Method for preparing polyester-based permanent antistatic material through in-situ polymerization and nano metal oxide compounding and product
By modifying nanometal oxides and combining in-situ polymerization technology, a polyester-based permanent anti-static material is prepared, which solves the problem that metal oxide anti-static agents are difficult to disperse uniformly in polymer matrix in the prior art, and achieves a comprehensive improvement of the good anti-static properties and material properties of polyester materials.
Patent Information
- Application Number
- CN202510247410.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-04
- Publication Date
- 2025-05-27
AI Technical Summary
The existing metal oxide antistatic agents are difficult to disperse uniformly in polymer matrix, resulting in a large amount of filling required for the formation of charge transport channels, resulting in a decrease in the overall physical properties of the material and limited application.
By modifying the doped nanometal oxides and combining in situ polymerization technology, a polyester-based permanent anti-static material is prepared, and the size and catalytic effects of the nanometal oxides are used to achieve their uniform dispersion and efficient anti-static properties in the polyester matrix.
It achieves good anti-static effect at a smaller amount of addition, ensures the transparency and mechanical properties of the material, reduces production costs, and improves the color of the material.
Smart Images
Figure BDA0005295946750000151 
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of polymer materials, and particularly relates to a method for preparing a polyester-based permanent antistatic material by in-situ polymerization and composite with nano metal oxides and the obtained product. Background Art
[0002] In plastic and rubber products, static electricity accumulation may lead to surface dirt adsorption of materials, performance degradation, and electrostatic discharge (ESD) problems during the production process. To solve these problems, researchers have gradually recognized that metal oxides such as aluminum oxide (Al 2 O 3 ), zinc oxide (ZnO), and titanium oxide (TiO 2 ) etc. can be used as antistatic agents in polymer materials.
[0003] However, the effective application of metal oxide antistatic agents faces several key technical challenges. The antistatic mechanism of metal oxides is to form a percolation conductive network in the polymer matrix by their particles to dissipate static charges and achieve the antistatic effect. However, since metal oxides are usually difficult to be uniformly dispersed in the polymer matrix, the formation of charge transport channels requires a large amount of metal oxide filling, which will lead to a decrease in the overall physical properties of the finally obtained polymer material, such as difficult coloring, easy falling off of fillers, etc., restricting their application in the field of polymer antistatic. Summary of the Invention
[0004] Aiming at the deficiencies of the prior art, the present invention modifies the nano metal oxides doped with metals, and combines in-situ polymerization to prepare an antistatic composite material, and a polyester-based permanent antistatic material can be obtained. It not only has a low addition amount, but also can utilize the catalytic effect of the metal oxide itself to accelerate the in-situ polymerization reaction of polyester, and can also improve the chromaticity of the material.
[0005] The specific technical solution of the present invention is as follows:
[0006] In the first aspect of the present invention, a method for preparing a polyester-based permanent antistatic material by in-situ polymerization and composite with nano metal oxides is provided, including the following steps:
[0007] 1) Preparation of composite antistatic agent solution: uniformly disperse the nano metal oxides doped with metals and a dispersant in a solvent to obtain a composite antistatic agent solution;
[0008] 2) Pulping of raw materials: select and prepare at least one dicarboxylic acid or its ester derivative and at least one diol as monomers of polyester, and add them to the composite antistatic agent solution obtained in step 1) for mixing and pulping;
[0009] 3) Esterification reaction: add the pulped slurry to a catalyst for esterification reaction;
[0010] 4) Polycondensation reaction: After the esterification is completed, a stabilizer and a co-dispersant are added, and polycondensation is carried out to obtain the polyester-based permanent antistatic material.
[0011] By selecting a composite of a doped-metal nano-metal oxide and a dispersant, its dispersibility in the polymer matrix is improved, so that the nano-metal oxide antistatic agent is uniformly dispersed in the polyester matrix, and the size effect of the nanoparticles is exerted. While endowing the polyester with antistatic performance, its original transparency and mechanical properties are ensured, the use of the antistatic agent is reduced, thereby reducing the impact on the mechanical properties and processing properties of the polyester matrix and lowering the production cost.
[0012] In some of the embodiments, the doped-metal nano-metal oxide is one or more of indium tin oxide, zinc oxide doped with gallium, zinc oxide doped with aluminum, and tin oxide doped with antimony.
[0013] In some of the embodiments, the dispersant is one or more of sodium citrate, terephthalic acid, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylamide, sodium dodecylbenzenesulfonate, cetyltrimethylammonium bromide, silicon dioxide, silane coupling agent, and sodium pyrophosphate.
