Modified copolyesters, methods of making and using the same

Abstract

This invention relates to the field of polyesters, and discloses a modified copolyester, its preparation method, and its applications. The modified copolyester comprises a germanium-containing compound and a modified inorganic material. The germanium-containing compound has a structure as shown in Formula (I), and the modified inorganic material includes an inorganic material and an alkyl alcohol modified on the inorganic material. This modified copolyester exhibits a low zero-shear viscosity and a high Vicat softening temperature, facilitating subsequent processing and applications. Formula (I).

Description

Technical Field

[0001] This invention relates to the field of polyesters, and more specifically to a modified copolyester, its preparation method, and its applications. Background Technology

[0002] Polyethylene terephthalate (PET) is widely used in various fields due to its excellent mechanical properties, good light transmittance, strong gas barrier properties, and ease of processing. However, conventional PET has insufficient light transmittance and impact resistance, and its glass transition temperature is only around 78°C, making it difficult to meet high-temperature application requirements.

[0003] To improve the heat resistance of PET, the industry mainly adds monomers with larger molecular structures, such as 2,2,4,4-tetramethyl-1,3-cyclobutanediol and isosorbide. The glass transition temperature (Tg) of copolyesters modified with these macromonomers is increased, even exceeding 100℃.

[0004] CN107955142A discloses a method for preparing polyester containing isosorbide. By improving the catalyst formulation, lowering the reaction temperature, reducing monomer decomposition, and increasing the residual proportion of isosorbide monomer, which is difficult to participate in the reaction, in the final polymer. However, the activity of titanium catalysts is difficult to control, which can easily lead to poor product color.

[0005] CN1675282A discloses a method for preparing a light-colored copolyester of ethylene glycol, isosorbide, and dimethyl terephthalate, wherein the catalyst used is selected from salts of Sb(III); salts of Ti(IV); acetates of Co(II); acetates of Sb(II); alkanoates of Co(II); alkanoates of Sb(III); oxides of Sb(III); oxides of Ge(IV); diol-soluble oxides of Sb(II), Sb(III), and Ge(IV); and Ti(OR)4, wherein R is an alkyl group with 2-12 carbon atoms, and b is -2 to +2 under the condition of no color correction additives. However, the prepared copolyester has a low viscosity, which will lead to insufficient impact strength of the final product.

[0006] CN103819324A discloses a method for preparing a terephthalic acid-ethylene glycol-isosorbate copolyester polymer. Using germanium dioxide as a catalyst, and adding cobalt acetate and CIariant@RSB violet for color adjustment, the resulting product has a b-value less than 2. To increase the glass transition temperature, a large amount of rigid monomers is added to the product, resulting in a melt dynamic viscosity greater than 900 Pa·s, requiring a specially designed high-viscosity reactor to meet the requirements.

[0007] US8586701B2 discloses a method for preparing a copolyester based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanediethanol. However, the physicochemical properties of the modified monomers are less stable than those of conventional diols, and the reaction is prone to sublimation upon heating. Furthermore, the reaction with 1,4-cyclohexanediethanol easily produces a copolyester rich in poly(1,4-cyclohexanedimethyl terephthalate) segments with a high melting point and easy crystallization and precipitation, resulting in a significant decrease in the molecular weight and transparency of the product, making it difficult to directly obtain high molecular weight copolyesters. Summary of the Invention

[0008] The purpose of this invention is to overcome the problems of unsuitable processing viscosity and poor color of existing polyesters, and to provide a modified copolyester, its preparation method and application. The modified copolyester has a low zero-shear viscosity and a good color, and also has a high Vicat softening temperature, which facilitates subsequent processing and application.

[0009] To achieve the above objectives, a first aspect of the present invention provides a modified copolyester comprising a germanium-containing compound and a modified inorganic material, wherein the germanium-containing compound has a structure as shown in formula (I), and the modified inorganic material comprises an inorganic material and an alkyl alcohol modified on the inorganic material. Formula (I).

[0010] A second aspect of the present invention provides a method for preparing a catalyst, the method comprising: subjecting a polyol monomer and a carbonyl-containing monomer to a contact reaction I in the presence of a catalyst and a modified inorganic material, wherein the carbonyl-containing monomer is a polyacid and / or a polyacid ester, the catalyst having the structure shown in formula (I), and the modified inorganic material comprising an inorganic material and an alkyl alcohol I modified on the inorganic material. Formula (I).

[0011] A third aspect of the present invention provides the application of the modified copolyester described above or the modified copolyester prepared by the above preparation method in food packaging, household appliances and medical devices.

[0012] Through the above technical solution, the modified copolyester provided by the present invention contains germanium-containing compounds with the structure shown in formula (I) and modified inorganic materials modified with alkyl alcohols. Through the interaction between germanium-containing compounds and modified inorganic materials in polyester, the Vicat softening temperature of polyester can be effectively increased and the zero-shear viscosity of polyester can be reduced. At the same time, the hue of the obtained polyester can also be improved, which is convenient for subsequent processing and application. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] As previously stated, a first aspect of the present invention provides a modified copolyester comprising a germanium-containing compound and a modified inorganic material, wherein the germanium-containing compound has a structure as shown in formula (I), and the modified inorganic material comprises an inorganic material and an alkyl alcohol modified on the inorganic material. Formula (I).

[0015] According to the present invention, the above structure can be detected by a combination of infrared, gas chromatography and ICP.

[0016] During the research process, the inventors discovered that the modified copolyester provided by the present invention contains germanium-containing compounds with the structure shown in formula (I) and modified inorganic materials modified with alkyl alcohols. Through the interaction between the germanium-containing compounds and the modified inorganic materials in the polyester, the Vicat softening temperature of the polyester can be effectively increased and the zero-shear viscosity of the polyester can be reduced. At the same time, the hue of the obtained polyester can also be improved, which is convenient for subsequent processing and application.

[0017] Preferably, the catalyst has a structure as shown in formula (VI). Formula (VI).

[0018] Preferably, the germanium-containing compound has the structural formula shown in formula (II) and / or formula (III). Formula (II); Formula (III); R1, R2, and R3 are each independently C1-C25 alkylene compounds. The two structures described above exhibit better interaction with modified inorganic materials, further increasing the Vicat softening temperature of polyester and reducing its zero-shear viscosity.

[0019] According to the present invention, R1, R2, and R3 can each independently be a C1-C25 straight-chain alkylene and / or a C1-C25 branched alkylene, specifically methylene, hexylene, propylene, butylene, pentylene, octylene, dodecylene, pentadecylene, heptadecanylene, octadecylene, eicosylene, or icosylene. Preferably, R1, R2, and R3 are each independently a C1-C25 straight-chain alkylene. During the research, it was found that limiting R1, R2, and R3 to a straight-chain structure can further improve their interaction with modified inorganic materials, thereby further increasing the Vicat softening temperature of the polyester and reducing the zero-shear viscosity of the polyester.

