WO2023044692A1 - Thermoplastic polyester used for thin film, and preparation method therefor - Google Patents

Thermoplastic polyester used for thin film, and preparation method therefor Download PDF

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Publication number
WO2023044692A1
WO2023044692A1 PCT/CN2021/120055 CN2021120055W WO2023044692A1 WO 2023044692 A1 WO2023044692 A1 WO 2023044692A1 CN 2021120055 W CN2021120055 W CN 2021120055W WO 2023044692 A1 WO2023044692 A1 WO 2023044692A1
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parts
add
terephthalic acid
ethylene glycol
reaction
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PCT/CN2021/120055
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French (fr)
Chinese (zh)
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林福亮
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郑荣志
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Priority to PCT/CN2021/120055 priority Critical patent/WO2023044692A1/en
Publication of WO2023044692A1 publication Critical patent/WO2023044692A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/682—Polyesters containing atoms other than carbon, hydrogen and oxygen containing halogens
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
    • C08G63/685—Polyesters containing atoms other than carbon, hydrogen and oxygen containing nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C08L67/06—Unsaturated polyesters

Definitions

  • the invention relates to a film material, in particular to a thermoplastic polyester used for film and a preparation method thereof.
  • Thermoplastic Polyester Saturated polyester with thermoplastic properties. More refers to the polyester terephthalate. In fact, it should also include other linear polyesters in a broad sense.
  • polyethylene terephthalates polyethylene terephthalate and polybutylene terephthalate have the largest output and wide application, and others are mostly used as high-performance films and fibers.
  • polyethylene terephthalate is the most commonly used thermoplastic polyester, polyethylene terephthalate, and its chemical formula is COC6H4COOCH2CH2O.
  • PET Polyethylene terephthalate
  • the purpose of the present invention is to provide one.
  • thermoplastic polyester for film comprising the following components by mass:
  • Terephthalic acid 1000 parts
  • Ethylene glycol 600 parts;
  • Tetrabromoterephthalic acid 5 parts;
  • thermoplastic polyester for film A method for the preparation of thermoplastic polyester for film
  • Step 1 Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
  • Step 2 Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
  • Step 3 Add 200 parts of terephthalic acid, 50 parts of maleic anhydride, 10 parts of 2-nitroterephthalic acid-4-methyl ester, cool down to 180-200°C, and react for 20-40 minutes;
  • Step 4 Add 100 parts of terephthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, 5 parts of 2,3-dibromo-2-butene-1,4-diol, and keep the temperature At 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst and react for 20-30 minutes;
  • Step 5 Add 200 parts of terephthalic acid, 100 parts of ethylene glycol, 8 parts of 1,4-benzenedimethanol, and 15 parts of 2-aminoterephthalic acid, heat up to 200-250°C, and react for 10-30 minutes. Get the main material for use;
  • Step 6 preparation of auxiliary materials, set up another reaction kettle, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 5 parts of tetrabromoterephthalic acid, 8 parts of bis(2-ethylhexyl) terephthalic acid, 5 parts of 4-bromophthalic anhydride; keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use;
  • Step 7 Slowly add the auxiliary materials into the reaction kettle of the main materials, stir while adding, keep the temperature at 40-50 degrees Celsius, slowly raise the temperature to 180-200 degrees Celsius after adding, keep stirring for 20-40 minutes;
  • Step 8 heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
  • Step 9 After completing the reaction, add 10 parts of dimethyl o-bromoterephthalate, 3 parts of 2,2-difluoro-1,3-benzodioxol, 5 parts of magnesium fluorosilicate, and 5 parts of antibacterial agent, The temperature is controlled at 100-120°C, after stirring for 30-40 minutes, continue to stir, naturally cool down to 50-60°C, and then granulate to obtain plastic particles;
  • Step 10 Make plastic particles into a film.
  • the plastic particles are formed into a film by a casting machine.
  • the antibacterial agent is prepared according to the following method:
  • Step A Add 2ml of p-chlorobenzoyl chloride, 1ml of 4-bromobutyryl chloride, and 1ml of phosphorus trichloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, Silicon for activation;
  • Step B After the reaction is completed, the mixture is centrifuged, washed with chloroform, ethylene glycol, and acetone in sequence, and dried to obtain activated nano-silica;
  • Step C Add 7g of polyethyleneimine, 2g of bis(trimethylsilyl)carbodiimide, 1g of polycarbodiimide to activated nano-silica, add 0.1g of KOH, and stir at 85°C 15-20 hours;
  • Step D Centrifuge after the reaction, fully wash with methanol, and dry;
  • Step E Put the air-dried nano silicon dioxide powder into 20ml of isobutanol, then add 2ml of 1,2-dibromoethane, 6ml of bromohexane, 0.1g of bromoacetyl bromide, 1ml of 1 -Bromo-3-methylbutane, then stirred at 70-80°C for 15-25 hours;
  • Step F After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, wash fully with methanol, and then dry to obtain an antibacterial agent.
  • step five in the step five, first add 50 parts of terephthalic acid, then add 100 parts of ethylene glycol, and divide the remaining 150 parts of terephthalic acid into three parts, and add 50 parts of terephthalic acid every 10 minutes. Phthalic acid, finally add 10 parts of 2,2-dimethyl-1,3-propanediol.
  • step 4 when adding the Ti/Si catalyst in the step 2, step 4, and step 6, first dilute the Ti/Si catalyst with 50ml of ethylene glycol, and then add it into the reaction vessel.
  • the present invention first uses terephthalic acid and ethylene glycol as the base material, and simultaneously adds other components to adjust the groups between the chain segments, and simultaneously prepares the auxiliary material and the base material separately.
  • terephthalic acid and ethylene glycol With a large number of functional groups, it is also based on terephthalic acid and ethylene glycol, so that in the later mixing and polymerization reactions, the dispersion will be better and better results will be achieved.
  • the impact of the one-time reaction on the functional groups is also eliminated, making the obtained polyester more stable in performance.
  • step 1 most of the terephthalic acid and ethylene glycol are added to the reaction vessel first, and a pre-mixing process is carried out, and the temperature is raised to 40°C at the same time, so that the pre-mixing can be made more uniform and the intermolecular freedom can be promoted. sports. It can effectively prevent the phenomenon of excessive polymerization caused by sudden addition of too much reaction raw material.
  • step 2 the temperature is raised to 200-220 degrees Celsius and Ti/Si catalyst is added to start the polyester reaction.
  • the amount of ethylene glycol in the entire reaction system is far greater than that of terephthalic acid.
  • ethylene glycol is The solvent can reduce and play a diluting effect, so that terephthalic acid can slowly react with ethylene glycol for polyester.
  • ethylene glycol is excessive, therefore fills in part terephthalic acid in step 3, to guarantee reaction rate.
  • the maleic anhydride added can increase the flexibility of the overall chain segment, regulate the length of the molecular chain, and ensure that the chain segment has good tensile strength, while the addition of 2-nitroterephthalic acid-4-methyl
  • amino groups and nitro groups can be introduced into the entire system, which can enhance the weather resistance of the entire system.
  • it also contains phenyl groups, which can be similarly compatible with the entire system and improve the overall compatibility. , so it can bring better uniformity and avoid the improvement of local performance.
  • step 4 add 2,2-dimethyl-1,3-propanediol and 2,3-dibromo-2-butene-1,4-diol simultaneously, by adding 2 , 2-dimethyl-1,3-propanediol, adjust the molecular chain, so that the molecular weight of the product is more uniform, and the light transmittance of the product can also be guaranteed.
  • 2,3-dibromo-2-butene-1,4-diol can participate in the reaction, and the bromine substituent is introduced into the continuous segment, which can improve the overall flame retardancy.
  • Step 5 ethylene glycol is also added while part of the terephthalic acid is replenished.
  • ethylene glycol has been almost consumed, and the addition of ethylene glycol can ensure that the reaction rate will not be reduced.
  • Step six is the preparation process of auxiliary materials, still using terephthalic acid and ethylene glycol as carriers, adding tetrabromoterephthalic acid, bis(2-ethylhexyl)terephthalic acid, and 4-bromophthalic anhydride;
  • tetrabromoterephthalic acid and 4-bromophthalic anhydride mainly introduces bromine substituents into the continuous segment, ensuring its overall flame retardancy.
  • the addition makes the polymerization positions of tetrabromoterephthalic acid and 4-bromophthalic anhydride not too close, and introduces side chain groups under the conditions of intermolecular interaction to ensure the uniformity and stability of the overall flame retardant performance.
  • step 6 slowly add the auxiliary materials in step 6 into the main material for mixing, and then pressurize and polymerize to obtain a polyester with uniform physical properties.
  • dimethyl bromoterephthalate can react with the polymer produced by the reaction to improve the overall flame retardancy
  • 2,2-difluoro-1,3-benzodioxol itself can enhance the overall strength of the product
  • its structure is similar to that of polyethylene terephthalate, so it has good compatibility and can be evenly distributed between molecular chains, which further strengthens the overall flame retardancy.
  • magnesium fluorosilicate can improve the strength of the polyester, and can also act as a stabilizer, so that the polyester can show a certain degree of stability whether it is processed or used.
  • antibacterial agent can improve its overall antibacterial performance.
  • the 2,6-di-tert-butyl-4-methylphenol added before the reaction is a general-purpose antioxidant, which is added to the container together with ethylene glycol. On the one hand, it has a cleaning effect on the reaction container, and on the other hand, it also It can prevent the polyester from being oxidized during the reaction.
  • the quaternary ammonium salt type antibacterial agent select the quaternary ammonium salt type antibacterial agent, and its quaternary ammonium salt conforms to the nano silicon dioxide.
  • nano-silica can be further activated under the conditions of chlorobenzoyl chloride, 4-bromobutyryl chloride, and phosphorus trichloride, especially the addition of phosphorus trichloride can improve the performance of nano-silica.
  • trichloromethane has good solubility to chlorobenzoyl chloride and phosphorus trichloride, and it can be taken out, while ethylene glycol can take out residual trichloromethane, and finally, it can be cleaned thoroughly with acetone. Remove residual material.
  • the reaction is mainly in polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide and 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo-
  • the reaction is mainly in polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide and 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo-
  • the quaternary ammonium salt generated by the reaction has strong stability, especially the addition of bis(trimethylsilyl)carbodiimide, which can make the binding force with silicon dioxide stronger Well, it is not easy to fall off from the nano-silica, and the addition of bromoacetyl bromide also improves the activity of the antibacterial agent.
  • thermoplastic polyester material prepared by the present invention has good flame retardancy, antibacterial property and high strength, and at the same time, it still has good flame retardancy, antibacterial property and high strength even after long-term use.