[0014] In some of the embodiments, the solution is a mixture of one or more of water, ethanol, ethylene glycol, propylene glycol, isopropanol, and butanediol.
[0015] In some of the embodiments, in the composite antistatic agent solution, by weight percentage, the doped-metal nano-metal oxide is 5% - 20%, the dispersant is 0.1% - 5%, and the balance is the solution.
[0016] In some of the embodiments, in step 1), the composite antistatic agent solution is obtained by dispersion through ultrasonic or ball milling. Among them, the ultrasonic dispersion time is 5 - 240 min, the frequency is 20 kHz, the interval is 10 s, and the power is 100 - 500 W; the ball milling dispersion time is 12 - 144 h, and the rotation speed is 50 - 1200 rpm.
[0017] The polyester synthesis raw materials in the embodiments of the present invention mainly include dibasic acids or their ester derivatives and diols. The dibasic acids or their ester derivatives include but are not limited to polyterephthalic acid, polyethylene terephthalate and its derivatives, poly(2,5-furandicarboxylic acid), poly(ethylene 2,5-furandicarboxylate), etc. The diols include or are not limited to ethylene glycol, isosorbide, etc.
[0018] The polyester raw materials need to be dried before pulping and should be taken immediately for pulping after drying.
[0019] In some of these embodiments, in step 2), the addition amount of the composite antistatic agent is 0.01 wt% to 18 wt% of the weight of the polyester monomer raw material; in the polyester monomer raw material, in terms of molar ratio, dibasic acid or its ester derivative: diol = 1: 1.1 to 1.6.
[0020] In some of these embodiments, in step 2), the beating time is 5 to 120 min and the temperature is 10 to 120 °C.
[0021] In some of these embodiments, in step 3), the catalyst is one or a combination of more of stibium-based, titanium-based, germanium-based, and aluminum-based catalysts; in terms of mass ratio, dibasic acid or its ester derivative: catalyst = 100: 0.01 to 0.1.
[0022] In some of these embodiments, step 3) includes the steps:
[0023] 3.1 Mix the beaten slurry and the catalyst, then control the temperature at 80 to 110 °C, and stir at 100 to 120 rpm for 10 to 15 min under nitrogen protection;
[0024] 3.2 In the initial stage of the esterification reaction, when the temperature is 150 to 200 °C, replace nitrogen continuously 2 to 3 times within 3 to 10 min to make the reaction pressure change rapidly periodically;
[0025] 3.3 Esterification stage: After replacing nitrogen, maintain the reaction temperature at 220 to 250 °C and the pressure at 370 to 390 kPa, adjust the rotation speed once every 30 min, and cycle and switch in the order of 60 rpm, 90 rpm, and 120 rpm for stirring in turn. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure.
[0026] In some of these embodiments, step 4) is: Add a stabilizer and a co-dispersant, first raise the temperature to 260 to 280 °C, react for 50 to 70 min, then reduce the absolute pressure in the kettle to 20 to 100 Pa, and continue to react until the intrinsic viscosity of the end condensate is 0.6 to 1.2 dL / g, and the reaction time is 0.5 to 4 h.
[0027] In some of these embodiments, the stabilizer is one or more of phosphoric acid, phosphorous acid, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, and triphenyl phosphite; the co-dispersant is one or more of silica, calcium carbonate, magnesium hydroxide, magnesium acetate, sodium silicate, magnesium stearate, zinc stearate, polyethylene glycol, polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylamide; in terms of mass ratio, dibasic acid or its ester derivative: stabilizer: co-dispersant = 100: 0.01 to 0.1: 0.05 to 0.25.
[0028] By controlling process conditions, adjusting the internal reaction environment during the reaction, and utilizing the protection of air pressure changes and co-dispersants, the surface energy of the nano-metal oxide is reduced, the mutual agglomeration between nano-particles is decreased, and at the same time, the reduction damage of groups such as aldehyde groups generated by side reactions to the nano-metal oxide is reduced, enabling it to be uniformly dispersed in the polymer matrix to form a conductive network. Moreover, due to the catalytic effect of the metal oxide itself, it can not only improve the antistatic performance of the polyester material, but also accelerate the reaction rates of esterification and polycondensation, thereby improving production efficiency. Meanwhile, doping with metal oxides can also improve the color of the sample.
[0029] In the second aspect of the present invention, there is also provided a polyester-based permanent antistatic material prepared by the described method.
[0030] The beneficial effects of the present invention are as follows:
[0031] 1. Low addition amount: Utilizing the size effect of the nano-metal oxide, the prepared polyester material can have good antistatic effects at a smaller addition amount, without affecting the processing performance at the same time, and reducing production costs.