[0020] Preferably, R1, R2, and R3 are each independently C4-C25 alkylene groups. Studies have found that controlling R1, R2, or R3 within the aforementioned range can further enhance their interaction with the modified inorganic material, thereby further increasing the Vicat softening temperature of the polyester and reducing its zero-shear viscosity. Further preferably, considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the polyester, R1, R2, and R3 are each independently C15-C20 alkylene groups. More preferably, R1 and R2 are the same.

[0021] The inorganic material can be at least one of nitrides, carbides, and oxides. Preferably, the inorganic material is selected from at least one of aluminum nitride, boron nitride, silicon carbide, and alumina. Studies have found that modified inorganic materials containing the above-mentioned inorganic materials have better synergistic effects with germanium-containing compounds, thereby further increasing the Vicat softening temperature of the polyester and reducing the zero-shear viscosity of the polyester. Further preferably, considering the ability to further increase the Vicat softening temperature of the polyester and reduce the zero-shear viscosity of the polyester, the inorganic material is boron nitride.

[0022] Preferably, the alkyl alcohol is a C1-C25 alkyl alcohol. During their research, the inventors discovered that inorganic materials modified with the aforementioned alkyl alcohol exhibit better synergistic effects with germanium-containing compounds, thereby further increasing the Vicat softening temperature of the polyester and reducing its zero-shear viscosity. Considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the polyester, it is further preferred that the alkyl alcohol is a C4-C25 alkyl alcohol. More preferably, the alkyl alcohol is a C15-C20 alkyl alcohol.

[0023] According to the present invention, the alkyl alcohol can be a cyclic alkyl alcohol and / or a chain alkyl alcohol, preferably a chain alkyl alcohol. The C1-C25 alkyl alcohol can be a C1-C25 alkyl monohydric alcohol, a C1-C25 alkyl dihydric alcohol, or a C1-C25 alkyl polyhydric alcohol. When the C1-C25 alkyl alcohol is a monohydric alcohol, it can be any one of the C1-C25 monohydric alkyl alcohols, for example, it can be methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol, 4-octanol, 1-nonanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 1-decanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 1-undecanol, 2-undecanol Alkyl alcohols, 3-undecyl alcohol, 4-undecyl alcohol, 5-undecyl alcohol, 6-undecyl alcohol, 1-dodecyl alcohol, 2-dodecyl alcohol, 3-dodecyl alcohol, 4-dodecyl alcohol, 5-dodecyl alcohol, 6-dodecyl alcohol, 1-tetane alcohol, 2-tetane alcohol, 3-tetane alcohol, 4-tetane alcohol, 5-tetane alcohol, 6-tetane alcohol, 7-tetane alcohol, 1-tetradecyl alcohol, 2-tetradecyl alcohol, 3-tetradecyl alcohol, 4-tetradecyl alcohol, 5-tetradecyl alcohol, 6-tetradecyl alcohol, 7-tetradecyl alcohol, 1-pentadecyl alcohol, 2-pentadecyl alcohol, 3-pentadecyl alcohol, 4-pentadecyl alcohol, 5 -Pentadecyl alcohol, 6-pentadecyl alcohol, 7-pentadecyl alcohol, 8-pentadecyl alcohol, 1-hexadecyl alcohol, 2-hexadecyl alcohol, 3-hexadecyl alcohol, 4-hexadecyl alcohol, 5-hexadecyl alcohol, 6-hexadecyl alcohol, 7-hexadecyl alcohol, 8-hexadecyl alcohol, 1-heptadecyl alcohol, 2-heptadecyl alcohol, 3-heptadecyl alcohol, 4-heptadecyl alcohol, 5-heptadecyl alcohol, 6-heptadecyl alcohol, 7-heptadecyl alcohol, 8-heptadecyl alcohol, 9-heptadecyl alcohol, 1-octadecyl alcohol, 2-octadecyl alcohol, 3-octadecyl alcohol, 6-octadecyl alcohol, 8-octadecyl alcohol, 9-octadecyl alcohol, 1-nonadecanyl alcohol, 2-nonadecanyl alcohol Alcohols, including 5-nonadecanol, 6-nonadecanol, 1-eicosylol, 2-eicosylol, 6-eicosylol, 9-eicosylol, 10-eicosylol, 1-eicosylol, 2-eicosylol, 8-eicosylol, 9-eicosylol, 10-eicosylol, 1-dococaprol, 3-dococaprol, 4-dococaprol, 6-dococaprol, 7-dococaprol, 10-dococaprol, 11-dococaprol, 1-trialkylol, 4-dococaprol, 5-dococaprol, 8-dococaprol, 9-dococaprol, and 11-dococaprol. When C1-C25 alkyl alcohols are diols, they can specifically be any one of the C1-C25 dialkyl alcohols; examples are not provided here. When the C1-C25 alkyl alcohol is a triol, it can be any one of the C1-C25 trialkyl alcohols, and examples will not be given here.

[0024] The alkyl alcohol can be a primary alcohol and / or a secondary alcohol. Preferably, the alkyl alcohol is a secondary alcohol. Studies have found that inorganic materials modified with secondary alcohols have better synergistic effects with germanium-containing compounds, which can further increase the Vicat softening temperature of polyesters and reduce the zero-shear viscosity of polyesters.

[0025] Preferably, the alkyl alcohol is modified onto the inorganic material by a coupling agent, which can improve the stability of the modified inorganic material, thereby further increasing the Vicat softening temperature of the polyester and reducing the zero-shear viscosity of the polyester. Further preferably, considering the ability to further increase the Vicat softening temperature of the polyester and reduce the zero-shear viscosity of the polyester, the coupling agent is a silane coupling agent. More preferably, the silane coupling agent is selected from at least one of γ-glycidoxypropyltrimethoxysilane (KH560), γ-aminopropyltriethoxysilane (KH550), and γ-methacryloyloxypropyltrimethoxysilane (KH570).

