Polyester copolymer and preparation method thereof, modified alloy composition, modified alloy material and preparation method and application thereof

Abstract

The invention relates to the field of polyester copolymer modified alloy materials, in particular to a polyester copolymer and a preparation method thereof, a modified alloy composition, a modified alloy material and a preparation method and application thereof. The polyester copolymer contains a repetitive unit as shown in a formula (1), the number-average molecular weight of the polyester copolymer is 26000-29000 g / mol, # imgabs0, and the polyester copolymer modified alloy material further prepared from the polyester copolymer has excellent high-temperature and high-humidity resistance, high-temperature aging resistance, damp-heat aging resistance and light aging resistance; and the application field of the polyester copolymer modified alloy material is widened.

Description

Technical Field

[0001] The present invention relates to the field of polyester copolymer modified alloy materials, and in particular to a polyester copolymer and a preparation method thereof, a modified alloy composition, a modified alloy material and a preparation method and application thereof. Background Art

[0002] Polycarbonate (PC), as a thermoplastic engineering plastic, is widely used in the fields of electronics and electrical, home appliance housings, rail transit, and automotive parts. However, since ordinary polycarbonate contains a large number of ester groups in its molecular chain, it is unstable under conditions such as high radiation, high and low temperatures, high humidity, and water environments. In addition, there are rigid benzene ring groups on the molecular chain of polycarbonate, which has poor stress cracking resistance, large steric effect, and poor processing fluidity. Its aging resistance still has room for improvement.

[0003] PC is usually mixed with acrylonitrile-styrene-acrylate graft copolymer (ASA) for modification. Since ASA has good formability and environmental stress cracking resistance, the synthesized PC / ASA alloy has better fluidity, processing resistance, and stress cracking resistance than PC. However, its comprehensive performance in harsh outdoor environments is far from the expected requirements, thus losing its application value. Moreover, PC is very likely to generate extremely high internal pressure under high temperature and high humidity environments, causing stress-induced hydrolysis. Long-term accumulation will form defects on the material surface and affect the glossiness. Therefore, it needs to be modified to improve its comprehensive performance.

[0004] Polycarbonate synthesized with fluorinated bis(4-hydroxyphenyl)alkane as raw material has higher heat resistance and can be used in some special high-temperature fields. However, for different application environments, high-temperature resistant polycarbonate with different heat resistance grades needs to be synthesized. In the actual production process, frequent switching of polycarbonate grades will bring more secondary and transitional materials, increase production costs, and fail to meet the sustainable development needs of environmental protection and energy saving.

[0005] PC / ASA alloy is in high temperature and high humidity environment for a long time, and its poor heat resistance will cause its deformation and significant performance degradation, while the aging problem of PC will further affect the appearance and safety. Therefore, how to ensure that the modified alloy material has good anti-aging performance, heat resistance and hydrolysis resistance is a problem that needs to be solved at present. Summary of the invention

[0006] The purpose of the present invention is to overcome the problems of poor aging resistance, heat resistance and hydrolysis resistance of polycarbonate in the prior art, and to provide a polyester copolymer and a preparation method thereof, a modified alloy composition, a modified alloy material and a preparation method and application thereof. The prepared polyester copolymer modified alloy material has good aging resistance, heat resistance, hydrolysis resistance, radiation resistance and mechanical properties at high temperature, and the process flow is simple, safe and environmentally friendly.

[0007] In order to achieve the above object, the present invention provides a polyester copolymer in a first aspect, wherein the polyester copolymer comprises a repeating unit represented by formula (1):

[0008] Where R 1 and R 2 Each is independently H, methyl or ethyl, m, n, a, b are natural numbers, wherein m+n=3 and m≠0, a+b=3 and a≠0.

[0009] A second aspect of the present invention provides a method for preparing a polyester copolymer, wherein the method comprises:

[0010] In the presence of a catalyst, the fluorinated bisphenol monomer and the carbonyl monomer represented by formula (2) are subjected to transesterification, polycondensation and final polymerization to obtain the polyester copolymer;

[0011] Where R 1 and R 2 Each is independently H, methyl or ethyl, m, n, a, b are natural numbers, wherein m+n=3 and m≠0, a+b=3 and a≠0.

[0012] The third aspect of the present invention provides a polyester copolymer modified alloy composition, which comprises the polyester copolymer described in the first aspect or the polyester copolymer prepared by the method described in the second aspect, polycarbonate, styrene-acrylonitrile-acrylic rubber copolymer, antioxidant, release agent, compatibilizer, toughening agent and UV absorber.

[0013] The fourth aspect of the present invention provides a polyester copolymer modified alloy material, which is obtained by melt extrusion of the composition described in the third aspect.