  • thermoplastic polyester for film comprises following composition by mass parts:
  • Terephthalic acid 1000 parts
  • Ethylene glycol 600 parts;
  • Tetrabromoterephthalic acid 5 parts;
  • thermoplastic polyester for film A method for the preparation of thermoplastic polyester for film
  • Step 1 Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
  • Step 2 Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
  • Step 3 Add 200 parts of terephthalic acid, 50 parts of maleic anhydride, 10 parts of 2-nitroterephthalic acid-4-methyl ester, cool down to 180-200°C, and react for 20-40 minutes;
  • Step 4 Add 100 parts of terephthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, 5 parts of 2,3-dibromo-2-butene-1,4-diol, and keep the temperature At 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst and react for 20-30 minutes;
  • Step 5 Add 200 parts of terephthalic acid, 100 parts of ethylene glycol, 8 parts of 1,4-benzenedimethanol, and 15 parts of 2-aminoterephthalic acid, heat up to 200-250°C, and react for 10-30 minutes. Get the main material for use;
  • Step 6 preparation of auxiliary materials, set up another reaction kettle, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 5 parts of tetrabromoterephthalic acid, 8 parts of bis(2-ethylhexyl) terephthalic acid, 5 parts of 4-bromophthalic anhydride; keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use;
  • Step 7 Slowly add auxiliary materials into the reaction kettle of main materials , Stir while adding, keep the temperature at 40-50 degrees Celsius, slowly heat up to 180-200 degrees Celsius after adding, keep stirring for 20-40 minutes;
  • Step 8 heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
  • Step 9 After completing the reaction, add 10 parts of dimethyl o-bromoterephthalate, 3 parts of 2,2-difluoro-1,3-benzodioxol, 5 parts of magnesium fluorosilicate, and 5 parts of antibacterial agent, The temperature is controlled at 100-120°C, after stirring for 30-40 minutes, continue to stir, naturally cool down to 50-60°C, and then granulate to obtain plastic particles;
  • Step 10 Make plastic particles into a film.
  • the plastic particles are formed into a film by a casting machine.
  • Described antibacterial agent is prepared according to the following method:
  • Step A Add 2ml of p-chlorobenzoyl chloride, 1ml of 4-bromobutyryl chloride, and 1ml of phosphorus trichloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, Silicon for activation;
  • Step B After the reaction is completed, the mixture is centrifuged, washed with chloroform, ethylene glycol, and acetone in sequence, and dried to obtain activated nano-silica;
  • Step C Add 7g of polyethyleneimine, 2g of bis(trimethylsilyl)carbodiimide, 1g of polycarbodiimide to activated nano-silica, add 0.1g of KOH, and stir at 85°C 15-20 hours;
  • Step D Centrifuge after the reaction, fully wash with methanol, and dry;
  • Step E Put the air-dried nano silicon dioxide powder into 20ml of isobutanol, then add 2ml of 1,2-dibromoethane, 6ml of bromohexane, 0.1g of bromoacetyl bromide, 1ml of 1 -Bromo-3-methylbutane, then stirred at 70-80°C for 15-25 hours;
  • Step F After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
  • step five first add 50 parts of terephthalic acid, then add 100 parts of ethylene glycol, and divide the remaining 150 parts of terephthalic acid into three parts, add 50 parts of terephthalic acid every 10 minutes, and finally add 2 , 10 parts of 2-dimethyl-1,3-propanediol.
  • first step before adding raw materials, first add 2,6-di-tert-butyl-4-methylphenol into the reaction vessel, add 200 parts of ethylene glycol, stir for 5 to 15 minutes, and then add the remaining 600 parts Parts of ethylene glycol and 400 parts of terephthalic acid, heated to 40°C for preliminary mixing.
  • step 4 When adding the Ti/Si catalyst in the step 2, step 4, and step 6, first dilute the Ti/Si catalyst with 50ml of ethylene glycol, and then add it into the reaction vessel.
  • Step A Add 4ml of 4-bromobutyryl chloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, and activate the nano-silica;
  • Step B After the reaction is completed, the mixture is centrifuged, washed with methanol, and dried to obtain activated nano-silica;
  • Step C Add 10 g of polyethyleneimine to the activated nano-silica, add 0.1 g of KOH, and stir at 85° C. for 15 to 20 hours;
  • Step D Centrifuge after the reaction, fully wash with methanol, and dry;
  • Step E Put the air-dried nano-silica powder into 20ml of isobutanol, then add 10ml of bromohexane and 0.1g of bromoacetyl bromide and stir at 70-80°C for 15-25 hours;
  • Step F After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
  • Example 2 Compared with Example 1, the difference is that the HM98 organosilicon antibacterial agent purchased from Guangzhou Nuokang Chemical Co., Ltd. is selected.
  • Step 1 Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
  • Step 2 Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
  • Step 3 Add 200 parts of terephthalic acid, lower the temperature to 180-200°C, and react for 20-40 minutes;
  • Step 4 Add 100 parts of terephthalic acid, keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 20-30 minutes;
  • Step 5 Add 200 parts of terephthalic acid and 100 parts of ethylene glycol, heat up to 200-250°C, and react for 10-30 minutes to obtain the main ingredients for later use;
  • Step 6 Preparation of auxiliary materials, set up another reactor, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use;
  • Step 7 Slowly add the auxiliary materials into the reaction kettle of the main materials, stir while adding, keep the temperature at 40-50 degrees Celsius, slowly raise the temperature to 180-200 degrees Celsius after the addition, keep stirring for 20-40 minutes;
  • Step 8 heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
  • Step 9 Making plastic particles into a film.
  • the plastic particles are formed into a film by a casting machine.
  • the antimicrobial steps are:
  • Step A Add 4ml of 4-bromobutyryl chloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, and activate the nano-silica;
  • Step B After the reaction is completed, the mixture is centrifuged, washed with methanol, and dried to obtain activated nano-silica;
  • Step C Add 10 g of polyethyleneimine to the activated nano-silica, add 0.1 g of KOH, and stir at 85° C. for 15 to 20 hours;
  • Step D Centrifuge after the reaction, fully wash with methanol, and dry;
  • Step E Put the air-dried nano-silica powder into 20ml of isobutanol, then add 10ml of bromohexane and 0.1g of bromoacetyl bromide and stir at 70-80°C for 15-25 hours;
  • Step F After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
  • Comparative Example 2 The difference with Comparative Example 2 is that the HM98 organosilicon antibacterial agent of Guangzhou Nuokang Chemical Co., Ltd. purchased in the city is selected.
  • the above materials were all prepared into cast films with a thickness of 200 ⁇ m, and their tensile strength, transparency, antibacterial properties, and flame retardant properties were tested. And the above tests were carried out after 50, 100, 150, 200 hours of exposure to the xenon lamp.
  • Staphylococcus aureus and Escherichia coli were selected as the strains.
  • Table 2 Test data after 50 hours of exposure to a xenon lamp
  • Table 3 Test data after 100 hours of exposure to a xenon lamp
  • Table 4 Test data after 150 hours of exposure to a xenon lamp
  • Table 5 Test data after 100 hours of exposure to a xenon lamp
  • the present invention first uses terephthalic acid and ethylene glycol as the base material, and simultaneously adds other components to adjust the groups between the chain segments, and simultaneously prepares the auxiliary material and the base material separately.
  • terephthalic acid and ethylene glycol With a large number of functional groups, it is also based on terephthalic acid and ethylene glycol, so that in the later mixing and polymerization reactions, the dispersion will be better and better results will be achieved.
  • the impact of the one-time reaction on the functional groups is also eliminated, making the obtained polyester more stable in performance.
  • step 1 most of the terephthalic acid and ethylene glycol are added to the reaction vessel first, and a pre-mixing process is carried out, and the temperature is raised to 40°C at the same time, so that the pre-mixing can be made more uniform and the intermolecular freedom can be promoted. sports. It can effectively prevent the phenomenon of excessive polymerization caused by sudden addition of too much reaction raw material.
  • step 2 the temperature is raised to 200-220 degrees Celsius and Ti/Si catalyst is added to start the polyester reaction.
  • the amount of ethylene glycol in the entire reaction system is far greater than that of terephthalic acid.
  • ethylene glycol is The solvent can reduce and play a diluting effect, so that terephthalic acid can slowly react with ethylene glycol for polyester.
  • ethylene glycol is excessive, therefore fills in part terephthalic acid in step 3, to guarantee reaction rate.
  • the maleic anhydride added can increase the flexibility of the overall chain segment, regulate the length of the molecular chain, and ensure that the chain segment has good tensile strength, while the addition of 2-nitroterephthalic acid-4-methyl
  • amino groups and nitro groups can be introduced into the entire system, which can enhance the weather resistance of the entire system.
  • it also contains phenyl groups, which can be similarly compatible with the entire system and improve the overall compatibility. , so it can bring better uniformity and avoid the improvement of local performance.
  • step 4 add 2,2-dimethyl-1,3-propanediol and 2,3-dibromo-2-butene-1,4-diol simultaneously, by adding 2 , 2-dimethyl-1,3-propanediol, adjust the molecular chain, so that the molecular weight of the product is more uniform, and the light transmittance of the product can also be guaranteed.
  • 2,3-dibromo-2-butene-1,4-diol can participate in the reaction, and the bromine substituent is introduced into the continuous segment, which can improve the overall flame retardancy.
  • Step 5 ethylene glycol is also added while part of the terephthalic acid is replenished.
  • ethylene glycol has been almost consumed, and the addition of ethylene glycol can ensure that the reaction rate will not be reduced.
  • Step six is the preparation process of auxiliary materials, still using terephthalic acid and ethylene glycol as carriers, adding tetrabromoterephthalic acid, bis(2-ethylhexyl)terephthalic acid, and 4-bromophthalic anhydride;
  • tetrabromoterephthalic acid and 4-bromophthalic anhydride mainly introduces bromine substituents into the continuous segment, ensuring its overall flame retardancy.
  • the addition makes the polymerization positions of tetrabromoterephthalic acid and 4-bromophthalic anhydride not too close, and introduces side chain groups under the conditions of intermolecular interaction to ensure the uniformity and stability of the overall flame retardant performance.
  • step 6 slowly add the auxiliary materials in step 6 into the main material for mixing, and then pressurize and polymerize to obtain a polyester with uniform physical properties.
  • dimethyl bromoterephthalate can react with the polymer produced by the reaction to improve the overall flame retardancy
  • 2,2-difluoro-1,3-benzodioxol itself can enhance the overall strength of the product
  • its structure is similar to that of polyethylene terephthalate, so it has good compatibility and can be evenly distributed between molecular chains, which further strengthens the overall flame retardancy.
  • magnesium fluorosilicate can improve the strength of the polyester, and can also act as a stabilizer, so that the polyester can show a certain degree of stability whether it is processed or used.
  • antibacterial agent can improve its overall antibacterial performance.
  • the 2,6-di-tert-butyl-4-methylphenol added before the reaction is a general-purpose antioxidant, which is added to the container together with ethylene glycol. On the one hand, it has a cleaning effect on the reaction container, and on the other hand, it also It can prevent the polyester from being oxidized during the reaction.