[0026] Preferably, in the modified copolyester, the content of the germanium-containing compound, calculated as germanium, is 50-500 μg / g, which can be 50 μg / g, 100 μg / g, 150 μg / g, 200 μg / g, 250 μg / g, 300 μg / g, 350 μg / g, 400 μg / g, 450 μg / g, 500 μg / g, or any value between these values; the content of the modified inorganic material, calculated as inorganic material, is 500-10000 μg / g, which can be 500 μg / g, 1000 μg / g, 1500 μg / g, 2000 μg / g, 2500 μg / g, 3000 μg / g, 3500 μg / g, 4000 μg / g, 4500 μg / g, 5000 μg / g, or any value between these values. Studies have found that controlling the content of germanium-containing compounds and modified inorganic materials within the aforementioned ranges results in modified copolyesters exhibiting higher Vicat softening temperatures and lower zero-shear viscosity. Further preferably, considering the potential to further increase the Vicat softening temperature and decrease the zero-shear viscosity of the modified copolyester, the content of the germanium-containing compounds (calculated as germanium) in the modified copolyester is 220-300 μg / g, and the content of the modified inorganic materials (calculated as inorganic materials) is 5000-10000 μg / g.

[0027] Preferably, in the modified copolyester, the mass ratio of the germanium-containing compound (calculated as germanium) to the modified inorganic material (calculated as inorganic material) is 1:1-200, and can be 1:1, 1:15, 1:20, 1:100, 1:200, or any value between the above ratios. Studies have found that controlling the mass ratio of the germanium-containing compound to the modified inorganic material within the above range can further improve the synergistic effect of the germanium-containing compound and the modified inorganic material, thereby further increasing the Vicat softening temperature of the modified copolyester and reducing its zero-shear viscosity. Considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the modified copolyester, preferably, the mass ratio of the germanium-containing compound (calculated as germanium) to the modified inorganic material (calculated as inorganic material) in the modified copolyester is 1:20-40.

[0028] Preferably, the modified copolyester further contains structural unit A as shown in formula (IV) and structural unit B as shown in formula (V); Formula (IV), Formula (V), Among them, R I R II R III R IV R V and R VI Each is independently selected from C1-C4 alkyl or hydrogen. Modified copolyesters having the above structural units exhibit better synergistic effects with germanium-containing compounds and modified inorganic materials, thereby further increasing the Vicat softening temperature and decreasing the zero-shear viscosity of the modified copolyester. Further preferably, considering the ability to further increase the Vicat softening temperature and decrease the zero-shear viscosity of the modified copolyester, R... I R II R III R IV R V and R VI Each is independently methyl or hydrogen. More preferably, R I R II R III R IV R V and R VI It is hydrogen.

[0029] Preferably, the modified copolyester has a Vicat softening temperature of 87-120℃, a zero-shear viscosity of 610-720 Pa·s, a color value L of 62-68, and a b value of -2-4.5.

[0030] The Vicat softening temperature was obtained according to the national standard GB / T1633-2000; the L value and b value were obtained according to the national standard GB17931-2018; and the dynamic zero-shear viscosity was obtained according to the standard JY / T 0590-2020.

[0031] A second aspect of the present invention provides a method for preparing a modified copolyester, the method comprising: subjecting a polyol monomer and a carbonyl-containing monomer to a contact reaction I in the presence of a catalyst and a modified inorganic material, wherein the carbonyl-containing monomer is a polyacid and / or a polyester, the catalyst has the structure shown in formula (I), and the modified inorganic material comprises an inorganic material and an alkyl alcohol I modified on the inorganic material. Formula (I).

[0032] During the research, it was found that adding a catalyst with the structure shown in formula (I) and an inorganic material modified with alkyl alcohol I during the above preparation process resulted in a modified copolyester with a high Vicat softening temperature and a low zero-shear viscosity, as well as a good hue, through the interaction between the two.

[0033] Preferably, the catalyst has a structure as shown in formula (VI). Formula (VI).

[0034] Preferably, the germanium-containing compound has the structural formula shown in formula (II) and / or formula (III). Formula (II); Formula (III); R1, R2, and R3 are each independently C1-C25 alkylene compounds. The two structures described above exhibit better interaction with modified inorganic materials, further increasing the Vicat softening temperature of polyester and reducing its zero-shear viscosity.

[0035] Preferably, R1, R2, and R3 are each independently C4-C25 alkylene groups. Studies have found that controlling R1, R2, or R3 within the aforementioned range can further enhance their interaction with the modified inorganic material, thereby further increasing the Vicat softening temperature of the polyester and reducing its zero-shear viscosity. Further preferably, considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the polyester, R1, R2, and R3 are each independently C15-C20 alkylene groups. More preferably, R1 and R2 are the same.

[0036] Preferably, the preparation method of the germanium-containing compound includes: reacting germanium phosphate with alkyl alcohol II in a contact reaction II, wherein alkyl alcohol II is a C1-C25 alkyl alcohol. The catalyst prepared by the above method has the structure shown in formula (I), thereby enabling the copolyester subsequently prepared to have a high Vicat softening temperature and a low zero-shear viscosity.

[0037] Preferably, the alkyl alcohol I is a secondary alcohol. Studies have found that catalysts prepared from secondary alcohols have higher catalytic activity, resulting in polyesters with higher Vicat softening temperatures and lower zero-shear viscosity.

[0038] Preferably, the alkyl alcohol I is a C4-C25 alkyl alcohol. The polyester prepared from the catalyst obtained by the above-mentioned alkyl alcohol I exhibits a high Vicat softening temperature and a low zero-shear viscosity. Further preferably, considering the ability to further increase the Vicat softening temperature and decrease the zero-shear viscosity of the polyester, the alkyl alcohol is a C15-C20 alkyl alcohol.

[0039] Preferably, the alkyl alcohol I is an alkyl monohydric alcohol and / or an alkyl dihydric alcohol. Studies have found that catalysts prepared using alkyl monohydric alcohols and / or alkyl dihydric alcohols, with structures as shown in formulas (II) and / or (III), exhibit better interaction with modified inorganic materials, resulting in polyesters with higher Vicat softening temperatures and lower zero-shear viscosity. Considering the potential to further increase the Vicat softening temperature and decrease the zero-shear viscosity of the polyester, preferably, the alkyl alcohol I is an alkyl dihydric alcohol.

[0040] Preferably, the conditions for contact reaction II are at least: a temperature of 100-150°C and a time of 2-4 hours. The catalyst prepared under the above conditions exhibits high catalytic activity.

[0041] Preferably, the contact reaction II is carried out in a solvent. Carrying the contact reaction II in a solvent allows for better reaction of the reactants. More preferably, the polar solvent is water.

[0042] Preferably, the molar ratio of germanium phosphate to the alkyl alcohol is 1:2-5.

[0043] Germanium phosphate is commercially available or can be prepared. Preferably, the preparation method of germanium phosphate includes: reacting sodium germanate and phosphoric acid in a contact reaction III. This method can prepare germanium phosphate and improve the reaction efficiency between germanium phosphate and alkyl alcohols.

[0044] Sodium germanate is commercially available or can be prepared. Preferably, the preparation method of sodium germanate includes: subjecting sodium carbonate, sodium peroxide, and metallic germanium to a contact reaction IV. This method can prepare sodium germanate and improve the reaction efficiency between sodium germanate and phosphoric acid.