[0014] A fifth aspect of the present invention provides a method for preparing a polyester copolymer modified alloy material, the method comprising:

[0015] (1) mixing a polyester copolymer, a polycarbonate, a styrene-acrylonitrile-acrylic rubber copolymer, an antioxidant, a release agent, a compatibilizer, a toughening agent and a UV absorber to obtain a premix;

[0016] (2) melt-extruding the premix under negative pressure to obtain the polyester copolymer modified alloy material;

[0017] Wherein, the polyester copolymer is the polyester copolymer described in the first aspect and the third aspect.

[0018] The sixth aspect of the present invention provides an application of the polyester copolymer modified alloy material described in the fourth aspect or the polyester copolymer modified alloy material prepared by the preparation method described in the fifth aspect in charging piles, outdoor electronic appliances, electric meter cases and vehicle exterior parts.

[0019] Through the above technical solution, the present invention has the following beneficial effects:

[0020] (1) The polyester copolymer provided by the present invention has a repeating unit of formula (1), and uses a fluorinated bisphenol monomer and a carbonyl monomer as raw materials. Under an appropriate raw material molar ratio, by adding an alkaline catalyst and using an adjustable vacuum pump system, the yield of the synthesized polyester copolymer is greater than 75%, and the catalyst has a high catalytic activity. The obtained polyester copolymer meets the actual use requirements;

[0021] (2) The polyester copolymer provided by the present invention increases the bond energy and reduces the risk of thermal oxidation degradation caused by chain scission by introducing fluorine groups, so that the polyester copolymer modified alloy material obtained by further alloying retains the respective advantages of the original PC and ASA phases, improves the mechanical properties and fluidity of the modified alloy material, and has good aging resistance, heat resistance, hydrolysis resistance and radiation resistance, and has a stable appearance color;

[0022] (3) The preparation method of the polyester copolymer and the polyester copolymer modified alloy material provided by the present invention is simple in process, conforms to the concept of green environmental protection, can realize the industrial production of aging-resistant polyester copolymer modified alloy materials, and meet the application requirements under special environments. DETAILED DESCRIPTION

[0023] The endpoints and any values ​​of the ranges disclosed in this article 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 each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0024] The first aspect of the present invention provides a polyester copolymer, wherein the polyester copolymer comprises a repeating unit represented by formula (1):

[0025] Where R 1 and R 2 Each is independently H, methyl or ethyl, m, n, a, b are natural numbers, wherein m+n=3 and m≠0, a+b=3 and a≠0.

[0026] In some embodiments of the present invention, preferably, m=3, a=3. In the present invention, among the polyester copolymers containing the repeating units represented by the above formula (1), the polyester copolymers containing the preferred repeating units are represented by the following formula (3):

[0027]

[0028] In some embodiments of the present invention, preferably, the number average molecular weight of the polyester copolymer is 26000-29000 g / mol.

[0029] In some embodiments of the present invention, preferably, the apparent viscosity of the polyester copolymer at 25°C is 1.25-1.45dl / g. In the present invention, the apparent viscosity of the polyester copolymer is within the above range, the fluidity is good, the compatibility between the components is improved, and it is conducive to full mixing with the components, and the obtained polyester copolymer modified alloy material has good comprehensive performance. The apparent viscosity of the polyester copolymer is greater than 1.45dl / g, the fluidity is poor, the compatibility with the components is poor, and the injection molding performance is poor; the apparent viscosity of the polyester copolymer is less than 1.25dl / g, the fluidity is good, but the impact strength of the material itself is low.

[0030] In some embodiments of the present invention, preferably, the polyester copolymer has a melt index of 8-11 g / 10 min at 300° C. and a load of 1.2 kg.

[0031] A second aspect of the present invention provides a method for preparing a polyester copolymer, the method comprising:

[0032] In the presence of a catalyst, the fluorinated bisphenol monomer and the carbonyl monomer represented by formula (2) are subjected to transesterification, polycondensation and final polymerization to obtain the polyester copolymer;

[0033] Where R 1 and R 2 Each is independently H, methyl or ethyl, m, n, a, b are natural numbers, wherein m+n=3 and m≠0, a+b=3 and a≠0.

[0034] In some embodiments of the present invention, preferably, m=3, a=3.

[0035] In some embodiments of the present invention, preferably, the carbonyl monomer is selected from at least one of diphenyl carbonate, dimethyl carbonate and diethyl carbonate, preferably diphenyl carbonate.