[0032] 2. Uniform dispersion of nano-particles: By controlling process conditions and formula selection, controlling the internal environment of the reaction during the reaction process, and utilizing the protection of air pressure changes and co-dispersants, the surface energy of the nano-metal oxide is reduced, the mutual agglomeration between nano-particles is decreased, and at the same time, the reduction damage of groups such as aldehyde groups generated by side reactions to the nano-metal oxide is reduced, enabling it to be uniformly dispersed in the polymer matrix to form a conductive network.
[0033] 3. Catalytic reaction: By using the catalytic effect of the metal oxide itself and producing the polyester material through in-situ polymerization, it can not only improve the antistatic performance of the polyester material, but also incorporate its functions into the polymerization reaction, accelerate the reaction rates of esterification and polycondensation, and improve production efficiency.
[0034] 4. Color improvement: After adding doped nano-metal oxides such as ITO to the polyester, not only the electrical conductivity is improved, but the color of its sliced products is also improved. With little change in the b value of the sliced samples, the whiteness of the slices increases.
[0035] The present invention combines a conductive nano-metal oxide antistatic agent with polyester raw materials, and then uses an in-situ polymerization method to prepare polyester. During the preparation process, the process is adjusted to enable the nano-metal oxide antistatic agent to be uniformly dispersed in the polyester matrix, exerting the size effect of the nano-particles, ensuring the antistatic performance of the polyester while maintaining its original transparency and mechanical properties, reducing the use of the antistatic agent, thereby reducing the impact on the mechanical properties and processing performance of the polyester matrix and lowering production costs. Specific embodiments
[0036] The present invention will be further described below in conjunction with specific embodiments, but the embodiments do not limit the present invention in any form. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field. Unless otherwise specified, the reagents and materials used in the following examples are commercially available.
[0037] Example 1
[0038] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0039] (1) Preparation of antistatic agent: Add 10 g of dried indium tin oxide (ITO) powder to 100 g of ethylene glycol solvent, add 2 g of polyvinylpyrrolidone, and use an ultrasonic crusher to ultrasonically treat the solution. The ultrasonic parameters are set as follows: frequency 20 kHz, time 30 min, interval 10 s, power 300 W.
[0040] (2) Pulping of raw materials: Pulp 10 g of composite antistatic agent with 1000 g of terephthalic acid (PTA) and 530 g of ethylene glycol (EG) at 30 °C for 20 min at high speed to obtain a pre-reaction raw material slurry.
[0041] (3) Esterification reaction: Add the raw material slurry and 0.6 g of antimony trioxide into a 5 L stainless steel high-pressure reactor. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80 °C. At the initial stage of the esterification reaction, set the jacket temperature at 260 °C. When the temperature in the reactor reaches 200 °C, purge nitrogen continuously and rapidly 3 times within 10 min to make the pressure in the reactor change rapidly and periodically. Carry out the esterification reaction at 220 °C and 390 kPa in the reactor, and adjust the rotation speed of the reactor every 30 min to switch sequentially among low speed 60 rpm, medium speed 90 rpm, and high speed 120 rpm. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total time of the esterification stage is 138 min.
[0042] (4) Polycondensation reaction: Add 0.5 g of triphenyl phosphite and 1.5 g of magnesium acetate, raise the temperature to 270 °C, and gradually reduce the absolute pressure in the reactor to 100 Pa within about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 1.0 dL / g. The total time of the polycondensation reaction is 102 min.
[0043] (5) After the reaction is completed, purge with nitrogen to extrude the melt, pelletize, and dry to obtain the polyester material.
[0044] Example 2
[0045] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0046] (1) Preparation of antistatic agent: Add 10 g of dried gallium-doped nano-zinc oxide (GZO) powder into 100 g of ethylene glycol solvent, add 2 g of polyvinyl alcohol, and use an ultrasonic crusher to perform ultrasonic treatment on the solution. The ultrasonic parameters are set as follows: frequency 20 kHz, time 30 min, interval 10 s, power 300 W, to obtain a composite antistatic agent suspension.
[0047] (2) Pulping of raw materials: Mix 100 g of the composite antistatic agent, 1000 g of terephthalic acid, and 430 g of ethylene glycol at 30 °C at high speed for 20 min to obtain a pre-reaction raw material slurry.