[0045] Preferably, the conditions for contact reaction III include at least a time of 0.5-2 hours. Under these conditions, sodium germanate and phosphoric acid exhibit good reaction performance.

[0046] Preferably, the molar ratio of sodium germanate to phosphoric acid is 1:1.8-2.2. More preferably, it is 1:2.

[0047] Preferably, the conditions for the contact reaction IV include at least: a temperature of 450-550°C and a time of 2-4 hours. Under these conditions, sodium carbonate, sodium peroxide, and metallic germanium exhibit good reaction performance.

[0048] Preferably, the molar ratio of sodium carbonate, sodium peroxide and metallic germanium is 1:1.5-2.5:0.8-1.2.

[0049] The method further includes separating water from the product obtained by the contact reaction II. The separation method may be distillation, drying, or other methods.

[0050] The inorganic material can be at least one of nitrides, carbides, and oxides. Preferably, the inorganic material is selected from at least one of aluminum nitride, boron nitride, silicon carbide, and alumina. Studies have found that modified inorganic materials containing the above-mentioned inorganic materials have better synergistic effects with germanium-containing compounds, thereby further increasing the Vicat softening temperature of the polyester and reducing the zero-shear viscosity of the polyester. Further preferably, considering the ability to further increase the Vicat softening temperature of the polyester and reduce the zero-shear viscosity of the polyester, the inorganic material is boron nitride.

[0051] Preferably, the alkyl alcohol I is a C1-C25 alkyl alcohol. During their research, the inventors discovered that inorganic materials modified with the aforementioned alkyl alcohol I exhibit better synergistic effects with germanium-containing compounds, thereby further increasing the Vicat softening temperature of the polyester and reducing its zero-shear viscosity. Considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the polyester, it is further preferred that the alkyl alcohol I is a C4-C25 alkyl alcohol. More preferably, the alkyl alcohol I is a C15-C20 alkyl alcohol.

[0052] The alkyl alcohol I can be a primary alcohol and / or a secondary alcohol. Preferably, the alkyl alcohol I is a secondary alcohol. Studies have found that inorganic materials modified with secondary alcohols have better synergistic effects with germanium-containing compounds, which can further increase the Vicat softening temperature of polyesters and reduce the zero-shear viscosity of polyesters.

[0053] Preferably, the alkyl alcohol I is modified onto the inorganic material by a coupling agent, which can improve the stability of the modified inorganic material, thereby further increasing the Vicat softening temperature of the polyester and reducing the zero-shear viscosity of the polyester. Further preferably, considering the ability to further increase the Vicat softening temperature of the polyester and reduce the zero-shear viscosity of the polyester, the coupling agent is a silane coupling agent. More preferably, the silane coupling agent is selected from at least one of γ-glycidoxypropyltrimethoxysilane (KH560), γ-aminopropyltriethoxysilane (KH550), and γ-methacryloyloxypropyltrimethoxysilane (KH570).

[0054] Preferably, the preparation method of the modified inorganic material includes: subjecting alkyl alcohol I, a coupling agent, and the inorganic material to a contact reaction V. The modified inorganic material prepared by the above method exhibits better synergy with the catalyst, further increasing the Vicat softening temperature of the copolyester and reducing its zero-shear viscosity.

[0055] Preferably, the conditions for the contact reaction V at least satisfy the following: the time is 1.5-2.5 hours. Controlling the conditions for the contact reaction V within the above range can further improve the reaction effect between the alkyl alcohol I, the coupling agent, and the inorganic material.

[0056] Preferably, the mass ratio of the alkyl alcohol I, the coupling agent, and the inorganic material is 3.7-4.3:0.02-0.08:1. Controlling the mass ratio of the alkyl alcohol I, the coupling agent, and the inorganic material within the above range can further improve the interaction effect between the obtained modified inorganic material and the catalyst, thereby further increasing the Vicat softening temperature of the copolyester and reducing the zero-shear viscosity of the copolyester.

[0057] Preferably, the polybasic acid is an aromatic dibasic acid, the polybasic acid ester is an aliphatic dibasic acid ester, and the polyol contains both chain diols and cyclic diols. The copolyester prepared under the above conditions exhibits a high Vicat softening temperature and a low zero-shear viscosity. More preferably, the molar ratio of the cyclic diol to the chain diol is 1:2-10.

[0058] Preferably, the cyclic diol is isosorbide and / or 1,4-cyclohexanediethanol, and the chain diol is a C2-C5 chain diol. Controlling the cyclic and chain diols to these types allows for the preparation of a copolyester with a higher Vicat softening temperature and a lower zero-shear viscosity. More preferably, the cyclic diol is isosorbide and 1,4-cyclohexanediethanol. Even more preferably, the molar ratio of isosorbide to 1,4-cyclohexanediethanol is 1:1.5-2.

[0059] Preferably, based on the theoretical yield of the copolyester, the amount of catalyst (calculated as germanium) is 50-500 μg / g, and the amount of modified inorganic material (calculated as inorganic material) is 500-10000 μg / g. Controlling the amounts of catalyst and modified inorganic material within these ranges further increases the Vicat softening temperature of the copolyester and decreases its zero-shear viscosity. Further preferably, considering the ability to further increase the Vicat softening temperature and decrease the zero-shear viscosity of the copolyester, the amount of catalyst (calculated as germanium) is 220-300 μg / g, and the amount of modified inorganic material (calculated as inorganic material) is 5000-10000 μg / g, based on the theoretical yield of the copolyester.

[0060] Preferably, in the modified copolyester, the mass ratio of the germanium-containing compound (calculated as germanium) to the modified inorganic material (calculated as inorganic material) is 1:1-200, and can be 1:1, 1:15, 1:20, 1:100, 1:200, or any value between the above ratios. Studies have found that controlling the mass ratio of the germanium-containing compound to the modified inorganic material within the above range can further improve the synergistic effect of the germanium-containing compound and the modified inorganic material, thereby further increasing the Vicat softening temperature of the modified copolyester and reducing its zero-shear viscosity. Considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the modified copolyester, preferably, the mass ratio of the germanium-containing compound (calculated as germanium) to the modified inorganic material (calculated as inorganic material) in the modified copolyester is 1:20-40.

[0061] Preferably, the contact reaction I includes a first-stage contact reaction and a second-stage contact reaction.

[0062] Preferably, the first stage of the contact reaction includes at least a temperature of 220-260°C and an initial pressure less than or equal to 0.25 MPa; the second stage of the contact reaction includes at least a temperature of 265-275°C and a vacuum degree less than or equal to 80 Pa. Under the above conditions, polyol monomers and monomers containing carbonyl groups exhibit good reaction performance.