[0036] In some embodiments of the present invention, preferably, the molar ratio of the fluorinated bisphenol monomer to the carbonyl monomer is 1:1.1-1.3; the mass ratio of the fluorinated bisphenol monomer to the catalyst is 1:0.0005-0.001. In the present invention, the molar ratio of the fluorinated bisphenol monomer to the carbonyl monomer and the mass ratio of the fluorinated bisphenol monomer to the catalyst are controlled within the above ranges, so that the polyester copolymer has a higher yield. In addition, in the present invention, the purity of the fluorinated bisphenol compound is 99.5%, and the purity of the carbonyl compound is 99.7%.

[0037] In some embodiments of the present invention, preferably, the catalyst is selected from at least one of sodium phenolate, potassium phenolate, sodium methoxide and sodium tetraphenylborate. In the present invention, the catalyst has a high catalytic activity, can make the polyester copolymer yield high and meet the actual use needs; in addition, the original mass concentration of the catalyst is 98%, and the catalyst is diluted with a phenol solution to prepare a catalyst phenol solution with a mass concentration of 1% to meet the experimental requirements.

[0038] In some embodiments of the present invention, preferably, the transesterification temperature is 150-240°C, and the time is 0.5-2h; the polycondensation temperature is 200-280°C, and the time is 0.5-2h; and the final polymerization temperature is 260-300°C, and the time is 0.5-2h.

[0039] In the present invention, raw materials and catalysts are added to a 2L reactor with a stirring device to carry out an ester exchange reaction, nitrogen is filled to replace air, and a liquid ring vacuum pump is used to evacuate and then nitrogen is sealed, and the vacuum degree is controlled at 10-20 kPa. The temperature of the reactor is raised to 140° C. by an electric heater and stirring is started. The temperature is continued to be raised to 150-240° C. and the liquid level is controlled to be 30-60%. During the ester exchange reaction, under the action of the liquid ring vacuum pump, the by-product phenol and a small amount of low molecular weight polycondensate are removed, so that the reaction proceeds in the forward direction; then the reactor is heated to 200-28 0°C, controlling the liquid level to be 30-60%, and performing a polycondensation reaction. During the polycondensation reaction, phenol and low molecular weight polycondensates are removed under the action of a liquid ring vacuum pump, so that the reaction proceeds in a forward direction. As the reaction proceeds, the molecular weight increases, and the difficulty of the reaction increases. The temperature is continued to be raised to perform a final polymerization reaction, and residual raw material diphenyl carbonate and low molecular weight polycondensates are removed under a high temperature environment, and the reaction is terminated. The temperature of the final polymerization reaction is 260-300°C, and the liquid level is 30-60%. After the reaction is completed, the block is taken out and crushed by a crusher to obtain the halogenated polycarbonate material.

[0040] According to the present invention, by using fluorinated bisphenol monomers and carbonyl monomers as raw materials and adding alkaline catalysts within the dosage range specified in the present invention, it is beneficial to achieve efficient and stable production of polyester copolymers to meet subsequent alloying requirements.

[0041] The third aspect of the present invention provides a polyester copolymer modified alloy composition, which comprises the polyester copolymer described in the first aspect or the polyester copolymer prepared by the method described in the second aspect, polycarbonate, acrylonitrile-styrene-acrylate copolymer, antioxidant, release agent, compatibilizer, toughening agent and UV absorber.

[0042] In some embodiments of the present invention, preferably, the polycarbonate is selected from aromatic polycarbonate, preferably bisphenol A polycarbonate.

[0043] In some embodiments of the present invention, preferably, the weight average molecular weight of the polycarbonate is 20000-40000 g / mol.

[0044] In some embodiments of the present invention, preferably, the polycarbonate has a melt index of 5-25 g / 10 min at 300° C. and a load of 1.2 kg.

[0045] In some embodiments of the present invention, preferably, in the acrylonitrile-styrene-acrylate copolymer, the content of the acrylate structural unit is 50-70 wt %. In the present invention, the acrylate structural unit is derived from an acrylate monomer.

[0046] In some embodiments of the present invention, preferably, the acrylonitrile-styrene-acrylate copolymer has a melt index of 5-15 g / 10 min at 220° C. and a load of 10 kg.

[0047] In some embodiments of the present invention, preferably, the antioxidant is selected from hindered phenol antioxidants and / or phosphite antioxidants, preferably selected from one or two of [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris[2,4-di-tert-butylphenyl]phosphite. In the present invention, the antioxidant can ensure that the performance of the modified alloy material during processing is more stable and provide long-term use guarantee.

[0048] In some embodiments of the present invention, preferably, the release agent is selected from at least one of stearic acid amide, hydrocarbon and fatty acid lubricants, preferably pentaerythritol tetrastearate. In the present invention, the release agent provides a certain lubricity, which is conducive to ensuring smooth demolding of the material.