  • the quaternary ammonium salt type antibacterial agent select the quaternary ammonium salt type antibacterial agent, and its quaternary ammonium salt conforms to the nano silicon dioxide.
  • nano-silica can be further activated under the conditions of chlorobenzoyl chloride, 4-bromobutyryl chloride, and phosphorus trichloride, especially the addition of phosphorus trichloride can improve the performance of nano-silica.
  • trichloromethane has good solubility to chlorobenzoyl chloride and phosphorus trichloride, and it can be taken out, while ethylene glycol can take out residual trichloromethane, and finally, it can be cleaned thoroughly with acetone. Remove residual material.
  • the reaction is mainly in polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide and 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo-
  • the reaction is mainly in polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide and 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo-
  • the quaternary ammonium salt generated by the reaction has strong stability, especially the addition of bis(trimethylsilyl)carbodiimide, which can make the binding force with silicon dioxide stronger Well, it is not easy to fall off from the nano-silica, and the addition of bromoacetyl bromide also improves the activity of the antibacterial agent.
  • thermoplastic polyester material prepared by the present invention has good flame retardancy, antibacterial property and high strength, and at the same time, it still has good flame retardancy, antibacterial property and high strength even after long-term use.
  • the above descriptions are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, some improvements and modifications without departing from the principles of the present invention should also be regarded as the protection scope of the present invention.

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  • Health & Medical Sciences (AREA)
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Abstract

Provided is a thermoplastic polyester used for a thin film. In a process of preparing a polyester, terephthalic acid and ethylene glycol are used to serve as a base material, another component is simultaneously added to adjust a group on a segment, and an auxiliary material is also prepared separate from the base material; the auxiliary material has a large quantity of functional groups, and terephthalic acid and ethylene glycol are also used to serve as a matrix. As a consequence, a better degree of dispersion during subsequent mixing and a polymerization reaction can be realized, and a better effect can be achieved. Also, the influence of a one-time reaction on a functional group is eliminated, allowing an obtained polyester to have more stable performance.

Description

一种用于薄膜的热塑性聚酯及其制备方法A kind of thermoplastic polyester for film and preparation method thereof 技术领域technical field
本发明涉及一种薄膜材料，更具体的说是涉及一种用于薄膜的热塑性聚酯及其制备方法。The invention relates to a film material, in particular to a thermoplastic polyester used for film and a preparation method thereof.
背景技术Background technique
热塑性聚酯具有热塑性特性的饱和聚酯。多指聚对苯二甲酸酯类。其实广义上还应包含其他线型聚酯。在聚对苯二甲酸酯中以聚对苯二甲酸乙二酯和聚对苯二甲酸丁二酯产量大、用途广，其他多用作高性能薄膜和纤维。Thermoplastic Polyester Saturated polyester with thermoplastic properties. More refers to the polyester terephthalate. In fact, it should also include other linear polyesters in a broad sense. Among polyethylene terephthalates, polyethylene terephthalate and polybutylene terephthalate have the largest output and wide application, and others are mostly used as high-performance films and fibers.
其中聚对苯二甲酸乙二酯是最为常用的热塑性聚酯，聚对苯二甲酸乙二醇酯，化学式为COC6H4COOCH2CH2O。(英文：Po1yethylene terephthalate，简称PET)，由对苯二甲酸二甲酯与乙二醇酯交换或以对苯二甲酸与乙二醇酯化先合成对苯二甲酸双羟乙酯，然后再进行缩聚反应制得。具有较好的强度，是一种常见的包装材料。但是，在一些食品包装上，对抗菌性能有一定的要求，否则包装中的食品很容易发生腐败。Among them, polyethylene terephthalate is the most commonly used thermoplastic polyester, polyethylene terephthalate, and its chemical formula is COC6H4COOCH2CH2O. (English: Po1ethylene terephthalate, referred to as PET), by transesterification of dimethyl terephthalate and ethylene glycol or esterification of terephthalic acid and ethylene glycol to synthesize bishydroxyethyl terephthalate, and then carry out Produced by polycondensation reaction. It has good strength and is a common packaging material. However, in some food packaging, there are certain requirements for antibacterial properties, otherwise the food in the packaging is prone to spoilage.
发明内容Contents of the invention
针对现有技术存在的不足，本发明的目的在于提供一种。Aiming at the deficiencies in the prior art, the purpose of the present invention is to provide one.
为实现上述目的，本发明提供了如下技术方案：一种用于薄膜的热塑性聚酯，包括下列质量份组成：In order to achieve the above object, the present invention provides the following technical solutions: a thermoplastic polyester for film, comprising the following components by mass:
对苯二甲酸：1000份；Terephthalic acid: 1000 parts;
乙二醇：600份；Ethylene glycol: 600 parts;
顺丁烯二酐：50份；Maleic anhydride: 50 parts;
2-硝基对苯二酸-4-甲酯：10份；2-nitroterephthalic acid-4-methyl ester: 10 parts;
2，2-二甲基-1，3-丙二醇：10份；2,2-Dimethyl-1,3-propanediol: 10 parts;
2，3-二溴-2-丁烯-1，4-二醇：5份；2,3-dibromo-2-butene-1,4-diol: 5 parts;
1，4-苯二甲醇：8份；1,4-Benzene dimethanol: 8 parts;
2-氨基对苯二甲酸：15份；2-aminoterephthalic acid: 15 parts;
四溴对苯二酸：5份；Tetrabromoterephthalic acid: 5 parts;
双(2-乙基己基)对苯二酸：8份；Bis(2-ethylhexyl)terephthalic acid: 8 parts;
4-溴代苯酐：5份；4-bromophthalic anhydride: 5 parts;
2，2-二氟-1，3-苯并二恶茂：3份；2,2-difluoro-1,3-benzodioxol: 3 parts;
氟硅酸镁：5份；Magnesium fluorosilicate: 5 parts;
抗菌剂5份。5 parts of antibacterial agent.
一种用于薄膜的热塑性聚酯的制备方法，A method for the preparation of thermoplastic polyester for film,
步骤一：将对苯二甲酸400份、乙二醇400份加入到反应釜中，升温至40℃进行预备混合；Step 1: Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
步骤二：升温至200～220摄氏度进行酯化反应，反应30～50分钟后，加入Ti/Si系催化剂0.01～0.5份，继续反应10～30分钟；Step 2: Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
步骤三：加入对苯二甲酸200份，顺丁烯二酐50份、2-硝基对苯二酸-4-甲酯10份，降温至180～200℃，反应20～40分钟；Step 3: Add 200 parts of terephthalic acid, 50 parts of maleic anhydride, 10 parts of 2-nitroterephthalic acid-4-methyl ester, cool down to 180-200°C, and react for 20-40 minutes;
步骤四：加入对苯二甲酸100份、2，2-二甲基-1，3-丙二醇10份、2，3-二溴-2-丁烯-1，4-二醇5份，温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应20～30分钟；Step 4: Add 100 parts of terephthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, 5 parts of 2,3-dibromo-2-butene-1,4-diol, and keep the temperature At 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst and react for 20-30 minutes;
步骤五：加入对苯二甲酸200份、乙二醇100份、1，4-苯二甲醇8份、2-氨基对苯二甲酸15份，升温至200～250℃，反应10～30分钟，得到主料备用；Step 5: Add 200 parts of terephthalic acid, 100 parts of ethylene glycol, 8 parts of 1,4-benzenedimethanol, and 15 parts of 2-aminoterephthalic acid, heat up to 200-250°C, and react for 10-30 minutes. Get the main material for use;
步骤六：辅料的制备，另起一反应釜，加入苯二甲酸100份、乙二醇100份、四溴对苯二酸5份、双(2-乙基己基)对苯二酸8份、4-溴代苯酐5份；温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应30～60分钟得到辅料备用；Step 6: preparation of auxiliary materials, set up another reaction kettle, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 5 parts of tetrabromoterephthalic acid, 8 parts of bis(2-ethylhexyl) terephthalic acid, 5 parts of 4-bromophthalic anhydride; keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use;
步骤七：将辅料缓慢加入到主料的反应釜中，加入的同时进 行搅拌，温度保持在40～50摄氏度，加入完毕后缓慢升温至180～200℃，保温搅拌20～40分钟；Step 7: Slowly add the auxiliary materials into the reaction kettle of the main materials, stir while adding, keep the temperature at 40-50 degrees Celsius, slowly raise the temperature to 180-200 degrees Celsius after adding, keep stirring for 20-40 minutes;
步骤八，升温至250～280℃，200～300Pa真空条件下反应30～60分钟；Step 8, heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
步骤九：完成反应后加入邻溴对苯二甲酸二甲酯10份、2，2-二氟-1，3-苯并二恶茂3份、氟硅酸镁5份、抗菌剂5份，温度控制在100～120℃，进行搅拌30～40分钟后，继续搅拌，自然降温至50～60℃后进行造粒得到塑料粒子；Step 9: After completing the reaction, add 10 parts of dimethyl o-bromoterephthalate, 3 parts of 2,2-difluoro-1,3-benzodioxol, 5 parts of magnesium fluorosilicate, and 5 parts of antibacterial agent, The temperature is controlled at 100-120°C, after stirring for 30-40 minutes, continue to stir, naturally cool down to 50-60°C, and then granulate to obtain plastic particles;
步骤十：将塑料粒子进行制膜。Step 10: Make plastic particles into a film.
作为本发明的进一步改进：所述步骤十中塑料粒子通过流延机制造成薄膜。As a further improvement of the present invention: in the tenth step, the plastic particles are formed into a film by a casting machine.
作为本发明的进一步改进：所述抗菌剂根据下述方法制备：As a further improvement of the present invention: the antibacterial agent is prepared according to the following method:
步骤A：10g纳米二氧化硅中，加入2ml的对氯苯甲酰氯、1ml的4-溴丁酰氯、1ml三氯化磷，20～30℃条件下搅拌反应10～15小时，对纳米二氧化硅进行活性化；Step A: Add 2ml of p-chlorobenzoyl chloride, 1ml of 4-bromobutyryl chloride, and 1ml of phosphorus trichloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, Silicon for activation;
步骤B：反应完成后对混合物进行离心，依次使用三氯甲烷、乙二醇、丙酮进行清洗，进行干燥，得到活化纳米二氧化硅；Step B: After the reaction is completed, the mixture is centrifuged, washed with chloroform, ethylene glycol, and acetone in sequence, and dried to obtain activated nano-silica;
步骤C：在活化纳米二氧化硅中加入7g聚乙烯亚胺、2g二(三甲基硅基)碳酰二亚胺、1g聚碳化二亚胺，加入0.1gKOH，在85℃的条件下搅拌15～20小时；Step C: Add 7g of polyethyleneimine, 2g of bis(trimethylsilyl)carbodiimide, 1g of polycarbodiimide to activated nano-silica, add 0.1g of KOH, and stir at 85°C 15-20 hours;
步骤D：反应结束后经过离心，并用甲醇进行充分洗涤，进行干燥；Step D: Centrifuge after the reaction, fully wash with methanol, and dry;
步骤E：将风干后的纳米二氧化硅粉末装入到20ml的异丁醇中，之后加入2ml的1，2-二溴乙烷、6ml的溴己烷、0.1g溴乙酰溴、1ml的1-溴-3-甲基丁烷，再70～80℃条件下搅拌15～25小时；Step E: Put the air-dried nano silicon dioxide powder into 20ml of isobutanol, then add 2ml of 1,2-dibromoethane, 6ml of bromohexane, 0.1g of bromoacetyl bromide, 1ml of 1 -Bromo-3-methylbutane, then stirred at 70-80°C for 15-25 hours;
步骤F：反应完成后降温到30～45℃，再向其中加入5ml碘化钾，搅拌8～12小时，经过离心，用甲醇充分洗涤，然后干燥 得到抗菌剂。Step F: After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, wash fully with methanol, and then dry to obtain an antibacterial agent.