[0048] (3) Esterification reaction: Add the raw material slurry and 0.6 g of antimony trioxide into a 5 L stainless steel high-pressure reactor. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80 °C. At the initial stage of the esterification reaction, set the jacket temperature at 260 °C. When the temperature in the reactor reaches 180 °C, purge nitrogen continuously and rapidly 2 times within 8 min to make the pressure in the reactor change rapidly periodically. Carry out the esterification reaction at 200 °C and 370 kPa in the reactor, and adjust the rotation speed of the reactor every 30 min to switch sequentially among low speed 60 rpm, medium speed 90 rpm, and high speed 120 rpm. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total time of the esterification stage is 130 min.
[0049] (4) Polycondensation reaction: Add 0.5 g of triphenyl phosphite and 2.5 g of magnesium acetate, raise the temperature to 270 °C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.6 dL / g. The total time of the polycondensation reaction is 90 min.
[0050] (5) After the reaction is completed, press out the melt with nitrogen, pelletize, and dry to obtain a polyester material.
[0051] Example 3
[0052] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0053] (1) Preparation of antistatic agent: Add 15 g of dried aluminum-doped nano-zinc oxide (AZO) powder into 100 g of ethylene glycol solvent, add 2 g of polyacrylic acid, and use an ultrasonic crusher to perform ultrasonic treatment on the solution. The ultrasonic parameters are set as follows: frequency 20 kHz, time 40 min, interval 10 s, power 300 W, to obtain a composite antistatic agent suspension.
[0054] (2) Pulping of raw materials: Mix 10 g of the composite antistatic agent, 1000 g of terephthalic acid, and 530 g of ethylene glycol at 30 °C at high speed for 20 min to obtain a pre-reaction raw material slurry.
[0055] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.6g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 200°C, purge nitrogen continuously and rapidly 2 times within 10 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 250°C and a pressure of 370 kPa in the reactor, and adjust the rotation speed of the reactor every 30 min to switch it sequentially among low-speed, medium-speed, and high-speed stirring. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total time for the esterification stage is 130 min.
[0056] (4) Polycondensation reaction: Add 0.5g of triphenyl phosphite and 1.5g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa within about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 1.0 dL / g. The total time for the polycondensation reaction is 100 min.
[0057] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize, and dry to obtain the polyester material.
[0058] Example 4
[0059] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0060] (1) Preparation of antistatic agent: Add 15g of dried aluminum-doped zinc oxide (AZO) powder to 100g of a solvent of ethylene glycol: 1,4-butanediol = 1:1, add 2g of polyacrylic acid, and use an ultrasonic crusher to ultrasonically process the solution. The ultrasonic parameters are set as follows: frequency 20 kHz, time 40 min, interval 10 s, power 300W, to obtain a composite antistatic agent suspension.
[0061] (2) Raw material pulping: Pulp 5g of the composite antistatic agent, 950g of terephthalic acid, 50g of isophthalic acid, and 530g of ethylene glycol at 30°C by high-speed mixing for 20 min to obtain a pre-reaction raw material slurry.
[0062] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 150°C, purge nitrogen continuously and rapidly 3 times within 8 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 220°C and a pressure of 370 kPa in the reactor. Adjust the rotation speed of the reactor every 30 min, and switch it sequentially among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm for stirring. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure. The total time of the esterification stage is 140 min.
[0063] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 2g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8 dL / g. The total time of the polycondensation reaction is 105 min.
[0064] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize and dry to obtain the polyester material.
[0065] Example 5
[0066] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0067] (1) Preparation of antistatic agent: Add 10g of dried antimony-doped tin oxide (ATO) powder to 100g of a solvent with ethylene glycol: water = 9:1, add 3g of cetyltrimethylammonium bromide, and use an ultrasonic crusher to perform ultrasonic treatment on the solution. The ultrasonic parameters are set as follows: frequency 20 kHz, time 40 min, interval 10 s, power 300W, to obtain a composite antistatic agent suspension.
[0068] (2) Raw material pulping: Mix 1g of the composite antistatic agent, 1000g of terephthalic acid, and 530g of ethylene glycol at 30°C at high speed for 30 min to obtain a pre-reaction raw material slurry.
[0069] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120rpm for 10min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 160°C, purge nitrogen continuously and rapidly 3 times within 6min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 240°C and a pressure of 380kPa in the reactor. Adjust the rotation speed of the reactor every 30min to switch sequentially among low speed of 60rpm, medium speed of 90rpm, and high speed of 120rpm. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure. The total time for the esterification stage is 142min.
[0070] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 2g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100Pa in about 1h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8dL / g. The total time for the polycondensation reaction is 110min.
[0071] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize, and dry to obtain the polyester material.