[0049] In some embodiments of the present invention, preferably, the compatibilizer is an epoxy functional group grafted polymer, preferably a glycidyl methacrylate grafted styrene-acrylonitrile copolymer, and the epoxy functional group grafted polymer has an epoxy resin structural unit content of 0.5-10wt%. In the present invention, the epoxy resin structural unit comes from epoxy resin; in addition, in the present invention, the content range of the epoxy resin structural unit is conducive to ensuring good compatibility between the polycarbonate phase and the acrylonitrile-styrene-acrylate copolymer phase, and reducing the risk of phase separation of the modified alloy material.

[0050] In some embodiments of the present invention, preferably, the toughening agent is a silicon-containing copolymer impact modifier. In the present invention, the toughening agent is S2501, wherein the toughening agent has a core-shell structure, and can be particularly well dispersed in the modified alloy material, and because its core is an organosilicon polymer, it can improve the notched impact strength and tensile strength, and improve the mechanical properties of the modified alloy material.

[0051] In some embodiments of the present invention, preferably, the UV absorber is selected from 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and / or 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol). In the present invention, the UV absorber can ensure that the performance of the modified alloy material is not destroyed in a long-term high-intensity irradiation environment, and the performance retention rate is high.

[0052] In the present invention, a fluorine-containing group is introduced to protect the isopropyl group, thereby increasing the bond energy and reducing the risk of thermal oxidation degradation caused by chain scission, thereby improving the heat resistance of the polyester copolymer modified alloy material, and being able to improve the hydrolysis resistance of the material to a certain extent. The fluorine-containing polyester copolymer is further alloyed, and the amount of each component is controlled within the above range, which is beneficial for the modified alloy material to have excellent aging resistance, good mechanical properties, heat resistance, hydrolysis resistance and radiation resistance, improve the fluidity of the modified alloy material, be easy to process, have good comprehensive performance, and meet the market demand for aging resistance.

[0053] The fourth aspect of the present invention provides a polyester copolymer modified alloy material, which is obtained by melt extrusion of the composition described in the third aspect.

[0054] In some embodiments of the present invention, preferably, the notched impact strength of the modified alloy material is 56-73 kJ / m 2 ; The tensile strength is 49-54MPa; the heat deformation temperature of 1.8MPa is 101-121℃.

[0055] A fifth aspect of the present invention provides a method for preparing a polyester copolymer modified alloy material, the method comprising:

[0056] (1) mixing a polyester copolymer, a polycarbonate, an acrylonitrile-styrene-acrylate copolymer, an antioxidant, a release agent, a compatibilizer, a toughening agent and a UV absorber to obtain a premix;

[0057] (2) melt-extruding the premix under negative pressure to obtain the polyester copolymer modified alloy material;

[0058] Wherein, the polyester copolymer is the polyester copolymer described in the first aspect or the polyester copolymer prepared by the method described in the second aspect.

[0059] In some embodiments of the present invention, preferably, the screw aspect ratio of the twin-screw extruder is 32-40:1, and the screw temperature is 170-270°C.

[0060] In some embodiments of the present invention, preferably, the negative pressure is -0.075 MPa to -0.08 MPa.

[0061] In the present invention, in step (1), the composition described in the fourth aspect is added to a high-speed mixer according to the corresponding weight and fully mixed for 3-5 minutes to obtain a premix; in step (2), the premix is ​​fed from the main feeding port of a twin-screw extruder, the pressure is controlled to be -0.075MPa to -0.08MPa, and the premix is ​​melted, plasticized, sheared, and dispersed, and then extruded through a die head, pulled, cooled, granulated, and homogenized to obtain the polyester copolymer modified alloy material.

[0062] According to the present invention, the temperatures of the screws in each section of the twin-screw extruder include: the temperature of the feeding zone in zone 1 is 170-190°C, the temperature of the pressure building zone in zone 2 is 230-260°C, the temperature of the pressure building zone in zone 3 is 230-260°C, the melting temperature in zone 4 is 230-260°C, the exhaust temperature in zone 5 is 220-250°C, the conveying temperature in zone 6 is 230-270°C, the pressure building temperature in zone 7 is 220-250°C, the temperature of the devolatilization zone in zone 8 is 230-260°C, the temperature of the pressure building zone in zone 9 is 220-250°C, and the head temperature is 230-260°C.

[0063] The sixth aspect of the present invention provides an application of the polyester copolymer modified alloy material described in the fourth aspect or the polyester copolymer modified alloy material prepared by the preparation method described in the fifth aspect in charging piles, outdoor electronic appliances, electric meter cases and vehicle exterior parts.

[0064] The present invention will be described in detail below through examples.