[0063] Preferably, the preparation method further includes: before the contact reaction I, mixing a polyol monomer, a carbonyl-containing monomer, and an auxiliary agent, wherein the auxiliary agent is selected from at least one of ether inhibitors, antioxidants, and colorants. Through the synergistic effect between the above-mentioned auxiliary agent, catalyst, modified inorganic compound, polyol monomer, and carbonyl-containing monomer, the Vicat softening temperature of the modified copolyester can be further increased and its zero-shear viscosity reduced. Further preferably, considering the ability to further increase the Vicat softening temperature and reduce the zero-shear viscosity of the modified copolyester, the amount of the auxiliary agent used is 500-5000 μg / g, based on the theoretical yield of the copolyester.

[0064] Preferably, the ether inhibitor is an alkali metal acetate inhibitor and / or an alkaline earth metal acetate inhibitor. More preferably, the alkali metal acetate inhibitor is selected from at least one of sodium acetate, lithium acetate, and potassium histidine; the alkaline earth metal acetate inhibitor is magnesium acetate and / or calcium acetate. More preferably, the amount of the ether inhibitor used is 5-100 μg / g, based on the theoretical yield of the copolyester.

[0065] Preferably, the antioxidant is selected from at least one of antioxidant 1010, antioxidant 1076, antioxidant 1500, antioxidant 425, antioxidant 168, and antioxidant PEPQ, and more preferably antioxidant 1010 and antioxidant PEPQ. More preferably, the mass ratio of antioxidant 1010 to antioxidant PEPQ is 1-4:1. More preferably, the amount of antioxidant used is 500-5000 μg / g, based on the theoretical yield of the copolyester.

[0066] Preferably, the colorant is an organic red or cobalt acetate.

[0067] Preferably, the additives may not include the colorant, and the colorant is added to the reaction product after the contact reaction IV is completed.

[0068] Preferably, the additives are ether inhibitors, antioxidants, and colorants. The combination of these additives can further increase the Vicat softening temperature of the modified copolyester and reduce its zero-shear viscosity. More preferably, the mass ratio of the ether inhibitor, the antioxidant, and the colorant is 1:0.03-38:25-500.

[0069] A third aspect of the present invention provides the application of the modified copolyester described above or the modified copolyester prepared by the above preparation method in food packaging, household appliances and medical devices.

[0070] The present invention will be described in detail below through examples. In the following examples, the intrinsic viscosity, L value, and b value were obtained according to the national standard GB17931-2018; Tg was obtained according to GB / T 14190-2017; the molecular weight distribution index, oligomer content, and number-average molecular weight were obtained according to GB / T 36214.1-2018; the dynamic zero-shear viscosity was obtained according to the standard JY / T0590-2020; and the Vicat softening temperature was obtained according to the standard GB / T1633-2000.

[0071] Preparation Example 1-1 S1. Add 3 mol of sodium carbonate, 6 mol of sodium peroxide, and 3 mol of metallic germanium to a crucible. React at 500°C under nitrogen protection for 3 hours to obtain sodium germanate. The reaction is as follows: Ge+2Na2O2+Na2CO3=Na2GeO3+CO2↑+2Na2O.

[0072] S2. Sodium germanate was placed in an Erlenmeyer flask, and 6 mol of phosphoric acid was added. The reaction was carried out for 1 hour to obtain an aqueous solution containing germanium phosphate. The reaction is as follows: 3Na2GeO3+6H3PO4=Ge3(PO4)4+2(Na)3PO4+9H2O.

[0073] S3. Then, 3 mol of 1-heptadecanool (CAS No.: 1454-85-9) was added to an aqueous solution containing germanium phosphate, and the mixture was reacted at 100℃ for 4 hours. The product was then separated from water by distillation and dried to obtain catalyst-1. The reaction is as follows: 2Ge3(PO4)4 + 3CH3(CH2) 15 CH2OH=3Ge2(PO4)2C 34 H 64 +2H3PO4.

[0074] Preparation Examples 1-2 S1. Add 3 mol of sodium carbonate, 4.5 mol of sodium peroxide and 2.4 mol of metallic germanium to a crucible, and react at 450 °C under nitrogen protection for 4 h to obtain sodium germanate.

[0075] S2. Sodium germanate was placed in an Erlenmeyer flask, and 6 mol of phosphoric acid was added and reacted for 2 hours to obtain an aqueous solution containing germanium phosphate.

[0076] S3. Then, add 3 mol of pentadecanool (CAS No.: 629-76-5) to the aqueous solution containing germanium phosphate, react at 150℃ for 2 h, and then separate the water from the product by distillation and dry to obtain catalyst-2.

[0077] Preparation Examples 1-3 S1. Add 3 mol of sodium carbonate, 7.5 mol of sodium peroxide and 3.6 mol of metallic germanium to a crucible, and react at 550 °C under nitrogen protection for 2 h to obtain sodium germanate.

[0078] S2. Place sodium germanate in an Erlenmeyer flask, add 6 mol of phosphoric acid and react for 0.5 h to obtain an aqueous solution containing germanium phosphate.

[0079] S3. Add 3 mol of 1-octadecanool (CAS No.: 112-92-5) to an aqueous solution containing germanium phosphate, react at 130℃ for 3 h, and then separate the water from the product by distillation and dry to obtain catalyst-3.

[0080] Preparation Examples 1-4 The catalyst was prepared according to the method described in Preparation Examples 1-2, except that in step S3, 1-pentadecanol (CAS No.: 629-76-5) was replaced with 1,15-pentadecanediol (CAS No.: 14722-40-8), and the resulting catalyst was designated as catalyst-4.

[0081] Preparation Examples 1-5 The catalyst was prepared according to the method described in Preparation Examples 1-3, except that in step S3, 1-octadecaneol (CAS No.: 112-92-5) was replaced with 1,18-octadecanediol (CAS No.: 3155-43-9), and the resulting catalyst was designated as Catalyst-5.

[0082] Preparation Examples 1-6 The catalyst was prepared according to the method described in Preparation Examples 1-3, except that in step S3, 1-octadecaneol (CAS No.: 112-92-5) was replaced with 1,12-octadecanediol (CAS No.: 2726-73-0), and the resulting catalyst was designated as Catalyst-6.

[0083] Preparation Examples 1-7 The catalyst was prepared according to the method described in Preparation Examples 1-3, except that in step S3, 1-octadecanool (CAS No.: 112-92-5) was replaced with eicosanol (CAS No.: 629-96-9), and the resulting catalyst was designated as Catalyst-7.