作为本发明的进一步改进：所述步骤五中，先加入对苯二甲酸50份、之后加入乙二醇100份，剩余的150份对苯二甲酸分成三份，每隔10分钟加入50份对苯二甲酸，最后加入2，2-二甲基-1，3-丙二醇10份。As a further improvement of the present invention: in the step five, first add 50 parts of terephthalic acid, then add 100 parts of ethylene glycol, and divide the remaining 150 parts of terephthalic acid into three parts, and add 50 parts of terephthalic acid every 10 minutes. Phthalic acid, finally add 10 parts of 2,2-dimethyl-1,3-propanediol.
作为本发明的进一步改进：所述步骤一中，在加入原料前，先在反应容器中加入2，6-二叔丁基-4-甲基苯酚，加入200份乙二醇，搅拌5～15分钟，再加入剩余的600份乙二醇和400份对苯二甲酸，升温至40℃进行预备混合。As a further improvement of the present invention: in the first step, before adding the raw materials, first add 2,6-di-tert-butyl-4-methylphenol into the reaction vessel, add 200 parts of ethylene glycol, stir for 5-15 Minutes, then add the remaining 600 parts of ethylene glycol and 400 parts of terephthalic acid, and raise the temperature to 40°C for preliminary mixing.
作为本发明的进一步改进：所述步骤二、步骤四、步骤六中加入Ti/Si系催化剂时，先将Ti/Si系催化剂用50ml乙二醇稀释，在加入到反应容器中。As a further improvement of the present invention: when adding the Ti/Si catalyst in the step 2, step 4, and step 6, first dilute the Ti/Si catalyst with 50ml of ethylene glycol, and then add it into the reaction vessel.
本发明在制备聚酯过程中，首先以对苯二甲酸和乙二醇作为基料，同时加入其它组分，以调整链段间上的基团，同时将辅料与基料分开制备，辅料中带有大量的功能基团，也是以对苯二甲酸和乙二醇为基体，这样能够在后期混合以及聚合反应中，分散度会更好，达到更好地效果。同时，也排除了一次性反应对功能基团的影响，使得得到的聚酯更加性能更加稳定。In the process of preparing the polyester, the present invention first uses terephthalic acid and ethylene glycol as the base material, and simultaneously adds other components to adjust the groups between the chain segments, and simultaneously prepares the auxiliary material and the base material separately. With a large number of functional groups, it is also based on terephthalic acid and ethylene glycol, so that in the later mixing and polymerization reactions, the dispersion will be better and better results will be achieved. At the same time, the impact of the one-time reaction on the functional groups is also eliminated, making the obtained polyester more stable in performance.
在步骤一中，首先将大部分的对苯二甲酸、乙二醇加入到反应容器中，首先进行一个预混合过程，同时升温至40℃，能够使得其预混合更加均匀，促进分子间的自由运动。能够有效防止突然加入过多量的反应原料会发生过度聚合的现象。之后的步骤二中，开始升温至200～220摄氏度以及加入Ti/Si系催化剂，开始聚酯反应，在整个反应体系中乙二醇的量远远大于对苯二甲酸，一方面乙二醇是溶剂，能够降低起到一个稀释作用，从而使得对苯二甲酸能够缓慢与乙二醇发生聚酯反应。In step 1, most of the terephthalic acid and ethylene glycol are added to the reaction vessel first, and a pre-mixing process is carried out, and the temperature is raised to 40°C at the same time, so that the pre-mixing can be made more uniform and the intermolecular freedom can be promoted. sports. It can effectively prevent the phenomenon of excessive polymerization caused by sudden addition of too much reaction raw material. In the subsequent step 2, the temperature is raised to 200-220 degrees Celsius and Ti/Si catalyst is added to start the polyester reaction. The amount of ethylene glycol in the entire reaction system is far greater than that of terephthalic acid. On the one hand, ethylene glycol is The solvent can reduce and play a diluting effect, so that terephthalic acid can slowly react with ethylene glycol for polyester.
由于上述步骤中，乙二醇是过量的，因此步骤三中补入部分对苯二甲酸，以保证反应速率。而加入的顺丁烯二酐能够增加整 体链段的柔性，调节分子链的长度，能够保证链段具有较好的拉伸强度，同时2-硝基对苯二酸-4-甲酯的加入能够消耗部分乙二醇的同时，能够在整个体系中引入氨基和硝基，能够增强整个体系的耐候性，同时还带有苯基团，能够和整个体系相似相容，提高整体的相容性，因此能够带来较好的均匀性，避免了局部性能的提升。Because in the above-mentioned steps, ethylene glycol is excessive, therefore fills in part terephthalic acid in step 3, to guarantee reaction rate. The maleic anhydride added can increase the flexibility of the overall chain segment, regulate the length of the molecular chain, and ensure that the chain segment has good tensile strength, while the addition of 2-nitroterephthalic acid-4-methyl While consuming part of ethylene glycol, amino groups and nitro groups can be introduced into the entire system, which can enhance the weather resistance of the entire system. At the same time, it also contains phenyl groups, which can be similarly compatible with the entire system and improve the overall compatibility. , so it can bring better uniformity and avoid the improvement of local performance.
步骤四中继续补入加入对苯二甲酸，同时加入2，2-二甲基-1，3-丙二醇和2，3-二溴-2-丁烯-1，4-二醇，通过加入2，2-二甲基-1，3-丙二醇，调节分子链，使得产品分子量更加均匀，同时产品的透光率也能够得到保证。2，3-二溴-2-丁烯-1，4-二醇能够参与反应，将溴取代基引入到连段中，能够提高整体的阻燃性能。Continue to add terephthalic acid in step 4, add 2,2-dimethyl-1,3-propanediol and 2,3-dibromo-2-butene-1,4-diol simultaneously, by adding 2 , 2-dimethyl-1,3-propanediol, adjust the molecular chain, so that the molecular weight of the product is more uniform, and the light transmittance of the product can also be guaranteed. 2,3-dibromo-2-butene-1,4-diol can participate in the reaction, and the bromine substituent is introduced into the continuous segment, which can improve the overall flame retardancy.
步骤五补入部分对苯二甲酸的同时，也加入乙二醇，在之前反应中，乙二醇己经被消耗的差不多了，补入乙二醇能够保证反应速率不会被降低。之后加入的1，4-苯二甲醇、2-氨基对苯二甲酸，1，4-苯二甲醇的加入增强了整体的强度，由于2-氨基对苯二甲酸的支链很容易被活化，因此降低温度在能够进行正常的聚酯反应的同时，还能够避免副反应的发生。In Step 5, ethylene glycol is also added while part of the terephthalic acid is replenished. In the previous reaction, ethylene glycol has been almost consumed, and the addition of ethylene glycol can ensure that the reaction rate will not be reduced. The addition of 1,4-benzenedimethanol, 2-aminoterephthalic acid, and 1,4-benzenedimethanol to enhance the overall strength, because the branch chain of 2-aminoterephthalic acid is easily activated, Therefore, lowering the temperature can avoid the occurrence of side reactions while normal polyester reactions can be carried out.
步骤六则是辅料的制备过程，依然是以对苯二甲酸和乙二醇为载体，加入四溴对苯二酸、双(2-乙基己基)对苯二酸、4-溴代苯酐；而四溴对苯二酸和4-溴代苯酐的加入，主要是将溴取代基引入到连段中，保证了其整体的阻燃性，双(2-乙基己基)对苯二酸的加入使得四溴对苯二酸和4-溴代苯酐的聚合位置不会靠的太近，在分子间作用里的条件下引入侧链基团，保证整体阻燃性能的均匀性和稳定性。Step six is the preparation process of auxiliary materials, still using terephthalic acid and ethylene glycol as carriers, adding tetrabromoterephthalic acid, bis(2-ethylhexyl)terephthalic acid, and 4-bromophthalic anhydride; The addition of tetrabromoterephthalic acid and 4-bromophthalic anhydride mainly introduces bromine substituents into the continuous segment, ensuring its overall flame retardancy. The addition makes the polymerization positions of tetrabromoterephthalic acid and 4-bromophthalic anhydride not too close, and introduces side chain groups under the conditions of intermolecular interaction to ensure the uniformity and stability of the overall flame retardant performance.
之后将步骤六中的辅料缓慢加入到主料中混合，很合后进行加压发生聚合反应，得到物性均匀的聚酯。Afterwards, slowly add the auxiliary materials in step 6 into the main material for mixing, and then pressurize and polymerize to obtain a polyester with uniform physical properties.
经过聚合反应后，整个体系已经基本成型，之后加入的溴对 苯二甲酸二甲酯、2，2-二氟-1，3-苯并二恶茂、氟硅酸镁、抗菌剂均属于改性剂，溴对苯二甲酸二甲酯能够与反应生成的聚合物进行反应，提高整体的阻燃性能，2，2-二氟-1，3-苯并二恶茂本身能够制品整体的强度，同时其本身结构上与聚对苯二甲酸乙二醇酯相近，因此具有较好的相容性，能够均匀分布在分子链之间，更进一步加强了整体的阻燃性。氟硅酸镁的加入能够使得提高聚酯的强度，同时也能够起到一个稳定剂的作用，使得聚酯不管在加工还是使用过程中都能体现出一定的稳定性。抗菌剂的加入能够提高其整体的抗菌性能。After the polymerization reaction, the whole system has been basically formed, and the added dimethyl bromoterephthalate, 2,2-difluoro-1,3-benzodioxol, magnesium fluorosilicate, and antibacterial agents are all modified As a neutral agent, dimethyl bromoterephthalate can react with the polymer produced by the reaction to improve the overall flame retardancy, and 2,2-difluoro-1,3-benzodioxol itself can enhance the overall strength of the product , At the same time, its structure is similar to that of polyethylene terephthalate, so it has good compatibility and can be evenly distributed between molecular chains, which further strengthens the overall flame retardancy. The addition of magnesium fluorosilicate can improve the strength of the polyester, and can also act as a stabilizer, so that the polyester can show a certain degree of stability whether it is processed or used. The addition of antibacterial agent can improve its overall antibacterial performance.