[0072] Example 6
[0073] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0074] (1) Preparation of antistatic agent: Add 20g of dried aluminum-doped zinc oxide powder to 100g of a solvent with ethylene glycol: water = 9:1, add 2g of cetyltrimethylammonium bromide, and use an ultrasonic crusher to ultrasonically treat the solution. The ultrasonic parameters are set as follows: frequency 20kHz, time 40min, interval 10s, power 300W, to obtain a composite antistatic agent suspension.
[0075] (2) Raw material pulping: Pulp 0.1g of the composite antistatic agent, 1000g of terephthalic acid, and 530g of ethylene glycol at 20°C at high speed for 40min to obtain a pre-reaction raw material slurry.
[0076] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 180°C, purge nitrogen continuously and rapidly 3 times within 10 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 230°C and a pressure of 380 kPa in the reactor. Adjust the rotation speed of the reactor every 30 min, and switch it sequentially among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm for stirring. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total time for the esterification stage is 148 min.
[0077] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 2g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8 dL / g. The total time for the polycondensation reaction is 125 min.
[0078] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize, and dry to obtain the polyester material.
[0079] Example 7
[0080] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0081] (1) Preparation of antistatic agent: Add 20g of dried tin-doped indium oxide powder to 100g of ethylene glycol solvent, add 4g of sodium polyacrylate, and use a planetary ball mill to grind the solution. The ball milling parameters are set as follows: time 48h, rotation speed 600 rpm, to obtain a composite antistatic agent suspension.
[0082] (2) Raw material pulping: Pulp 0.1g of the composite antistatic agent, 1000g of terephthalic acid, and 530g of ethylene glycol at 20°C at high speed for 40 min to obtain a pre-reaction raw material slurry.
[0083] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 160°C, purge nitrogen continuously and rapidly 3 times within 8 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 220°C and a pressure of 380 kPa in the reactor. Adjust the rotation speed of the reactor every 30 min to sequentially switch among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm for stirring. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure. The total time for the esterification stage is 141 min.
[0084] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 2.5g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8 dL / g. The total time for the polycondensation reaction is 113 min.
[0085] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize, and dry to obtain the polyester material.
[0086] Example 8
[0087] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0088] (1) Preparation of antistatic agent: Add 20g of dried gallium-doped zinc oxide powder to 100g of a solvent with ethylene glycol: isopropanol = 8:2, add 4g of polyacrylic acid, and use a planetary ball mill to grind the solution. The ball milling parameters are set as follows: time 144h, rotation speed 500 rpm, to obtain a composite antistatic agent suspension.
[0089] (2) Raw material pulping: Mix 1g of the composite antistatic agent, 950g of terephthalic acid, 50g of 2,5-furandicarboxylic acid, and 540g of ethylene glycol at 20°C at high speed for 40 min to obtain a pre-reaction raw material slurry.
[0090] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 150°C, purge nitrogen continuously and rapidly 2 times within 5 min to make the pressure in the reactor change rapidly periodically. Conduct the esterification reaction at 220°C and 390 kPa in the reactor, and adjust the rotation speed of the reactor every 30 min to switch sequentially among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total time of the esterification stage is 142 min.
[0091] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 1g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8 dL / g. The total time of the polycondensation reaction is 110 min.
[0092] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize and dry to obtain the polyester material.
[0093] Example 9
[0094] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0095] (1) Preparation of antistatic agent: Add 15g of dried antimony-doped nano-tin oxide powder into 100g of a solvent with ethylene glycol: water = 8:2, add 2g of polyvinylpyrrolidone, and use a planetary ball mill to ball-mill the solution. The ball-milling parameters are set as follows: time 96h, rotation speed 500 rpm, to obtain a composite antistatic agent suspension.
[0096] (2) Raw material pulping: Pulp 200g of the composite antistatic agent, 950g of terephthalic acid, 50g of 2,5-furandicarboxylic acid, and 340g of ethylene glycol at 20°C at high speed for 40 min to obtain a pre-reaction raw material slurry.
[0097] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 150°C, purge nitrogen continuously and rapidly 3 times within 6 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 220°C and a pressure of 370 kPa in the reactor. Adjust the rotation speed of the reactor once every 30 min, and switch it sequentially among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm for stirring. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total esterification time stage is 130 min.
[0098] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 1g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8 dL / g. The total time for the polycondensation reaction is 98 min.
[0099] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize and dry to obtain the polyester material.
[0100] Example 10
[0101] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0102] (1) Preparation of antistatic agent: Add 8g of dried aluminum-doped zinc oxide powder to a solvent of 100g of ethylene glycol: water = 8:2, add 1.5g of polyvinylpyrrolidone, and use a planetary ball mill to mill the solution. The ball milling parameters are set as follows: time 72h, rotation speed 600 rpm, to obtain a composite antistatic agent suspension.