[0065] The structure of the polyester copolymer obtained in the embodiment is 1The content of repeating units in the polyester copolymer is determined by feeding.

[0066] Yield: The white solid obtained by the reaction was washed with ethanol, dried and weighed using an analytical balance. The obtained data was divided by the theoretical maximum yield of 535.75 g to obtain the actual yield. The actual yield of the polyester copolymer (%) = (weighed value / 535.75) × 100%.

[0067] The differences in the number average molecular weight (Mn) and distribution (PDI) of synthesized PC with different hydroxyl end group contents were tested by gel permeation chromatography (GPC). Test conditions: sample mass 10 mg, solvent tetrahydrofuran, test temperature 40 ° C, mobile phase N, N-dimethylformamide, flow rate 1.0 mL / min, standard sample monodisperse polystyrene.

[0068] The apparent viscosity of the polyester copolymer was tested by capillary rheometer at a test temperature of 25°C.

[0069] The performance testing described includes the following tests:

[0070] The prepared product particles were dried in a blast oven at 90°C for 4 hours, and injection molded into standard samples using an injection molding machine at an injection molding temperature of 260°C. The samples were placed under standard conditions of 50% relative humidity and 23°C for 24 hours before performance testing.

[0071] Fluidity test: The test is carried out in accordance with ISO1133 "Determination of mass flow rate and volume flow rate of thermoplastic melts", and the test conditions are 260℃ / 5kg·10min;

[0072] Tensile strength and elongation at break test: The test was conducted in accordance with ISO 527-2 "Test method for tensile properties of plastics", with a specimen length of 75 mm, a thickness of 3 mm, a gauge length of 20 mm, and a tensile test rate of 50 mm / min;

[0073] IZOD notched impact strength test: The test is carried out in accordance with ISO 179 "Determination of impact strength of simply supported beams of plastics", and the specimen is 80 mm long, 10 mm wide and 4 mm thick;

[0074] Heat deformation temperature test: The test is carried out in accordance with ISO 75-1 "Determination of load deformation temperature of plastics", and the specimen length is 80mm, the width is 10mm, and the thickness is 4mm;

[0075] Aging test: 40 notched impact test strips, 20 tensile test strips, and 20 color plates were selected and divided into groups for high temperature and high humidity, high temperature aging, water boiling test, and irradiation test. The long-term test conditions of high temperature and high humidity are 75°C, 95%RH, and 1000h; the high temperature aging test conditions are 100°C and 1000h; the water boiling test conditions are to completely immerse the test piece in a 70°C constant temperature water tank for 240h; the irradiation test conditions are to use a xenon lamp for irradiation, refer to the ISO 4892.2Cycle1 test method, and the total test time is 1000h.

[0076] Performance retention rate: The performance change of the specimen before and after the aging test is intuitively reflected through testing and retention rate calculation, performance retention rate % = (performance after aging / original performance) × 100%;

[0077] The color change of the test color plate before and after the aging test was measured by a colorimeter, and the ΔE color difference was calculated according to the relevant provisions of GB / T3979-2008 "Measurement method of object color" and GB / T7921-2008 "Uniform color space and color difference formula".

[0078] The raw materials used in the following examples are:

[0079] Bisphenol AF was purchased from Wuhan Lanabai Pharmaceutical Chemicals with a purity of 99.5%;

[0080] Diphenyl carbonate was purchased from Zhejiang Iron and Steel Dafeng Chemical Industry with a purity of 99.7%;

[0081] The catalyst mass concentration is 98%, purchased from Aladdin Reagent (Shanghai) Co., Ltd., 1# catalyst is sodium phenolate, 2# catalyst is potassium phenolate, 3# catalyst is sodium methoxide, 4# catalyst is sodium tetraphenylborate, and the catalyst configuration is a phenol solution of the catalyst;

[0082] Polycarbonate was purchased from Dafeng Chemical, with a grade of 02-20, a melt index of 20 g / 10 min at 300°C and a load of 1.2 kg, and a weight average molecular weight of 26,000 g / mol;

[0083] The halogenated polycarbonate is prepared according to the third aspect of the present invention;

[0084] Acrylonitrile-styrene-acrylate copolymer was purchased from Kumho, South Korea, with a brand name of XC-230, and a melt index of 5 g / 10 min at 220°C and a load of 10 kg;

[0085] The toughening agent was purchased from Mitsubishi Rayon of Japan, with the brand name S2501;

[0086] The antioxidants were purchased from BASF Corporation, hindered phenol and / or phosphite antioxidants;

[0087] The mold release agent was purchased from Minke New Materials: pentaerythritol tetrastearate;

[0088] The compatibilizer was purchased from Jiangsu Jiayirong, brand SAG-002;

[0089] The UV absorber was purchased from the benzotriazole class of Lianlong New Materials.