在催化剂加入过程中，将其稀释，能够防止局部浓度过大而导致局部团聚的现象。During the addition of the catalyst, diluting it can prevent local agglomeration caused by excessive local concentration.
在反应前加入的2，6-二叔丁基-4-甲基苯酚是一种通用的抗氧剂，与乙二醇一同加入容器，一方面对反应容器有一个清洁作用，另一方面也能够防止聚酯在反应过程中被氧化。The 2,6-di-tert-butyl-4-methylphenol added before the reaction is a general-purpose antioxidant, which is added to the container together with ethylene glycol. On the one hand, it has a cleaning effect on the reaction container, and on the other hand, it also It can prevent the polyester from being oxidized during the reaction.
在抗菌剂上，选用季铵盐型抗菌剂，其季铵盐符合在纳米二氧化硅上。On the antibacterial agent, select the quaternary ammonium salt type antibacterial agent, and its quaternary ammonium salt conforms to the nano silicon dioxide.
抗菌剂的制备过程中，纳米二氧化硅能够在氯苯甲酰氯、4-溴丁酰氯、三氯化磷的条件下进一步被活化，特别是三氯化磷的加入，能够提高纳米二氧化硅的活化性能，同时使得最终得到的抗菌剂具有更好地耐候性，即在长时间使用过程中也能够起到较好的抗菌效果。During the preparation of antibacterial agents, nano-silica can be further activated under the conditions of chlorobenzoyl chloride, 4-bromobutyryl chloride, and phosphorus trichloride, especially the addition of phosphorus trichloride can improve the performance of nano-silica. Activation performance, while making the final antibacterial agent have better weather resistance, that is, it can also play a better antibacterial effect during long-term use.
之后对其进行清洗，三氯甲烷对氯苯甲酰氯、三氯化磷的溶解性较好，能够将其取出，而乙二醇则能够取出残留的三氯甲烷，最终用丙酮清洗，能够彻底取出残留物质。Afterwards, it is cleaned, and trichloromethane has good solubility to chlorobenzoyl chloride and phosphorus trichloride, and it can be taken out, while ethylene glycol can take out residual trichloromethane, and finally, it can be cleaned thoroughly with acetone. Remove residual material.
将活性纳米二氧化硅与聚乙烯亚胺、二(三甲基硅基)碳酰二亚胺、聚碳化二亚胺反应，将聚乙烯亚胺、二(三甲基硅基)碳酰二亚胺、聚碳化二亚胺上的基团固定在纳米二氧化硅上。最后加入1，2-二溴乙烷、溴己烷、溴乙酰溴、1-溴-3-甲基丁烷与固定 在活性纳米二氧化硅的基团发生反应，得到季铵盐抗菌剂，而季铵盐抗菌剂已经被固定在了纳米二氧化硅的载体上。这样的抗菌剂不易发生流失，在纳米二氧化硅的载体上使得抗菌效果更佳稳定。其中反应主要在聚乙烯亚胺、二(三甲基硅基)碳酰二亚胺、聚碳化二亚胺和1，2-二溴乙烷、溴己烷、溴乙酰溴、1-溴-3-甲基丁烷之间发生反应，反应生成的季铵盐具有强稳定性，特别是二(三甲基硅基)碳酰二亚胺的加入，能够使得与二氧化硅的结合力更好，不易从纳米二氧化硅上脱落，同时溴乙酰溴的加入也提高了抗菌剂的活性。Reaction of active nano-silica with polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide, polyethyleneimine, bis(trimethylsilyl) carbonyl diimide Groups on imine and polycarbodiimide are fixed on nano silicon dioxide. Finally, 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo-3-methylbutane are added to react with groups fixed on active nano silicon dioxide to obtain quaternary ammonium salt antibacterial agent, And the quaternary ammonium antibacterial agent has been immobilized on the carrier of nano silicon dioxide. Such an antibacterial agent is not easy to be lost, and the antibacterial effect is better and more stable on the carrier of nano silicon dioxide. The reaction is mainly in polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide and 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo- There is a reaction between 3-methylbutane, and the quaternary ammonium salt generated by the reaction has strong stability, especially the addition of bis(trimethylsilyl)carbodiimide, which can make the binding force with silicon dioxide stronger Well, it is not easy to fall off from the nano-silica, and the addition of bromoacetyl bromide also improves the activity of the antibacterial agent.
因此，本发明制备的热塑性聚酯材料，具有较好的阻燃性、抗菌性、高强度的同时，及时在长时间使用过后，仍然具有较好的阻燃性、抗菌性、高强度。Therefore, the thermoplastic polyester material prepared by the present invention has good flame retardancy, antibacterial property and high strength, and at the same time, it still has good flame retardancy, antibacterial property and high strength even after long-term use.
具体实施方式Detailed ways
实施例一：Embodiment one:
一种用于薄膜的热塑性聚酯，包括下列质量份组成：A kind of thermoplastic polyester for film, comprises following composition by mass parts:
对苯二甲酸：1000份；Terephthalic acid: 1000 parts;
乙二醇：600份；Ethylene glycol: 600 parts;
顺丁烯二酐：50份；Maleic anhydride: 50 parts;
2-硝基对苯二酸-4-甲酯：10份；2-nitroterephthalic acid-4-methyl ester: 10 parts;
2，2-二甲基-1，3-丙二醇：10份；2,2-Dimethyl-1,3-propanediol: 10 parts;
2，3-二溴-2-丁烯-1，4-二醇：5份；2,3-dibromo-2-butene-1,4-diol: 5 parts;
1，4-苯二甲醇：8份；1,4-Benzene dimethanol: 8 parts;
2-氨基对苯二甲酸：15份；2-aminoterephthalic acid: 15 parts;
四溴对苯二酸：5份；Tetrabromoterephthalic acid: 5 parts;
双(2-乙基己基)对苯二酸：8份；Bis(2-ethylhexyl)terephthalic acid: 8 parts;
4-溴代苯酐：5份；4-bromophthalic anhydride: 5 parts;
2，2-二氟-1，3-苯并二恶茂：3份；2,2-difluoro-1,3-benzodioxol: 3 parts;
氟硅酸镁：5份；Magnesium fluorosilicate: 5 parts;
抗菌剂5份。5 parts of antibacterial agent.
一种用于薄膜的热塑性聚酯的制备方法，A method for the preparation of thermoplastic polyester for film,
步骤一：将对苯二甲酸400份、乙二醇400份加入到反应釜中，升温至40℃进行预备混合；Step 1: Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
步骤二：升温至200～220摄氏度进行酯化反应，反应30～50分钟后，加入Ti/Si系催化剂0.01～0.5份，继续反应10～30分钟；Step 2: Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
步骤三：加入对苯二甲酸200份，顺丁烯二酐50份、2-硝基对苯二酸-4-甲酯10份，降温至180～200℃，反应20～40分钟；Step 3: Add 200 parts of terephthalic acid, 50 parts of maleic anhydride, 10 parts of 2-nitroterephthalic acid-4-methyl ester, cool down to 180-200°C, and react for 20-40 minutes;
步骤四：加入对苯二甲酸100份、2，2-二甲基-1，3-丙二醇10份、2，3-二溴-2-丁烯-1，4-二醇5份，温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应20～30分钟；Step 4: Add 100 parts of terephthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, 5 parts of 2,3-dibromo-2-butene-1,4-diol, and keep the temperature At 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst and react for 20-30 minutes;
步骤五：加入对苯二甲酸200份、乙二醇100份、1，4-苯二甲醇8份、2-氨基对苯二甲酸15份，升温至200～250℃，反应10～30分钟，得到主料备用；Step 5: Add 200 parts of terephthalic acid, 100 parts of ethylene glycol, 8 parts of 1,4-benzenedimethanol, and 15 parts of 2-aminoterephthalic acid, heat up to 200-250°C, and react for 10-30 minutes. Get the main material for use;
步骤六：辅料的制备，另起一反应釜，加入苯二甲酸100份、乙二醇100份、四溴对苯二酸5份、双(2-乙基己基)对苯二酸8份、4-溴代苯酐5份；温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应30～60分钟得到辅料备用；步骤七：将辅料缓慢加入到主料的反应釜中，加入的同时进行搅拌，温度保持在40～50摄氏度，加入完毕后缓慢升温至180～200℃，保温搅拌20～40分钟；Step 6: preparation of auxiliary materials, set up another reaction kettle, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 5 parts of tetrabromoterephthalic acid, 8 parts of bis(2-ethylhexyl) terephthalic acid, 5 parts of 4-bromophthalic anhydride; keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use; Step 7: Slowly add auxiliary materials into the reaction kettle of main materials , Stir while adding, keep the temperature at 40-50 degrees Celsius, slowly heat up to 180-200 degrees Celsius after adding, keep stirring for 20-40 minutes;
步骤八，升温至250～280℃，200～300Pa真空条件下反应30～60分钟；Step 8, heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
步骤九：完成反应后加入邻溴对苯二甲酸二甲酯10份、2，2-二氟-1，3-苯并二恶茂3份、氟硅酸镁5份、抗菌剂5份，温度控制在100～120℃，进行搅拌30～40分钟后，继续搅拌，自 然降温至50～60℃后进行造粒得到塑料粒子；Step 9: After completing the reaction, add 10 parts of dimethyl o-bromoterephthalate, 3 parts of 2,2-difluoro-1,3-benzodioxol, 5 parts of magnesium fluorosilicate, and 5 parts of antibacterial agent, The temperature is controlled at 100-120°C, after stirring for 30-40 minutes, continue to stir, naturally cool down to 50-60°C, and then granulate to obtain plastic particles;
步骤十：将塑料粒子进行制膜。Step 10: Make plastic particles into a film.
所述步骤十中塑料粒子通过流延机制造成薄膜。In the tenth step, the plastic particles are formed into a film by a casting machine.
