for 3.5 hours, and the by-product water produced by the reaction was completely evaporated to obtain a copolyester prepolymer.

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

[0120] Comparative Example 2

[0121] (1) In a 5L reactor, 1660 g (10 mol) of terephthalic acid, 589 g (9.5 mol) of ethylene glycol, and 365 g (2.5 mol) of isosorbide (the molar ratio of dibasic acid to diol is 1:1.2) were added under a nitrogen atmosphere. Under a pressure of 280 kPa, the system temperature was gradually increased to 252°C and reacted for 3.7 hours. The by-product water produced by the reaction was completely evaporated to obtain a copolyester prepolymer.

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

[0123] The above is an explanation of the embodiments of the present invention. However, the present invention is not limited to the above embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. A modified polyester polycarbonate copolyester, characterized in that: Prepared by copolymerization of polyester prepolymer 1 and polycarbonate prepolymer represented by formula II, The polyester prepolymer 1 is prepared by esterification reaction and / or transesterification reaction of the compound represented by formula A, ethylene glycol, 1,4;3,6-dihydrohexanedol, and the diol represented by formula B. Formula A: R 1 OOC-L-COOR 1 Formula B: HO-R-OH R 1 The same or different, independently selected from H, unsubstituted or optionally substituted by one, two or more Ra: C 1-12 Alkyl or C 6-20 Aryl; L is selected from C which is unsubstituted or optionally substituted with one, two or more Rb 6-20 Aryl; 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; Ra and Rb are the same or different and are independently selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy; The 1,4;3,6-dihydrohexanedol is selected from at least one of isosorbide, isomannide and isoidide, T is selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rc: 3-12 Alkyl, C 3-20 Cycloalkyl, -C 1-6 Alkyl-C 3-20 Cycloalkyl-C 1-6 Alkyl-, 3-12 membered heterocyclyl or 3-12 membered heterocyclyl and 3-12 membered heterocyclyl; Rc is selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy.

2. The modified polyester polycarbonate copolyester according to claim 1, characterized in that: The prepolymer 1 has a structure as shown in the following formula I: Wherein, L is selected from C 6-14 aryl, such as phenyl or naphthyl; 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, for example propyl, butyl, pentyl, hexyl, cyclohexyl or -methyl-cyclohexyl-methyl-.

3. The modified polyester polycarbonate copolyester according to claim 1 or 2, characterized in that: R 1 Selected from H, C 1-10 Alkyl or C 6-14 Aryl, such as R 1 is 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.

4. The modified polyester polycarbonate copolyester according to any one of claims 1 to 3, characterized in that: T is selected from C 3-10 Alkyl, C 3-6 Cycloalkyl, C 1-3 Alkyl-C 3-6 Cycloalkyl-C 1-3 alkyl, 3-6 membered heterocyclyl and 3-6 membered heterocyclyl, for example, T is selected from propyl, butyl, pentyl, hexyl, cyclohexyl, -methyl-cyclohexyl-methyl- or 5. The modified polyester polycarbonate copolyester according to any one of claims 1 to 4, characterized in that: Based on the total mass of the modified polyester polycarbonate copolyester, the mass fraction of the polyester prepolymer of formula I is 70-95%, and the mass fraction of the polycarbonate prepolymer represented by formula II is 5-30%. Preferably, 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 impact strength of the modified polyester polycarbonate copolyester is 240-550 J / m. Preferably, the light transmittance of the modified polyester polycarbonate copolyester is not less than 82%.

6. The method for preparing the modified polyester polycarbonate copolyester according to any one of claims 1 to 5, characterized in that: The steps include: (1) Esterification / transesterification reaction of polyester: the compound represented by formula A, ethylene glycol, 1,4;3,6-dihydrohexanedol, and the diol represented by formula B are mixed and subjected to esterification reaction and / or transesterification reaction to obtain a polyester prepolymer 1; Formula A: R 1 OOC-L-COOR 1 Formula B: HO-R-OH Among them, L, R, R 1 Has the meaning of any one of claims 1 to 3; (2) Transesterification reaction of polycarbonate: a carbonic acid diester represented by formula C and a diol represented by formula D are mixed and subjected to transesterification reaction to obtain a polycarbonate prepolymer represented by formula II; Formula C: R 2 O-CO-OR 2 Formula D: HO-T-OH Wherein, T has the meaning as stated in claims 1 and 4; R 2 The same or different, independently selected from the following groups which are unsubstituted or optionally substituted by one, two or more Rf: C 1-12 Alkyl or C 6-20 Aryl; Rf is selected from halogen, C 1-12 Alkyl, haloC 1-12 Alkyl or C 1-12 Alkoxy; (3) Melt polycondensation reaction: The polyester prepolymer 1 and the polycarbonate prepolymer represented by formula II are mixed and subjected to polycondensation reaction to prepare a modified polyester-polycarbonate copolyester.

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

8. The preparation method according to claim 6, characterized in that: In step (1), the molar ratio of the compound represented by formula A to the diol is 1:1 to 3.

9. The preparation method according to any one of claims 6 to 8, characterized in that: Step (1) is carried out in the presence of an ester exchange catalyst 1, and the added ester exchange catalyst 1 is at least one of metal oxides, metal hydroxides, alkoxy metal compounds, metal phosphates, metal sulfates, metal acetylacetonate complexes, metal acetates and metal halides containing magnesium, zinc, manganese, aluminum, cobalt and tin. Preferably, 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 acetylacetonate complexes, titanium organic compounds, tin organic compounds, alkoxy metal compounds, metal carbonates, metal bicarbonates, metal phosphites, inorganic acids, organic acids, tertiary amines, metal acetates and metal halides. Preferably, the reaction of step (3) is carried out in the presence of a condensation polymerization catalyst, wherein the condensation polymerization catalyst is at least one of an organic metal compound, oxide or complex containing titanium, antimony, silicon, germanium or zirconium; preferably at least one of titanium dioxide, silicon dioxide / titanium dioxide composite, zirconium dioxide / titanium dioxide composite, tetrabutyl titanate, tetraethyl titanate, antimony trioxide, antimony glycol, antimony acetate, germanium dioxide and germanium acetate.

10. Use of the modified polyester polycarbonate copolyester according to any one of claims 1 to 6 as engineering plastics in the fields of fiber, film and packaging.

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