[0103] (2) Raw material pulping: Mix 1g of the composite antistatic agent, 980g of terephthalic acid, 490g of ethylene glycol, and 50g of isosorbide at 80°C at high speed for 20 min to obtain a pre-reaction raw material slurry.
[0104] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 180°C, purge nitrogen continuously and rapidly 3 times within 10 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 200°C and a pressure of 390 kPa in the reactor. Adjust the rotation speed of the reactor every 30 min, so that it switches sequentially among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm for stirring. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total time for the esterification stage is 141 min.
[0105] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 1.5g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 1.2 dL / g. The total time for the polycondensation reaction is 110 min.
[0106] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize, and dry to obtain the polyester material.
[0107] Example 11
[0108] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0109] (1) Preparation of antistatic agent: Add 8g of dried aluminum-doped zinc oxide powder to 100g of ethylene glycol solvent, add 1.5g of polyacrylic acid, and 3g of terephthalic acid. Use a planetary ball mill to ball mill the solution. The ball milling parameters are set as follows: time 72h, rotation speed 600 rpm, to obtain a composite antistatic agent suspension.
[0110] (2) Raw material pulping: Mix 16g of the composite antistatic agent, 950g of terephthalic acid, 50g of 2,5-furandicarboxylic acid, and 520g of ethylene glycol at 20°C at high speed for 30 min to obtain a pre-reaction raw material slurry.
[0111] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120rpm for 10min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 180°C, purge nitrogen continuously and rapidly 3 times within 8min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 200°C and a pressure of 390kPa in the reactor. Adjust the rotation speed of the reactor every 30min to switch sequentially among low speed of 60rpm, medium speed of 90rpm, and high speed of 120rpm. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure. The total time for the esterification stage is 132min.
[0112] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 2g of magnesium acetate, raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100Pa in about 1h. Then continue the reaction until the intrinsic viscosity of the end condensate is 0.8dL / g. The total time for the polycondensation reaction is 98min.
[0113] (5) After the reaction is completed, purge nitrogen to press out the melt, pelletize, and dry to obtain the polyester material.
[0114] Example 12
[0115] This example provides a transparent permanent antistatic polyester material, which is prepared by the following steps:
[0116] (1) Preparation of antistatic agent: Add 8g of dried tin-doped indium oxide powder to 100g of ethylene glycol solvent, add 1.5g of polyacrylic acid, and 3g of terephthalic acid. Use a planetary ball mill to ball-mill the solution. The ball-milling parameters are set as follows: time 84h, rotation speed 600rpm, to obtain a composite antistatic agent suspension.
[0117] (2) Raw material pulping: Mix 2g of the composite antistatic agent with 980g of terephthalic acid and 500g of ethylene glycol at 20°C at high speed for 30min to obtain a pre-reaction raw material slurry.
[0118] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.8g of antimony trioxide. After purging the air in the reactor with nitrogen, stir at 120 rpm for 10 min under nitrogen protection, and control the temperature at 80°C. At the initial stage of the esterification reaction, set the jacket temperature at 260°C. When the temperature in the reactor reaches 180°C, purge nitrogen continuously and rapidly 3 times within 8 min to cause the pressure in the reactor to change rapidly and periodically. Conduct the esterification reaction at a temperature of 220°C and a pressure of 390 kPa in the reactor. Adjust the rotation speed of the reactor every 30 min, and switch it sequentially among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure. The total time for the esterification stage is 139 min.
[0119] (4) Polycondensation reaction: Add 0.6g of triphenyl phosphite and 1.8g of magnesium acetate. Raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa within about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 1.2 dL / g. The total time for the polycondensation reaction is 108 min.
[0120] (5) After the reaction is completed, purge nitrogen to extrude the melt, pelletize, and dry to obtain the polyester material.
[0121] Comparative Example 1
[0122] This example provides a common polyester material, which is prepared by the following steps:
[0123] (1) Esterification reaction: In a 5L stainless steel high-pressure reactor, add 1000g of terephthalic acid, 530g of ethylene glycol, and 0.6g of antimony trioxide. After purging the air in the reactor with nitrogen, conduct the esterification reaction at a temperature of 220°C and a pressure of 390 kPa in the reactor. When the water output reaches above the theoretical value, relieve the pressure to atmospheric pressure. The total esterification time is 150 min.
[0124] (2) Polycondensation reaction: Add 0.5g of triphenyl phosphite. Raise the temperature to 270°C, and gradually reduce the absolute pressure in the reactor to 100 Pa within about 1 h. Then continue the reaction until the intrinsic viscosity of the end condensate is 1.0 dL / g. The total polycondensation reaction time is 194 min.