所述抗菌剂根据下述方法制备：Described antibacterial agent is prepared according to the following method:
步骤A：10g纳米二氧化硅中，加入2ml的对氯苯甲酰氯、1ml的4-溴丁酰氯、1ml三氯化磷，20～30℃条件下搅拌反应10～15小时，对纳米二氧化硅进行活性化；Step A: Add 2ml of p-chlorobenzoyl chloride, 1ml of 4-bromobutyryl chloride, and 1ml of phosphorus trichloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, Silicon for activation;
步骤B：反应完成后对混合物进行离心，依次使用三氯甲烷、乙二醇、丙酮进行清洗，进行干燥，得到活化纳米二氧化硅；Step B: After the reaction is completed, the mixture is centrifuged, washed with chloroform, ethylene glycol, and acetone in sequence, and dried to obtain activated nano-silica;
步骤C：在活化纳米二氧化硅中加入7g聚乙烯亚胺、2g二(三甲基硅基)碳酰二亚胺、1g聚碳化二亚胺，加入0.1gKOH，在85℃的条件下搅拌15～20小时；Step C: Add 7g of polyethyleneimine, 2g of bis(trimethylsilyl)carbodiimide, 1g of polycarbodiimide to activated nano-silica, add 0.1g of KOH, and stir at 85°C 15-20 hours;
步骤D：反应结束后经过离心，并用甲醇进行充分洗涤，进行干燥；Step D: Centrifuge after the reaction, fully wash with methanol, and dry;
步骤E：将风干后的纳米二氧化硅粉末装入到20ml的异丁醇中，之后加入2ml的1，2-二溴乙烷、6ml的溴己烷、0.1g溴乙酰溴、1ml的1-溴-3-甲基丁烷，再70～80℃条件下搅15～25小时；Step E: Put the air-dried nano silicon dioxide powder into 20ml of isobutanol, then add 2ml of 1,2-dibromoethane, 6ml of bromohexane, 0.1g of bromoacetyl bromide, 1ml of 1 -Bromo-3-methylbutane, then stirred at 70-80°C for 15-25 hours;
步骤F：反应完成后降温到30～45℃，再向其中加入5ml碘化钾，搅拌8～12小时，经过离心，用甲醇充分洗涤，然后干燥得到抗菌剂。Step F: After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
所述步骤五中，先加入对苯二甲酸50份、之后加入乙二醇100份，剩余的150份对苯二甲酸分成三份，每隔10分钟加入50份对苯二甲酸，最后加入2，2-二甲基-1，3-丙二醇10份。In the step five, first add 50 parts of terephthalic acid, then add 100 parts of ethylene glycol, and divide the remaining 150 parts of terephthalic acid into three parts, add 50 parts of terephthalic acid every 10 minutes, and finally add 2 , 10 parts of 2-dimethyl-1,3-propanediol.
所述步骤一中，在加入原料前，先在反应容器中加入2，6-二叔丁基-4-甲基苯酚，加入200份乙二醇，搅拌5～15分钟，再加入剩余的600份乙二醇和400份对苯二甲酸，升温至40℃进行预备混合。In the first step, before adding raw materials, first add 2,6-di-tert-butyl-4-methylphenol into the reaction vessel, add 200 parts of ethylene glycol, stir for 5 to 15 minutes, and then add the remaining 600 parts Parts of ethylene glycol and 400 parts of terephthalic acid, heated to 40°C for preliminary mixing.
所述步骤二、步骤四、步骤六中加入Ti/Si系催化剂时，先将Ti/Si系催化剂用50ml乙二醇稀释，在加入到反应容器中。When adding the Ti/Si catalyst in the step 2, step 4, and step 6, first dilute the Ti/Si catalyst with 50ml of ethylene glycol, and then add it into the reaction vessel.
实施例二：Embodiment two:
与实施例一的区别在于其制备抗菌剂步骤为：The difference with embodiment one is that its preparation antibacterial agent step is:
步骤A：10g纳米二氧化硅中，加入4ml的4-溴丁酰氯，20～30℃条件下搅拌反应10～15小时，对纳米二氧化硅进行活性化；Step A: Add 4ml of 4-bromobutyryl chloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, and activate the nano-silica;
步骤B：反应完成后对混合物进行离心，使用甲醇进行清洗，进行干燥，得到活化纳米二氧化硅；Step B: After the reaction is completed, the mixture is centrifuged, washed with methanol, and dried to obtain activated nano-silica;
步骤C：在活化纳米二氧化硅中加入10g聚乙烯亚胺，加入0.1gKOH，在85℃的条件下搅拌15～20小时；Step C: Add 10 g of polyethyleneimine to the activated nano-silica, add 0.1 g of KOH, and stir at 85° C. for 15 to 20 hours;
步骤D：反应结束后经过离心，并用甲醇进行充分洗涤，进行干燥；Step D: Centrifuge after the reaction, fully wash with methanol, and dry;
步骤E：将风干后的纳米二氧化硅粉末装入到20ml的异丁醇中，之后加入10ml的溴己烷、0.1g溴乙酰溴在70～80℃条件下搅拌15～25小时；Step E: Put the air-dried nano-silica powder into 20ml of isobutanol, then add 10ml of bromohexane and 0.1g of bromoacetyl bromide and stir at 70-80°C for 15-25 hours;
步骤F：反应完成后降温到30～45℃，再向其中加入5ml碘化钾，搅拌8～12小时，经过离心，用甲醇充分洗涤，然后干燥得到抗菌剂。Step F: After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
实施例三Embodiment three
与实施例一相比，区别在于选用市购买的广州市诺康化工有限公司的HM98有机硅抗菌剂。Compared with Example 1, the difference is that the HM98 organosilicon antibacterial agent purchased from Guangzhou Nuokang Chemical Co., Ltd. is selected.
对比例一：Comparative example one:
采用市购的杜邦公司透明PET薄膜。A commercially available DuPont transparent PET film was used.
对比例二Comparative example two
步骤一：将对苯二甲酸400份、乙二醇400份加入到反应釜中，升温至40℃进行预备混合；Step 1: Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
步骤二：升温至200～220摄氏度进行酯化反应，反应30～50分钟后，加入Ti/Si系催化剂0.01～0.5份，继续反应10～ 30分钟；Step 2: Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
步骤三：加入对苯二甲酸200份，降温至180～200℃，反应20～40分钟；Step 3: Add 200 parts of terephthalic acid, lower the temperature to 180-200°C, and react for 20-40 minutes;
步骤四：加入对苯二甲酸100份，温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应20～30分钟；Step 4: Add 100 parts of terephthalic acid, keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 20-30 minutes;
步骤五：加入对苯二甲酸200份、乙二醇100份，升温至200～250℃，反应10～30分钟，得到主料备用；Step 5: Add 200 parts of terephthalic acid and 100 parts of ethylene glycol, heat up to 200-250°C, and react for 10-30 minutes to obtain the main ingredients for later use;
步骤六：辅料的制备，另起一反应釜，加入苯二甲酸100份、乙二醇100份、加入Ti/Si系催化剂0.01～0.5份，反应30～60分钟得到辅料备用；Step 6: Preparation of auxiliary materials, set up another reactor, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use;
步骤七：将辅料缓慢加入到主料的反应釜中，加入的同时进行搅拌，温度保持在40～50摄氏度，加入完毕后缓慢升温至180～200℃，保温搅拌20～40分钟；Step 7: Slowly add the auxiliary materials into the reaction kettle of the main materials, stir while adding, keep the temperature at 40-50 degrees Celsius, slowly raise the temperature to 180-200 degrees Celsius after the addition, keep stirring for 20-40 minutes;
步骤八，升温至250～280℃，200～300Pa真空条件下反应30～60分钟；Step 8, heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
步骤九：将塑料粒子进行制膜。Step 9: Making plastic particles into a film.
所述步骤九中塑料粒子通过流延机制造成薄膜。In said step nine, the plastic particles are formed into a film by a casting machine.
抗菌剂步骤为：The antimicrobial steps are:
步骤A：10g纳米二氧化硅中，加入4ml的4-溴丁酰氯，20～30℃条件下搅拌反应10～15小时，对纳米二氧化硅进行活性化；Step A: Add 4ml of 4-bromobutyryl chloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, and activate the nano-silica;
步骤B：反应完成后对混合物进行离心，使用甲醇进行清洗，进行干燥，得到活化纳米二氧化硅；Step B: After the reaction is completed, the mixture is centrifuged, washed with methanol, and dried to obtain activated nano-silica;
步骤C：在活化纳米二氧化硅中加入10g聚乙烯亚胺，加入0.1gKOH，在85℃的条件下搅拌15～20小时；Step C: Add 10 g of polyethyleneimine to the activated nano-silica, add 0.1 g of KOH, and stir at 85° C. for 15 to 20 hours;
步骤D：反应结束后经过离心，并用甲醇进行充分洗涤，进行干燥；Step D: Centrifuge after the reaction, fully wash with methanol, and dry;
步骤E：将风干后的纳米二氧化硅粉末装入到20ml的异丁醇中，之后加入10ml的溴己烷、0.1g溴乙酰溴在70～80℃条件下 搅拌15～25小时；Step E: Put the air-dried nano-silica powder into 20ml of isobutanol, then add 10ml of bromohexane and 0.1g of bromoacetyl bromide and stir at 70-80°C for 15-25 hours;
步骤F：反应完成后降温到30～45℃，再向其中加入5ml碘化钾，搅拌8～12小时，经过离心，用甲醇充分洗涤，然后干燥得到抗菌剂。Step F: After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
对比例三：Comparative example three:
与对比例二的区别在于选用市购买的广州市诺康化工有限公司的HM98有机硅抗菌剂。The difference with Comparative Example 2 is that the HM98 organosilicon antibacterial agent of Guangzhou Nuokang Chemical Co., Ltd. purchased in the city is selected.
测试，将上述材料均制备成流延膜，厚度为200μm，测试其拉伸强度、透明度、抗菌性、阻燃性能。以及在在疝气灯照射50、100、150、200小时试验后进行上述测试。For testing, the above materials were all prepared into cast films with a thickness of 200 μm, and their tensile strength, transparency, antibacterial properties, and flame retardant properties were tested. And the above tests were carried out after 50, 100, 150, 200 hours of exposure to the xenon lamp.
准确称取0.1g样品，加入到装有99mL无菌水的三角瓶中，用超声波分20min。加入1mL浓度为107CFU/mL菌悬液。另取一个装有99mL无菌水的三角瓶作为空白对照，只加入1mL菌悬液。将上述三角瓶置于振荡培养箱，于37℃、200r/min条件下振荡培养30min。三角瓶中各取0.2mL混合液，适当稀释后，涂布在培养皿上，于35℃下恒温培养48～72h，进行菌落计数。上述两组样品各做3个平行实验，抗菌率按以下公式计算：R＝[(A-B)/A]*100％Accurately weigh 0.1 g of the sample, add it into a conical flask filled with 99 mL of sterile water, and separate it by ultrasonic waves for 20 min. Add 1 mL of bacterial suspension with a concentration of 107 CFU/mL. Take another triangular flask filled with 99mL of sterile water as a blank control, and only add 1mL of bacterial suspension. The above-mentioned Erlenmeyer flask was placed in a shaking incubator, and shaken at 37°C and 200r/min for 30min. Take 0.2mL of the mixture in each Erlenmeyer flask, after appropriate dilution, spread it on a petri dish, incubate at a constant temperature of 35°C for 48-72h, and count the colonies. The above-mentioned two groups of samples are each done 3 parallel experiments, and the antibacterial rate is calculated according to the following formula: R=[(A-B)/A]*100%
R——抗菌率，R——antibacterial rate,
A——空白对照组的平均菌落数；A - the average number of colonies in the blank control group;
B——加入待测抗菌样品的平均菌落数。B - the average number of colonies added to the antibacterial sample to be tested.