[0084] Preparation Examples 1-8 The catalyst was prepared according to the method described in Preparation Examples 1-2, except that in step S3, 1-pentadecanol (CAS No.: 629-76-5) was replaced with n-dodecanool (CAS No.: 112-53-8), and the resulting catalyst was designated as Catalyst-8.

[0085] Preparation Examples 1-9 The catalyst was prepared according to the method described in Preparation Examples 1-2, except that in step S3, 1-pentadecanol (CAS No.: 629-76-5) was replaced with n-butanol, and the resulting catalyst was designated as Catalyst-9.

[0086] Preparation Examples 1-10 The catalyst was prepared according to the method described in Preparation Examples 1-3, except that in step S3, 1-octadecanool (CAS No.: 112-92-5) was replaced with tetracosanool (CAS No.: 506-51-4), and the resulting catalyst was designated as Catalyst-10.

[0087] Preparation Example 2-1 7.9g of 1-heptadecanool (CAS No.: 1454-85-9) and 0.1g of silane coupling agent KH560 were heated to 90℃ until the 1-heptadecanool was completely dissolved. Then, 2g of boron nitride was added, and the mixture was stirred for 2 hours. After cooling and pulverizing, modified inorganic material-1 was obtained.

[0088] Preparation Example 2-2 7.5g of pentadecanoic acid (CAS No.: 629-76-5) and 0.15g of silane coupling agent KH560 were heated to 80℃ until the pentadecanoic acid was completely dissolved. Then, 2g of boron nitride was added, and the mixture was stirred for 1.5 hours. After cooling and pulverizing, modified inorganic material-2 was obtained.

[0089] Preparation Examples 2-3 8.5g of 1-octadecanool (CAS No.: 112-92-5) and 0.05g of silane coupling agent KH560 were heated to 100℃ until the 1-octadecanool was completely dissolved. Then, 2g of boron nitride was added, and the mixture was stirred for 2.5 hours. After cooling and pulverizing, modified inorganic material-3 was obtained.

[0090] Preparation Examples 2-4 The modified inorganic material was prepared according to the method of Preparation Example 2-3, except that 1-octadecanool (CAS No.: 112-92-5) was replaced with eicosanol (CAS No.: 629-96-9). The resulting modified inorganic material is denoted as Modified Inorganic Material-4.

[0091] Preparation Examples 2-5 The modified inorganic material was prepared according to the method of Preparation Example 2-2, except that 1-pentadecanol (CAS No.: 629-76-5) was replaced with n-dodecanool (CAS No.: 112-53-8). The resulting modified inorganic material is denoted as Modified Inorganic Material-5.

[0092] Preparation Examples 2-6 The modified inorganic material was prepared according to the method of Preparation Example 2-2, except that 1-pentadecanol (CAS No.: 629-76-5) was replaced with n-butanol. The resulting modified inorganic material is denoted as Modified Inorganic Material-6.

[0093] Preparation Examples 2-7 The modified inorganic material was prepared according to the method of Preparation Example 2-1, except that boron nitride was replaced with aluminum nitride. The resulting modified inorganic material is denoted as Modified Inorganic Material-7.

[0094] Preparation Examples 2-8 The modified inorganic material was prepared according to the method of Preparation Example 2-1, except that boron nitride was replaced with silicon carbide. The resulting modified inorganic material is denoted as Modified Inorganic Material-8.

[0095] Preparation Examples 2-9 The modified inorganic material was prepared according to the method of Preparation Example 2-1, except that boron nitride was replaced with aluminum oxide. The resulting modified inorganic material is denoted as Modified Inorganic Material-9.

[0096] Preparation Example 2-10 The modified inorganic material was prepared according to the method of Preparation Example 2-1, except that the silane coupling agent KH560 was replaced with the silane coupling agent KH550. The modified inorganic material obtained was denoted as Modified Inorganic Material-10.

[0097] Preparation Example 2-11 The modified inorganic material was prepared according to the method of Preparation Example 2-1, except that the silane coupling agent KH560 was replaced with the silane coupling agent KH570. The modified inorganic material prepared was denoted as Modified Inorganic Material-11.

[0098] Example 1 A slurry was prepared by mixing 350g of purified terephthalic acid, 182g of ethylene glycol, 48g of isosorbide, 98g of CHDM, 4.8g of modified inorganic material-1, 0.254g of catalyst-1, 0.02g of ether inhibitor sodium acetate, and 0.075g of colorant cobalt acetate. This slurry was added to a polymerization reactor, and esterification was carried out at 240℃ and an initial pressure of 0.25MPa. When the esterification liquid temperature reached 260℃ and the temperature at the top of the fractionation column was less than 120℃, the pressure in the polymerization reactor was reduced to atmospheric pressure, and esterification was completed. The reactor then entered a low-vacuum stage, and after 45 minutes, a high-vacuum stage was initiated, controlling the temperature at 270℃ and the vacuum degree to be less than 80Pa. The reaction was stopped after 2 hours, and the reaction product was extruded from the bottom of the polymerization reactor, cooled, and granulated to obtain the modified copolyester.

[0099] Example 2 A slurry was prepared by mixing 350g of purified terephthalic acid, 182g of ethylene glycol, 48g of isosorbide, 98g of CHDM, 0.24g of modified inorganic material-1, 2.54g of catalyst-1, 0.002g of ether inhibitor magnesium acetate, 0.075g of colorant cobalt acetate, 0.5g of antioxidant 1010, and 0.5g of antioxidant 425. This slurry was then added to a polymerization reactor. Esterification was carried out at 220℃ and an initial pressure of 0.25MPa. When the esterification liquid temperature reached 260℃ and the temperature at the top of the fractionation column was less than 120℃, the pressure in the polymerization reactor was reduced to atmospheric pressure, ending the esterification. The reactor then entered a low-vacuum stage, followed by a high-vacuum stage after 45 minutes, maintaining a temperature of 275℃ and a vacuum degree less than 80Pa. The reaction was stopped after 2 hours. The reaction product was extruded from the bottom of the polymerization reactor, cooled, and granulated to obtain the modified copolyester.

[0100] Example 3 350g of purified terephthalic acid, 122g of ethylene glycol, 96g of isosorbide, 98g of CHDM, 2.4g of modified inorganic material-1, 1.61g of catalyst-1, 0.02g of ether inhibitor calcium acetate, 0.257mg of redness agent, 0.514mg of blueness agent, 0.25g of antioxidant 1076, and 2.5g of antioxidant 168 were mixed into a slurry and added to a polymerization reactor. Esterification was carried out at a temperature of 255℃ and an initial pressure of 0.25MPa. When the esterification liquid temperature reached 260℃ and the temperature at the top of the fractionation column was less than 120℃, the pressure of the polymerization reactor was reduced to atmospheric pressure, and the esterification was completed. The reaction begins in a low vacuum stage, and after 45 minutes it enters a high vacuum stage. The temperature is controlled at 265℃ and the vacuum degree is less than 80Pa. The reaction is stopped after 2 hours. The reaction product is then extruded from the bottom of the polymerization reactor, cooled, and granulated to obtain the modified copolyester.