[0125] (3) After the reaction is completed, purge nitrogen to extrude the melt, pelletize, and dry to obtain the polyester material.
[0126] The difference from Example 1 is that since it is a common polyester, no antistatic agent is added, and no dispersing aid is added during the polycondensation reaction.
[0127] Comparative Example 2
[0128] This comparative example provides an antistatic polyester material, which is prepared by the following steps:
[0129] (1) Pulping of raw materials: 10 g of dried indium tin oxide (ITO) powder is mixed with 1000 g of terephthalic acid (PTA) and 530 g of ethylene glycol (EG) at 30 °C and pulped at high speed for 20 min to obtain a pre-reaction raw material slurry.
[0130] (2) Esterification reaction: In a 5 L stainless steel high-pressure reactor, the raw material slurry and 0.6 g of antimony trioxide are added. After purging the air in the reactor with nitrogen, it is stirred at 120 rpm for 10 min under nitrogen protection, and the temperature is controlled at 80 °C. At the initial stage of the esterification reaction, the jacket temperature is set at 260 °C. When the temperature in the reactor reaches 200 °C, nitrogen is continuously and rapidly replaced 3 times, causing the pressure in the reactor to change rapidly and periodically. The esterification reaction is carried out at 220 °C and 390 kPa in the reactor. The rotation speed of the reactor is adjusted every 30 min, and it is sequentially switched among low speed of 60 rpm, medium speed of 90 rpm, and high speed of 120 rpm for stirring. When the water output reaches above the theoretical value, the pressure is released to atmospheric pressure, and the total esterification time is 130 min.
[0131] (3) Polycondensation reaction: 0.5 g of triphenyl phosphite and 1.5 g of magnesium acetate are added, the temperature is raised to 270 °C, and the absolute pressure in the reactor is gradually reduced to 100 Pa in about 1 h. Then the reaction continues until the intrinsic viscosity of the end condensate is 1.0 dL / g. The total polycondensation reaction time is 95 min.
[0132] (5) After the reaction is completed, nitrogen is introduced to extrude the melt, pelletize, and dry to obtain the polyester material.
[0133] The difference from Example 1 is that the nano-oxide has not been modified.
[0134] Comparative Example 3
[0135] This comparative example provides an antistatic polyester material, which is prepared by the following steps:
[0136] (1) Preparation of antistatic agent: 10 g of dried indium tin oxide (ITO) powder is added to 100 g of ethylene glycol solvent, 2 g of polyvinylpyrrolidone is added, and the solution is ultrasonically treated using an ultrasonic crusher. The ultrasonic parameters are set as follows: time 30 min, interval 10 s, power 300 W.
[0137] (2) Pulping of raw materials: 10 g of the composite antistatic agent is mixed with 1000 g of terephthalic acid (PTA) and 530 g of ethylene glycol (EG) at 30 °C and pulped at high speed for 20 min to obtain a pre-reaction raw material slurry.
[0138] (3) Esterification reaction: In a 5L stainless steel high-pressure reactor, add the raw material slurry and 0.6g of antimony trioxide. After purging the air in the reactor with nitrogen, carry out the esterification reaction at a reactor temperature of 220°C and 390 kPa. When the water output reaches above the theoretical value, release the pressure to atmospheric pressure. The total esterification time is 140 min.
[0139] (4) Polycondensation reaction: Add 0.5g of triphenyl phosphite and 1.5g of magnesium acetate. Raise the temperature to 270°C and gradually reduce the absolute pressure in the reactor to 100 Pa in about 1h. Then continue the reaction until the intrinsic viscosity of the end condensate is 1.0 dL / g. The total time for the polycondensation reaction is 108 min.
[0140] (5) After the reaction is completed, introduce nitrogen to extrude the melt, pelletize and dry to obtain the polyester material.
[0141] The difference from Example 1 is that the esterification reaction step in step (3) is different.
[0142] The polyester samples obtained in each example and comparative example were respectively tested for surface resistivity and color values (L value, b value), and the test data were compared. The performance test results are shown in Table 1.
[0143] Table 1 Performance comparison between examples and comparative examples
[0144]
[0145]
[0146] In summary, it can be seen that the examples of the present invention can obtain a polyester composite material with a permanent antistatic effect through the modification of doped nano-metal oxides, in-situ polymerization together with polyester raw materials, and the regulation of the polycondensation process. Moreover, the chromaticity of the polyester material is also improved to a certain extent. And due to the catalytic effect of the metal oxide itself, it can also accelerate the reaction rates of esterification and polycondensation, improving production efficiency.