菌种的选择上选用金黄色葡萄球菌和大肠杆菌。Staphylococcus aureus and Escherichia coli were selected as the strains.
表一：未经疝气灯照射试验数据Table 1: Test data without Xenon lamp irradiation
Figure PCTCN2021120055-appb-000001
Figure PCTCN2021120055-appb-000001
表二：经疝气灯照射50小时试验数据Table 2: Test data after 50 hours of exposure to a xenon lamp
Figure PCTCN2021120055-appb-000002
Figure PCTCN2021120055-appb-000002
表三：经疝气灯照射100小时试验数据Table 3: Test data after 100 hours of exposure to a xenon lamp
Figure PCTCN2021120055-appb-000003
Figure PCTCN2021120055-appb-000003
表四：经疝气灯照射150小时试验数据Table 4: Test data after 150 hours of exposure to a xenon lamp
Figure PCTCN2021120055-appb-000004
Figure PCTCN2021120055-appb-000004
表五：经疝气灯照射100小时试验数据Table 5: Test data after 100 hours of exposure to a xenon lamp
Figure PCTCN2021120055-appb-000005
Figure PCTCN2021120055-appb-000005
本发明在制备聚酯过程中，首先以对苯二甲酸和乙二醇作为基料，同时加入其它组分，以调整链段间上的基团，同时将辅料与基料分开制备，辅料中带有大量的功能基团，也是以对苯二甲酸和乙二醇为基体，这样能够在后期混合以及聚合反应中，分散度会更好，达到更好地效果。同时，也排除了一次性反应对功能基团的影响，使得得到的聚酯更加性能更加稳定。In the process of preparing the polyester, the present invention first uses terephthalic acid and ethylene glycol as the base material, and simultaneously adds other components to adjust the groups between the chain segments, and simultaneously prepares the auxiliary material and the base material separately. With a large number of functional groups, it is also based on terephthalic acid and ethylene glycol, so that in the later mixing and polymerization reactions, the dispersion will be better and better results will be achieved. At the same time, the impact of the one-time reaction on the functional groups is also eliminated, making the obtained polyester more stable in performance.
在步骤一中，首先将大部分的对苯二甲酸、乙二醇加入到反应容器中，首先进行一个预混合过程，同时升温至40℃，能够使得其预混合更加均匀，促进分子间的自由运动。能够有效防止突然加入过多量的反应原料会发生过度聚合的现象。之后的步骤二中，开始升温至200～220摄氏度以及加入Ti/Si系催化剂，开始聚酯反应，在整个反应体系中乙二醇的量远远大于对苯二甲酸，一方面乙二醇是溶剂，能够降低起到一个稀释作用，从而使得对苯二甲酸能够缓慢与乙二醇发生聚酯反应。In step 1, most of the terephthalic acid and ethylene glycol are added to the reaction vessel first, and a pre-mixing process is carried out, and the temperature is raised to 40°C at the same time, so that the pre-mixing can be made more uniform and the intermolecular freedom can be promoted. sports. It can effectively prevent the phenomenon of excessive polymerization caused by sudden addition of too much reaction raw material. In the subsequent step 2, the temperature is raised to 200-220 degrees Celsius and Ti/Si catalyst is added to start the polyester reaction. The amount of ethylene glycol in the entire reaction system is far greater than that of terephthalic acid. On the one hand, ethylene glycol is The solvent can reduce and play a diluting effect, so that terephthalic acid can slowly react with ethylene glycol for polyester.
由于上述步骤中，乙二醇是过量的，因此步骤三中补入部分对苯二甲酸，以保证反应速率。而加入的顺丁烯二酐能够增加整体链段的柔性，调节分子链的长度，能够保证链段具有较好的拉伸强度，同时2-硝基对苯二酸-4-甲酯的加入能够消耗部分乙二醇的同时，能够在整个体系中引入氨基和硝基，能够增强整个体系的耐候性，同时还带有苯基团，能够和整个体系相似相容，提 高整体的相容性，因此能够带来较好的均匀性，避免了局部性能的提升。Because in the above-mentioned steps, ethylene glycol is excessive, therefore fills in part terephthalic acid in step 3, to guarantee reaction rate. The maleic anhydride added can increase the flexibility of the overall chain segment, regulate the length of the molecular chain, and ensure that the chain segment has good tensile strength, while the addition of 2-nitroterephthalic acid-4-methyl While consuming part of ethylene glycol, amino groups and nitro groups can be introduced into the entire system, which can enhance the weather resistance of the entire system. At the same time, it also contains phenyl groups, which can be similarly compatible with the entire system and improve the overall compatibility. , so it can bring better uniformity and avoid the improvement of local performance.
步骤四中继续补入加入对苯二甲酸，同时加入2，2-二甲基-1，3-丙二醇和2，3-二溴-2-丁烯-1，4-二醇，通过加入2，2-二甲基-1，3-丙二醇，调节分子链，使得产品分子量更加均匀，同时产品的透光率也能够得到保证。2，3-二溴-2-丁烯-1，4-二醇能够参与反应，将溴取代基引入到连段中，能够提高整体的阻燃性能。Continue to add terephthalic acid in step 4, add 2,2-dimethyl-1,3-propanediol and 2,3-dibromo-2-butene-1,4-diol simultaneously, by adding 2 , 2-dimethyl-1,3-propanediol, adjust the molecular chain, so that the molecular weight of the product is more uniform, and the light transmittance of the product can also be guaranteed. 2,3-dibromo-2-butene-1,4-diol can participate in the reaction, and the bromine substituent is introduced into the continuous segment, which can improve the overall flame retardancy.
步骤五补入部分对苯二甲酸的同时，也加入乙二醇，在之前反应中，乙二醇己经被消耗的差不多了，补入乙二醇能够保证反应速率不会被降低。之后加入的1，4-苯二甲醇、2-氨基对苯二甲酸，1，4-苯二甲醇的加入增强了整体的强度，由于2-氨基对苯二甲酸的支链很容易被活化，因此降低温度在能够进行正常的聚酯反应的同时，还能够避免副反应的发生。In Step 5, ethylene glycol is also added while part of the terephthalic acid is replenished. In the previous reaction, ethylene glycol has been almost consumed, and the addition of ethylene glycol can ensure that the reaction rate will not be reduced. The addition of 1,4-benzenedimethanol, 2-aminoterephthalic acid, and 1,4-benzenedimethanol to enhance the overall strength, because the branch chain of 2-aminoterephthalic acid is easily activated, Therefore, lowering the temperature can avoid the occurrence of side reactions while normal polyester reactions can be carried out.
步骤六则是辅料的制备过程，依然是以对苯二甲酸和乙二醇为载体，加入四溴对苯二酸、双(2-乙基己基)对苯二酸、4-溴代苯酐；而四溴对苯二酸和4-溴代苯酐的加入，主要是将溴取代基引入到连段中，保证了其整体的阻燃性，双(2-乙基己基)对苯二酸的加入使得四溴对苯二酸和4-溴代苯酐的聚合位置不会靠的太近，在分子间作用里的条件下引入侧链基团，保证整体阻燃性能的均匀性和稳定性。Step six is the preparation process of auxiliary materials, still using terephthalic acid and ethylene glycol as carriers, adding tetrabromoterephthalic acid, bis(2-ethylhexyl)terephthalic acid, and 4-bromophthalic anhydride; The addition of tetrabromoterephthalic acid and 4-bromophthalic anhydride mainly introduces bromine substituents into the continuous segment, ensuring its overall flame retardancy. The addition makes the polymerization positions of tetrabromoterephthalic acid and 4-bromophthalic anhydride not too close, and introduces side chain groups under the conditions of intermolecular interaction to ensure the uniformity and stability of the overall flame retardant performance.
之后将步骤六中的辅料缓慢加入到主料中混合，很合后进行加压发生聚合反应，得到物性均匀的聚酯。Afterwards, slowly add the auxiliary materials in step 6 into the main material for mixing, and then pressurize and polymerize to obtain a polyester with uniform physical properties.
经过聚合反应后，整个体系已经基本成型，之后加入的溴对苯二甲酸二甲酯、2，2-二氟-1，3-苯并二恶茂、氟硅酸镁、抗菌剂均属于改性剂，溴对苯二甲酸二甲酯能够与反应生成的聚合物进行反应，提高整体的阻燃性能，2，2-二氟-1，3-苯并二恶茂本身能够制品整体的强度，同时其本身结构上与聚对苯二甲酸乙二 醇酯相近，因此具有较好的相容性，能够均匀分布在分子链之间，更进一步加强了整体的阻燃性。氟硅酸镁的加入能够使得提高聚酯的强度，同时也能够起到一个稳定剂的作用，使得聚酯不管在加工还是使用过程中都能体现出一定的稳定性。抗菌剂的加入能够提高其整体的抗菌性能。After the polymerization reaction, the whole system has been basically formed, and the added dimethyl bromoterephthalate, 2,2-difluoro-1,3-benzodioxol, magnesium fluorosilicate, and antibacterial agents are all modified As a neutral agent, dimethyl bromoterephthalate can react with the polymer produced by the reaction to improve the overall flame retardancy, and 2,2-difluoro-1,3-benzodioxol itself can enhance the overall strength of the product , At the same time, its structure is similar to that of polyethylene terephthalate, so it has good compatibility and can be evenly distributed between molecular chains, which further strengthens the overall flame retardancy. The addition of magnesium fluorosilicate can improve the strength of the polyester, and can also act as a stabilizer, so that the polyester can show a certain degree of stability whether it is processed or used. The addition of antibacterial agent can improve its overall antibacterial performance.
在催化剂加入过程中，将其稀释，能够防止局部浓度过大而导致局部团聚的现象。During the addition of the catalyst, diluting it can prevent local agglomeration caused by excessive local concentration.
在反应前加入的2，6-二叔丁基-4-甲基苯酚是一种通用的抗氧剂，与乙二醇一同加入容器，一方面对反应容器有一个清洁作用，另一方面也能够防止聚酯在反应过程中被氧化。The 2,6-di-tert-butyl-4-methylphenol added before the reaction is a general-purpose antioxidant, which is added to the container together with ethylene glycol. On the one hand, it has a cleaning effect on the reaction container, and on the other hand, it also It can prevent the polyester from being oxidized during the reaction.
在抗菌剂上，选用季铵盐型抗菌剂，其季铵盐符合在纳米二氧化硅上。On the antibacterial agent, select the quaternary ammonium salt type antibacterial agent, and its quaternary ammonium salt conforms to the nano silicon dioxide.