[0101] Example 4 350g of purified terephthalic acid, 30g of ethylene glycol, 144g of isosorbide, 120g of CHDM, 2.4g of modified inorganic material-1, 1.24g of catalyst-1, 0.02g of ether inhibitor lithium acetate, 0.257mg of redness agent, 0.514mg of blueness agent, 0.25g of antioxidant 1500, and 0.5g of antioxidant PEPQ were mixed into a slurry and added to a polymerization reactor. Esterification was carried out at a temperature of 255℃ and an initial pressure of 0.25MPa. When the esterification liquid temperature reached 260℃ and the temperature at the top of the fractionation column was less than 120℃, the pressure of the polymerization reactor was reduced to atmospheric pressure, and the esterification was completed. The reaction begins in a low vacuum stage, and after 45 minutes it enters a high vacuum stage. The temperature is controlled at 275℃ and the vacuum degree is less than 80Pa. The reaction is stopped after 2 hours. The reaction product is then extruded from the bottom of the polymerization reactor, cooled, and granulated to obtain the modified copolyester.

[0102] Example 5 350g of purified terephthalic acid, 30g of ethylene glycol, 96g of isosorbide, 98g of CHDM, 3.84g of modified inorganic material-1, 1.57g of catalyst-1, 0.02g of ether inhibitor sodium acetate, 0.257mg of redness agent, 0.514mg of blueness agent, 0.25g of antioxidant 1010, and 0.5g of antioxidant PEPQ were mixed into a slurry and added to a polymerization reactor. Esterification was carried out at a temperature of 255℃ and an initial pressure of 0.25MPa. When the esterification liquid temperature reached 260℃ and the temperature at the top of the fractionation column was less than 120℃, the pressure of the polymerization reactor was reduced to atmospheric pressure, and the esterification was completed. The reaction begins in a low vacuum stage, and after 45 minutes it enters a high vacuum stage. The temperature is controlled at 275℃ and the vacuum degree is less than 80Pa. The reaction is stopped after 2 hours. The reaction product is then extruded from the bottom of the polymerization reactor, cooled, and granulated to obtain the modified copolyester.

[0103] Example 6 The modified copolyester was prepared according to the method described in Example 1, except that the amount of catalyst-1 added was 0.508 g.

[0104] Example 7 The modified copolyester was prepared according to the method described in Example 1, except that the amount of catalyst-1 added was 0.762 g.

[0105] Example 8 The modified copolyester was prepared according to the method described in Example 1, except that the amount of catalyst-1 added was 1.778 g.

[0106] Example 9 The modified copolyester was prepared according to the method described in Example 1, except that the amount of catalyst-1 added was 2.032 g.

[0107] Example 10 The modified copolyester was prepared according to the method described in Example 1, except that the amount of catalyst-1 added was 2.286 g.

[0108] Example 11 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-2, and the amount of catalyst-2 added, calculated in germanium, was 50 μg·g based on the theoretical yield of the polyester. -1 .

[0109] Example 12 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-3, and the amount of catalyst-3 added, calculated in germanium, was 50 μg∙g based on the theoretical yield of the polyester. -1 .

[0110] Example 13 The modified copolyester was prepared according to the method described in Example 1, except that catalyst 1 was replaced with catalyst 4, and the amount of catalyst 4 added, calculated in germanium, was 50 μg·g based on the theoretical yield of the polyester. -1 .

[0111] Example 14 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-5, and the amount of catalyst-5 added, calculated in germanium, was 50 μg·g based on the theoretical yield of the polyester. -1 .

[0112] Example 15 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-6, and the amount of catalyst-6 added, calculated in germanium, was 50 μg∙g based on the theoretical yield of the polyester. -1 .

[0113] Example 16 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-7, and the amount of catalyst-7 added, calculated in germanium, was 50 μg·g based on the theoretical yield of the polyester. -1 .

[0114] Example 17 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-8, and the amount of catalyst-8 added, calculated in germanium, was 50 μg∙g based on the theoretical yield of the polyester. -1 .

[0115] Example 18 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-9, and the amount of catalyst-9 added, calculated in germanium, was 50 μg·g based on the theoretical yield of the polyester. -1 .

[0116] Example 19 The modified copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with catalyst-10, and the amount of catalyst-10 added, calculated in germanium, was 50 μg∙g based on the theoretical yield of the polyester. -1 .

[0117] Example 20 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-2, and the amount of modified inorganic material-2 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0118] Example 21 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-3, and the amount of modified inorganic material-3 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0119] Example 22 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-4, and the amount of modified inorganic material-4 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0120] Example 23 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-5, and the amount of modified inorganic material-5 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0121] Example 24 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-6, and the amount of modified inorganic material-6 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0122] Example 25 The modified copolyester was prepared according to the method described in Example 4, except that modified inorganic material-1 was replaced with modified inorganic material-7, and the amount of modified inorganic material-7 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0123] Example 26 The modified copolyester was prepared according to the method described in Example 2, except that modified inorganic material-1 was replaced with modified inorganic material-8, and the amount of modified inorganic material-8 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0124] Example 27 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-9, and the amount of modified inorganic material-9 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0125] Example 28 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-10, and the amount of modified inorganic material-10 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0126] Example 29 The modified copolyester was prepared according to the method described in Example 1, except that modified inorganic material-1 was replaced with modified inorganic material-11, and the amount of modified inorganic material-11 added, based on the theoretical yield of the polyester, was 10000 μg∙g. -1 .

[0127] Example 30 The modified copolyester was prepared according to the method described in Example 1, except that the colorant cobalt acetate was not added.

[0128] Example 31 The modified copolyester was prepared according to the method described in Example 1, except that the ether inhibitor sodium acetate was not added.

[0129] Comparative Example 1 The copolyester was prepared according to the method described in Example 1, except that 0.254 g of catalyst-1 was replaced with 0.038 g of germanium dioxide.

[0130] Comparative Example 2 The copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with 0.084 g of germanium phosphate prepared in step S2 of Example 1-1.

[0131] Comparative Example 3 The copolyester was prepared according to the method described in Example 1, except that catalyst-1 was replaced with 0.084 g of germanium phosphate prepared in step S2 of Preparation Example 1-1 and 0.171 g of heptadecanol (CAS No.: 1454-85-9).