[0090] Example 1

[0091] Preparation of polyester copolymers:

[0092] The reaction is carried out in a reactor equipped with a stirring and temperature control device. 500g of bisphenol AF, 349.7g of diphenyl carbonate and 0.3g of 1# catalyst phenol solution are added to a 2L reactor, the air is replaced by nitrogen, and a liquid ring vacuum pump is used to evacuate and nitrogen seal is performed, the vacuum degree is controlled to be 10-20kPa, the temperature is raised to 140°C and stirring is started; the temperature is continued to be raised to 210°C, an ester exchange reaction is performed, the liquid level is controlled to be 40-60%, and the reaction is performed for 1h; then the reactor is heated to 260°C, a condensation reaction is performed, the liquid level is controlled to be 30-50%, and the reaction is performed for 1h; the reactor is heated to 280°C, a final polymerization reaction is performed, the liquid level is controlled to be 30-50%, and the reaction is performed for 1h to obtain a mass; after the reaction is completed, the mass is taken out, washed and dried with anhydrous ethanol, and crushed by a crusher.

[0093] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0094]

[0095] Preparation of polyester copolymer modified alloy:

[0096] (1) 20 parts by weight of polyester copolymer, 50 parts by weight of polycarbonate, 30 parts by weight of acrylonitrile-styrene-acrylate copolymer, 0.2 parts by weight of antioxidant, 0.3 parts by weight of release agent, 1 part by weight of compatibilizer, 4 parts by weight of toughening agent and 0.3 parts by weight of UV absorber were weighed, added into a high-speed mixer and mixed thoroughly for 3 minutes to obtain a premix;

[0097] (2) The premix is ​​fed into the main feed port of the twin-screw extruder, the pressure is controlled to be -0.075 to -0.08 MPa, the aspect ratio of the screw is controlled to be 40:1, and the temperature of the screw is 170-270° C. The premix is ​​melted, plasticized, sheared, and dispersed in the extruder, extruded through a die head, pulled, cooled, granulated, and homogenized to obtain a polyester copolymer modified alloy material.

[0098] Example 2

[0099] Preparation of polyester copolymers:

[0100] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 2,2,4,4-tetrafluoro-3,3-bis(4-hydroxyphenyl)pentane, the amount of diphenyl carbonate was 391.87 g, and 0.3 g of 1# catalyst phenol solution was replaced by 0.3 g of 2# catalyst phenol solution.

[0101] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0102]

[0103] Preparation of polyester copolymer modified alloy materials:

[0104] The polyester copolymer modified alloy material was prepared according to the method of Example 1.

[0105] Example 3

[0106] Preparation of polyester copolymers:

[0107] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 2,4-difluoro-3,3-bis(4-hydroxyphenyl)pentane, the amount of diphenyl carbonate was 421.84 g, and 0.3 g of 1# catalyst phenol solution was replaced by 0.3 g of 3# catalyst phenol solution.

[0108] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0109]

[0110] Preparation of polyester copolymer modified alloy materials:

[0111] The polyester copolymer modified alloy material was prepared according to the method of Example 1.

[0112] Example 4

[0113] Preparation of polyester copolymers:

[0114] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 3,3,5,5-tetrafluoro-4,4-bis(4-hydroxyphenyl)heptane, and the amount of diphenyl carbonate was 346.17 g.

[0115] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0116]

[0117] Preparation of polyester copolymer modified alloy materials:

[0118] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 30 parts by weight of the polyester copolymer and 40 parts by weight of the polycarbonate were weighed.

[0119] Example 5

[0120] Preparation of polyester copolymers:

[0121] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 3,5-difluoro-4,4-bis(4-hydroxyphenyl)heptane, and the amount of diphenyl carbonate was 401.66 g.

[0122] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0123]

[0124] Preparation of polyester copolymer modified alloy materials:

[0125] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 30 parts by weight of the polyester copolymer, 40 parts by weight of the polycarbonate and 6 parts by weight of the toughening agent were weighed.

[0126] Example 6

[0127] Preparation of polyester copolymers:

[0128] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 2,2,4,4-tetrafluoro-3,3-bis(4-hydroxyphenyl)hexane, and the amount of diphenyl carbonate was 375.82 g.

[0129] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0130]

[0131] Preparation of polyester copolymer modified alloy materials:

[0132] The polyester copolymer modified alloy material was prepared according to the method of Example 1.

[0133] Comparative Example 1

[0134] Preparation of polyester copolymers:

[0135] A polyester copolymer was prepared according to the method of Example 1, except that the amount of diphenyl carbonate was 478.17 g.