[0147] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of this invention patent shall be subject to the appended claims.
Claims
1. A method for preparing a polyester-based permanent antistatic material by in-situ polymerization and nano-metal oxide composite, characterized in that: The steps include: 1) Preparation of composite antistatic agent solution: uniformly dispersing metal-doped nano-metal oxide and dispersant in a solvent to obtain a composite antistatic agent solution; 2) Raw material beating: selecting and preparing at least one dibasic acid or its ester derivative and at least one diol as monomers of polyester, adding them into the composite antistatic agent solution obtained in step 1) for mixing and beating; 3) Esterification reaction: adding a catalyst to the pulp after beating to carry out esterification reaction; 4) Polycondensation reaction: After the esterification is completed, a stabilizer and a dispersant are added to carry out polycondensation to obtain the polyester-based permanent antistatic material.
2. The method according to claim 1, characterized in that The metal-doped nano-metal oxide is one or more of tin-doped nano-indium oxide, gallium-doped nano-zinc oxide, aluminum-doped nano-zinc oxide, and antimony-doped nano-tin oxide; The dispersant is one or more of sodium citrate, terephthalic acid, polyacrylic acid, sodium polyacrylate, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylamide, sodium dodecylbenzene sulfonate, hexadecyltrimethylammonium bromide, silicon dioxide, silane coupling agent, and sodium pyrophosphate; The solution is a mixture of one or more of water, ethanol, ethylene glycol, propylene glycol, isopropanol, and butylene glycol; In the composite antistatic agent solution, according to weight percentage, the metal-doped nano-metal oxide comprises 5% to 20%, the dispersant comprises 0.1% to 5%, and the balance is the solution.
3. The method according to claim 1, characterized in that In step 1), a composite antistatic agent solution is obtained by dispersing by ultrasound or ball milling, wherein the ultrasonic dispersion time is 5 to 240 minutes, the frequency is 20 kHz, and the power is 100 to 500 W; the ball milling dispersion time is 12 to 144 hours, and the rotation speed is 50 to 1200 rpm.
4. The method according to claim 1, characterized in that: In the step 2), the added amount of the composite antistatic agent is 0.01wt% to 18wt% of the weight of the polyester monomer raw material; in the polyester monomer raw material, the molar ratio of dibasic acid or its ester derivative: diol is 1:1.1 to 1.
6.
5. The method according to claim 1, characterized in that In the step 2), the beating time is 5 to 120 minutes and the temperature is 10 to 120°C.
6. The method according to claim 1, characterized in that In the step 3), the catalyst is a composite of one or more antimony-based, titanium-based, germanium-based, and aluminum-based catalysts; in terms of mass ratio, the dibasic acid or its ester derivative: the catalyst = 100: 0.01-0.
1.
7. The method according to claim 1, characterized in that The step 3) comprises the steps of: 3.1 Mix the slurry and catalyst after beating, then control the temperature at 80-110°C, and stir at 100-120 rpm for 10-15 min under nitrogen protection; 3.2 In the initial stage of esterification reaction, nitrogen is replaced 2-3 times within 3-10 minutes at 150-200°C to make the reaction pressure change rapidly and periodically; 3.3 Esterification stage: After nitrogen replacement, maintain the reaction temperature at 220-250°C and the pressure at 370-390 kPa. Adjust the rotation speed every 30 minutes, and cycle through the stirring in the order of 60 rpm, 90 rpm, and 120 rpm. When the water output reaches above the theoretical value, release the pressure to normal pressure.
8. The method according to claim 1, characterized in that The step 4) is: First, the temperature is raised to 260-280°C and the reaction is carried out for 50-70 minutes. Then, the absolute pressure in the autoclave is reduced to 20-100 Pa and the reaction is continued until the intrinsic viscosity of the final condensate is 0.6-1.2 dL / g. The reaction time is 0.5-4 hours.
9. The preparation method according to claim 1, characterized in that: The stabilizer is one or more of phosphoric acid, phosphorous acid, dimethyl phosphate, trimethyl phosphate, triethyl phosphate, and triphenyl phosphite; The dispersant is one or more of silicon dioxide, calcium carbonate, magnesium hydroxide, magnesium acetate, sodium silicate, magnesium stearate, zinc stearate, polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylamide; According to the mass ratio, dibasic acid or its ester derivative: stabilizer: dispersant = 100: 0.01~0.1: 0.05~0.
25.
10. The polyester-based permanent antistatic material prepared by the method according to any one of claims 1 to 9.