[0132] Comparative Example 4 The copolyester was prepared according to the method described in Example 1, except that the modified inorganic material-1 was replaced with 1 g of boron nitride and 3.8 g of heptadecanol (CAS No.: 1454-85-9).

[0133] Comparative Example 5 The copolyester was prepared according to the method described in Example 1, except that 0.254 g of catalyst-1 was replaced with 0.038 g of germanium dioxide, and no modified inorganic material-1 was added.

[0134] The parameters of the copolyesters prepared in the examples and comparative examples are shown in Table 1.

[0135] Table 1

[0136] As can be seen from the results in Table 1, the Vicat softening temperature of the polyester provided in the embodiments of the present invention is higher than that of the polyester provided in the comparative example, and the zero-shear viscosity of the polyester provided in the embodiments is lower than that of the polyester provided in the comparative example, indicating that the polyester provided in the present invention has a higher Vicat softening temperature and a lower zero-shear viscosity.

[0137] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A modified copolyester, characterized in that, The modified copolyester comprises a germanium-containing compound and a modified inorganic material. The germanium-containing compound has a structure as shown in formula (I). The modified inorganic material includes an inorganic material and an alkyl alcohol modified on the inorganic material. Formula (I).

2. The modified copolyester according to claim 1, characterized in that, The structural formulas of the germanium-containing compounds are shown in formula (II) and / or formula (III). Formula (II); Formula (III); Among them, R1, R2 and R3 are each independently C1-C25 alkylene groups; Preferably, R1, R2, and R3 are all straight-chain alkylene groups; Preferably, R1, R2, and R3 are each independently a C4-C25 alkylene group; Preferably, R1, R2, and R3 are each independently a C15-C20 alkylene group; Preferably, R1 and R2 are the same.

3. The modified copolyester according to claim 1 or 2, characterized in that, The inorganic material is selected from at least one of aluminum nitride, boron nitride, silicon carbide, and aluminum oxide, preferably boron nitride; The alkyl alcohol is a C1-C25 alkyl alcohol, preferably a C4-C25 alkyl alcohol, and more preferably a C15-C20 alkyl alcohol; Preferably, the alkyl alcohol is a secondary alcohol; Preferably, the alkyl alcohol is modified onto the inorganic material by a coupling agent; Preferably, the coupling agent is a silane coupling agent; Preferably, the silane coupling agent is selected from at least one of γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane.

4. The modified copolyester according to claim 1 or 2, characterized in that, In the modified copolyester, the content of the germanium-containing compound, calculated as germanium, is 50-500 μg / g, preferably 220-300 μg / g; the content of the modified inorganic material, calculated as inorganic material, is 500-10000 μg / g, preferably 5000-10000 μg / g. Preferably, in the modified copolyester, the mass ratio of the germanium-containing compound (calculated as germanium) to the modified inorganic material (calculated as inorganic material) is 1:1-200, more preferably 1:20-40.

5. The modified copolyester according to claim 1 or 2, characterized in that, The modified copolyester also contains structural unit A as shown in formula (IV) and structural unit B as shown in formula (V); Formula (IV), Formula (V), wherein R I , R II , R III , R IV , R V and R VI are each independently selected from C1-C4 alkyl or hydrogen, preferably each independently methyl or hydrogen, further preferably hydrogen; Preferably, the modified copolyester has a Vicat softening temperature of 87-120℃, a zero-shear viscosity of 610-720 Pa·s, a color value L of 62-68, and a b value of -2-4.

5.

6. A method for preparing a modified copolyester, characterized in that, The preparation method includes: in the presence of a catalyst and a modified inorganic material, a contact reaction I is carried out between a polyol monomer and a carbonyl-containing monomer, wherein the carbonyl-containing monomer is a polyacid and / or a polyacid ester, the catalyst has the structure shown in formula (I), and the modified inorganic material includes an inorganic material and an alkyl alcohol I modified on the inorganic material. Equation (I).

7. The preparation method according to claim 6, characterized in that, The structural formulas of the germanium-containing compounds are shown in formula (II) and / or formula (III). Formula (II); Formula (III); Among them, R1, R2 and R3 are each independently C1-C25 alkylene groups; Preferably, R1, R2, and R3 are all straight-chain alkylene groups; Preferably, R1, R2, and R3 are each independently a C4-C25 alkylene group; Preferably, R1, R2, and R3 are each independently a C15-C20 alkylene group; Preferably, R1 and R2 are the same; Preferably, the method for preparing the germanium-containing compound includes: subjecting germanium phosphate and alkyl alcohol II to a contact reaction II, wherein the alkyl alcohol II is a C1-C25 alkyl alcohol; Preferably, the conditions for the contact reaction II are at least: a temperature of 100-150°C and a time of 2-4 hours.

8. The preparation method according to claim 6 or 7, characterized in that, The inorganic material is selected from at least one of aluminum nitride, boron nitride, silicon carbide, and aluminum oxide, preferably boron nitride; The alkyl alcohol I is a C1-C25 alkyl alcohol, preferably a C4-C25 alkyl alcohol, and more preferably a C15-C20 alkyl alcohol; Preferably, the alkyl alcohol I is a secondary alcohol; Preferably, the alkyl alcohol I is modified onto the inorganic material by a coupling agent; Preferably, the coupling agent is a silane coupling agent; Preferably, the silane coupling agent is selected from at least one of γ-glycidoxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-methacryloyloxypropyltrimethoxysilane; Preferably, the preparation method of the modified inorganic material includes: subjecting alkyl alcohol I, coupling agent and inorganic material to a contact reaction V; Preferably, the conditions for the contact reaction V are at least satisfied as follows: the time is 1.5-2.5h.

9. The preparation method according to claim 6 or 7, characterized in that, The polybasic acid is an aromatic dibasic acid, and the polybasic acid ester is an aromatic dibasic acid ester; the polyol contains chain diols and cyclic diols; Preferably, the cyclic diol is isosorbide and / or 1,4-cyclohexanediol; Preferably, based on the theoretical yield of the copolyester, the amount of the catalyst, calculated as germanium, is 50-500 μg / g, more preferably 220-300 μg / g; and the amount of the modified inorganic material, calculated as inorganic material, is 500-10000 μg / g, more preferably 5000-10000 μg / g. Preferably, the mass ratio of the catalyst, calculated as germanium, to the modified inorganic material, calculated as inorganic material, is 1:1-200, more preferably 1:20-40; Preferably, the cyclic diol is isosorbide and 1,4-cyclohexanediethanol, wherein the molar ratio of isosorbide to 1,4-cyclohexanediethanol is 1:1.5-2.

10. The use of the modified copolyester according to any one of claims 1 to 5 or the modified copolyester prepared by the preparation method according to any one of claims 6 to 10 in food packaging, household appliances and medical devices.

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