[0136] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0137]

[0138] Preparation of polyester copolymer modified alloy materials:

[0139] The polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 30 parts by weight of the polyester copolymer and 40 parts by weight of the polycarbonate were weighed, and no compatibilizer was added.

[0140] Comparative Example 2

[0141] Preparation of polyester copolymers:

[0142] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 2,2,4,4-tetrafluoro-3,3-bis(4-hydroxyphenyl)pentane, and the amount of diphenyl carbonate was 342.88 g.

[0143] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0144]

[0145] Preparation of polyester copolymer modified alloy materials:

[0146] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 10 parts by weight of the polyester copolymer and 60 parts by weight of the polycarbonate were weighed.

[0147] Comparative Example 3

[0148] Preparation of polyester copolymers:

[0149] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 2,2,4,4-tetrafluoro-3,3-bis(4-hydroxyphenyl)pentane, the amount of diphenyl carbonate was 326.55 g, and 0.3 g of 1# catalyst phenol solution was replaced by 0.3 g of 4# catalyst phenol solution.

[0150] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0151]

[0152] Preparation of polyester copolymer modified alloy materials:

[0153] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 30 parts by weight of the polyester copolymer and 40 parts by weight of the polycarbonate were weighed.

[0154] Comparative Example 4

[0155] Preparation of polyester copolymers:

[0156] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 3,3,5,5-tetrafluoro-4,4-bis(4-hydroxyphenyl)octane, and the amount of diphenyl carbonate was 391.86 g.

[0157] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0158]

[0159] Preparation of polyester copolymer modified alloy materials:

[0160] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 30 parts by weight of the polyester copolymer, 40 parts by weight of the polycarbonate and 1 part by weight of the toughening agent were weighed.

[0161] Comparative Example 5

[0162] Preparation of polyester copolymers:

[0163] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 4,4,6,6-tetrafluoro-5,5-bis(4-hydroxyphenyl)nonane, and the amount of diphenyl carbonate was 334.72 g.

[0164] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0165]

[0166] Preparation of polyester copolymer modified alloy materials:

[0167] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 40 parts by weight of the polyester copolymer, 40 parts by weight of polycarbonate and 20 parts by weight of acrylonitrile-styrene-acrylate copolymer were weighed.

[0168] Comparative Example 6

[0169] Preparation of polyester copolymers:

[0170] A polyester copolymer was prepared according to the method of Example 1, except that bisphenol AF was replaced by 4,4,6,6-tetrafluoro-5,5-bis(4-hydroxyphenyl)decane and the amount of diphenyl carbonate was 336.4 g.

[0171] The obtained solid product was analyzed and determined to be a polyester copolymer containing the following repeating units:

[0172]

[0173] Preparation of polyester copolymer modified alloy materials:

[0174] A polyester copolymer modified alloy material was prepared according to the method of Example 1, except that 30 parts by weight of the polyester copolymer and 40 parts by weight of the polycarbonate were weighed.

[0175] Table 1 Test results

[0176]

[0177]

[0178] Table 1 (continued)

[0179]

[0180]

[0181] It can be seen from the results in Table 1 that the polyester copolymer modified alloy material with good aging resistance can be obtained by the method of the present invention. It can be seen from Examples 1-6 in Table 1 that the yield of the polyester copolymer prepared by the catalyst defined in the present invention is greater than 75%, indicating that the catalyst has a high catalytic activity, and the number average molecular weight of the obtained product is higher than 26000g / mol, and the apparent viscosity (25°C) is ≥1.25dl / g, which meets the needs of practical application; It can be seen from Examples 1-6 that the polyester copolymer modified alloy material prepared by the polyester copolymer provided by the present invention can improve the impact strength, high temperature and humidity resistance, high temperature aging resistance, wet heat aging resistance and light aging resistance of the modified alloy material, and broaden the application field of the polyester copolymer modified alloy material; Comparative Examples 1-6 do not use the method defined in the present invention, the yield of the polyester copolymer obtained is low, and the number average molecular weight and apparent viscosity (25°C) are low, which do not meet the use requirements, and the further obtained modified alloy material cannot meet the use under high temperature and humidity, high temperature aging, boiling and irradiation environments at the same time, and the comprehensive performance is poor.

[0182] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A polyester copolymer comprising a repeating unit represented by formula (1), Where R 1 and R 2 Each independently represents H, methyl or ethyl, m, n, a, b are natural numbers, in, m+n=3 and m≠0, a+b=3 and a≠0.

2. The polyester copolymer according to claim 1, in, m=3, a=3.

3. The polyester copolymer according to claim 1 or 2, in, The number average molecular weight of the polyester copolymer is 26000-29000 g / mol; Preferably, the apparent viscosity of the polyester copolymer at 25° C. is 1.25-1.45 dl / g; Preferably, the polyester copolymer has a melt index of 8-11 g / 10 min at 300° C. and a load of 1.2 kg.

4. A method for preparing a polyester copolymer, It is characterized in that The method includes: In the presence of a catalyst, the fluorinated bisphenol monomer and the carbonyl monomer represented by formula (2) are subjected to transesterification, polycondensation and final polymerization to obtain the polyester copolymer; Where R 1 and R 2 Each is independently H, methyl or ethyl, m, n, a, b are natural numbers, wherein m+n=3 and m≠0, a+b=3 and a≠0.

5. The preparation method according to claim 4, in, m=3, a=3; Preferably, the carbonyl monomer is selected from at least one of diphenyl carbonate, dimethyl carbonate and diethyl carbonate, preferably diphenyl carbonate; Preferably, the molar ratio of the fluorinated bisphenol monomer to the carbonyl monomer is 1:1.1-1.3; Preferably, the mass ratio of the fluorinated bisphenol monomer to the catalyst is 1:0.0005-0.001; Preferably, the catalyst is selected from at least one of sodium phenolate, potassium phenolate, sodium methoxide and sodium tetraphenylborate; Preferably, the transesterification temperature is 150-240°C and the time is 0.5-2h; Preferably, the polycondensation temperature is 200-280°C and the time is 0.5-2h; Preferably, the final polymerization temperature is 260-300° C., and the time is 0.5-2 h.

6. A polyester copolymer modified alloy composition, It is characterized in that The composition comprises: the polyester copolymer according to claims 1 to 3 or the polyester copolymer prepared by the method according to claim 4 or 5, polycarbonate, acrylonitrile-styrene-acrylate copolymer, antioxidant, release agent, compatibilizer, toughening agent and UV absorber.

7. The composition according to claim 6, in, The polycarbonate is selected from aromatic polycarbonate, preferably bisphenol A polycarbonate; Preferably, the weight average molecular weight of the polycarbonate is 20000-40000 g / mol; Preferably, the polycarbonate has a melt index of 5-25 g / 10 min at 300° C. and a load of 1.2 kg; Preferably, in the acrylonitrile-styrene-acrylate copolymer, the content of the acrylate structural unit is 50-70wt%; Preferably, the acrylonitrile-styrene-acrylate copolymer has a melt index of 5-15 g / 10 min at 220° C. and a load of 10 kg; Preferably, the antioxidant is selected from hindered phenol antioxidants and / or phosphite antioxidants, preferably selected from one or two of [β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester, β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris[2,4-di-tert-butylphenyl]phosphite; Preferably, the release agent is selected from at least one of stearic acid amide, hydrocarbon and fatty acid lubricants, preferably pentaerythritol tetrastearate; Preferably, the compatibilizer is an epoxy functional group grafted polymer, preferably a glycidyl methacrylate grafted styrene-acrylonitrile copolymer, and the content of the epoxy resin structural unit in the epoxy functional group grafted polymer is 0.5-10wt%; Preferably, the toughening agent is a silicon-containing copolymer impact modifier; Preferably, the UV absorber is selected from 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole and / or 2,2'-methylenebis(4-tert-octyl-6-benzotriazolephenol).

8. A polyester copolymer modified alloy material, It is characterized in that Obtained by melt extrusion of the composition according to claim 6 or 7; Preferably, the notched impact strength of the modified alloy material is 56-73 kJ / m 2 ;Tensile strength is 49-54MPa; The heat deformation temperature of 1.8MPa is 101-121℃.

9. A method for preparing a polyester copolymer modified alloy material, It is characterized in that The method includes: (1) mixing a polyester copolymer, a polycarbonate, an acrylonitrile-styrene-acrylate copolymer, an antioxidant, a release agent, a compatibilizer, a toughening agent and a UV absorber to obtain a premix; (2) melt-extruding the premix under negative pressure to obtain the polyester copolymer modified alloy material; Wherein, the polyester copolymer is the polyester copolymer described in claims 1-3 or the polyester copolymer prepared by the method described in claim 4 or 5; Preferably, the screw aspect ratio of the twin-screw extruder is 32-40:1, and the screw temperature is 170-270°C; Preferably, the negative pressure is -0.075 MPa to -0.08 MPa.

10. Use of the polyester copolymer modified alloy material according to claim 8 or the polyester copolymer modified alloy material obtained by the method according to claim 9 in charging piles, outdoor electronic appliances, electric meter housings and vehicle exterior trims.

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