抗菌剂的制备过程中，纳米二氧化硅能够在氯苯甲酰氯、4-溴丁酰氯、三氯化磷的条件下进一步被活化，特别是三氯化磷的加入，能够提高纳米二氧化硅的活化性能，同时使得最终得到的抗菌剂具有更好地耐候性，即在长时间使用过程中也能够起到较好的抗菌效果。During the preparation of antibacterial agents, nano-silica can be further activated under the conditions of chlorobenzoyl chloride, 4-bromobutyryl chloride, and phosphorus trichloride, especially the addition of phosphorus trichloride can improve the performance of nano-silica. Activation performance, while making the final antibacterial agent have better weather resistance, that is, it can also play a better antibacterial effect during long-term use.
之后对其进行清洗，三氯甲烷对氯苯甲酰氯、三氯化磷的溶解性较好，能够将其取出，而乙二醇则能够取出残留的三氯甲烷，最终用丙酮清洗，能够彻底取出残留物质。Afterwards, it is cleaned, and trichloromethane has good solubility to chlorobenzoyl chloride and phosphorus trichloride, and it can be taken out, while ethylene glycol can take out residual trichloromethane, and finally, it can be cleaned thoroughly with acetone. Remove residual material.
将活性纳米二氧化硅与聚乙烯亚胺、二(三甲基硅基)碳酰二亚胺、聚碳化二亚胺反应，将聚乙烯亚胺、二(三甲基硅基)碳酰二亚胺、聚碳化二亚胺上的基团固定在纳米二氧化硅上。最后加入1，2-二溴乙烷、溴己烷、溴乙酰溴、1-溴-3-甲基丁烷与固定在活性纳米二氧化硅的基团发生反应，得到季铵盐抗菌剂，而季铵盐抗菌剂已经被固定在了纳米二氧化硅的载体上。这样的抗菌剂不易发生流失，在纳米二氧化硅的载体上使得抗菌效果更佳稳定。其中反应主要在聚乙烯亚胺、二(三甲基硅基)碳酰二亚胺、 聚碳化二亚胺和1，2-二溴乙烷、溴己烷、溴乙酰溴、1-溴-3-甲基丁烷之间发生反应，反应生成的季铵盐具有强稳定性，特别是二(三甲基硅基)碳酰二亚胺的加入，能够使得与二氧化硅的结合力更好，不易从纳米二氧化硅上脱落，同时溴乙酰溴的加入也提高了抗菌剂的活性。Reaction of active nano-silica with polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide, polyethyleneimine, bis(trimethylsilyl) carbonyl diimide Groups on imine and polycarbodiimide are fixed on nano silicon dioxide. Finally, 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo-3-methylbutane are added to react with groups fixed on active nano silicon dioxide to obtain quaternary ammonium salt antibacterial agent, And the quaternary ammonium antibacterial agent has been immobilized on the carrier of nano silicon dioxide. Such an antibacterial agent is not easy to be lost, and the antibacterial effect is better and more stable on the carrier of nano silicon dioxide. The reaction is mainly in polyethyleneimine, bis(trimethylsilyl) carbodiimide, polycarbodiimide and 1,2-dibromoethane, bromohexane, bromoacetyl bromide, 1-bromo- There is a reaction between 3-methylbutane, and the quaternary ammonium salt generated by the reaction has strong stability, especially the addition of bis(trimethylsilyl)carbodiimide, which can make the binding force with silicon dioxide stronger Well, it is not easy to fall off from the nano-silica, and the addition of bromoacetyl bromide also improves the activity of the antibacterial agent.
因此，本发明制备的热塑性聚酯材料，具有较好的阻燃性、抗菌性、高强度的同时，及时在长时间使用过后，仍然具有较好的阻燃性、抗菌性、高强度。以上所述仅是本发明的优选实施方式，本发明的保护范围并不仅局限于上述实施例，凡属于本发明思路下的技术方案均属于本发明的保护范围。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理前提下的若干改进和润饰，这些改进和润饰也应视为本发明的保护范围。Therefore, the thermoplastic polyester material prepared by the present invention has good flame retardancy, antibacterial property and high strength, and at the same time, it still has good flame retardancy, antibacterial property and high strength even after long-term use. The above descriptions are only preferred implementations of the present invention, and the protection scope of the present invention is not limited to the above-mentioned embodiments, and all technical solutions under the idea of the present invention belong to the protection scope of the present invention. It should be pointed out that for those skilled in the art, some improvements and modifications without departing from the principles of the present invention should also be regarded as the protection scope of the present invention.

Claims (7)

  1. 一种用于薄膜的热塑性聚酯，其特征在于：包括下列质量份组成：A kind of thermoplastic polyester for film is characterized in that: comprise following composition by mass parts:
    对苯二甲酸：1000份；Terephthalic acid: 1000 parts;
    乙二醇：600份；Ethylene glycol: 600 parts;
    顺丁烯二酐：50份；Maleic anhydride: 50 parts;
    2-硝基对苯二酸-4-甲酯：10份；2-nitroterephthalic acid-4-methyl ester: 10 parts;
    2，2-二甲基-1，3-丙二醇：10份；2,2-Dimethyl-1,3-propanediol: 10 parts;
    2，3-二溴-2-丁烯-1，4-二醇：5份；2,3-dibromo-2-butene-1,4-diol: 5 parts;
    1，4-苯二甲醇：8份；1,4-Benzene dimethanol: 8 parts;
    2-氨基对苯二甲酸：15份；2-aminoterephthalic acid: 15 parts;
    四溴对苯二酸：5份；Tetrabromoterephthalic acid: 5 parts;
    双(2-乙基己基)对苯二酸：8份；Bis(2-ethylhexyl)terephthalic acid: 8 parts;
    4-溴代苯酐：5份；4-bromophthalic anhydride: 5 parts;
    2，2-二氟-1，3-苯并二恶茂：3份；2,2-difluoro-1,3-benzodioxol: 3 parts;
    氟硅酸镁：5份；Magnesium fluorosilicate: 5 parts;
    抗菌剂5份。5 parts of antibacterial agent.
  2. 如权利要求1所述的一种用于薄膜的热塑性聚酯的制备方法，其特征在于：包括：A kind of preparation method for the thermoplastic polyester of film as claimed in claim 1, it is characterized in that: comprising:
    步骤一：将对苯二甲酸400份、乙二醇400份加入到反应釜中，升温至40℃进行预备混合；Step 1: Add 400 parts of terephthalic acid and 400 parts of ethylene glycol into the reaction kettle, and heat up to 40°C for preliminary mixing;
    步骤二：升温至200～220摄氏度进行酯化反应，反应30～50分钟后，加入Ti/Si系催化剂0.01～0.5份，继续反应10～30分钟；Step 2: Elevate the temperature to 200-220 degrees Celsius to carry out the esterification reaction. After reacting for 30-50 minutes, add 0.01-0.5 parts of Ti/Si catalyst and continue the reaction for 10-30 minutes;
    步骤三：加入对苯二甲酸200份，顺丁烯二酐50份、2-硝基对苯二酸-4-甲酯10份，降温至180～200℃，反应20～40分钟；Step 3: Add 200 parts of terephthalic acid, 50 parts of maleic anhydride, 10 parts of 2-nitroterephthalic acid-4-methyl ester, cool down to 180-200°C, and react for 20-40 minutes;
    步骤四：加入对苯二甲酸100份、2，2-二甲基-1，3-丙二醇10份、2，3-二溴-2-丁烯-1，4-二醇5份，温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应20～30分钟；Step 4: Add 100 parts of terephthalic acid, 10 parts of 2,2-dimethyl-1,3-propanediol, 5 parts of 2,3-dibromo-2-butene-1,4-diol, and keep the temperature At 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst and react for 20-30 minutes;
    步骤五：加入对苯二甲酸200份、乙二醇100份、1，4-苯二甲醇8份、2-氨基对苯二甲酸15份，升温至200～250℃，反应10～30分钟，得到主料备用；Step 5: Add 200 parts of terephthalic acid, 100 parts of ethylene glycol, 8 parts of 1,4-benzenedimethanol, and 15 parts of 2-aminoterephthalic acid, heat up to 200-250°C, and react for 10-30 minutes. Get the main material for use;
    步骤六：辅料的制备，另起一反应釜，加入苯二甲酸100份、乙二醇100份、四溴对苯二酸5份、双(2-乙基己基)对苯二酸8份、4-溴代苯酐5份；温度保持在180～200℃，加入Ti/Si系催化剂0.01～0.5份，反应30～60分钟得到辅料备用；Step 6: preparation of auxiliary materials, set up another reaction kettle, add 100 parts of phthalic acid, 100 parts of ethylene glycol, 5 parts of tetrabromoterephthalic acid, 8 parts of bis(2-ethylhexyl) terephthalic acid, 5 parts of 4-bromophthalic anhydride; keep the temperature at 180-200°C, add 0.01-0.5 parts of Ti/Si catalyst, and react for 30-60 minutes to obtain auxiliary materials for later use;
    步骤七：将辅料缓慢加入到主料的反应釜中，加入的同时进行搅拌，温度保持在40～50摄氏度，加入完毕后缓慢升温至180～200℃，保温搅拌20～40分钟；Step 7: Slowly add the auxiliary materials into the reaction kettle of the main materials, stir while adding, keep the temperature at 40-50 degrees Celsius, slowly raise the temperature to 180-200 degrees Celsius after the addition, keep stirring for 20-40 minutes;
    步骤八，升温至250～280℃，200～300Pa真空条件下反应30～60分钟；Step 8, heating up to 250-280°C, and reacting for 30-60 minutes under vacuum conditions of 200-300Pa;
    步骤九：完成反应后加入邻溴对苯二甲酸二甲酯10份、2，2-二氟-1，3-苯并二恶茂3份、氟硅酸镁5份、抗菌剂5份，温度控制在100～120℃，进行搅拌30～40分钟后，继续搅拌，自然降温至50～60℃后进行造粒得到塑料粒子；Step 9: After completing the reaction, add 10 parts of dimethyl o-bromoterephthalate, 3 parts of 2,2-difluoro-1,3-benzodioxol, 5 parts of magnesium fluorosilicate, and 5 parts of antibacterial agent, The temperature is controlled at 100-120°C, after stirring for 30-40 minutes, continue to stir, naturally cool down to 50-60°C, and then granulate to obtain plastic particles;
    步骤十：将塑料粒子进行制膜。Step 10: Make plastic particles into a film.
  3. 根据权利要求2所述的一种用于薄膜的热塑性聚酯的制备方法，其特征在于：所述步骤十中塑料粒子通过流延机制造成薄膜。A method for preparing thermoplastic polyester for film according to claim 2, characterized in that: in step ten, the plastic particles are formed into a film by a casting machine.
  4. 根据权利要求2所述的一种用于薄膜的热塑性聚酯的制备方法，其特征在于：所述抗菌剂根据下述方法制备：A kind of preparation method for the thermoplastic polyester of film according to claim 2, is characterized in that: described antibacterial agent is prepared according to following method:
    步骤A：10g纳米二氧化硅中，加入2ml的对氯苯甲酰氯、1ml的4-溴丁酰氯、1ml三氯化磷，20～30℃条件下搅拌反应10～15小时，对纳米二氧化硅进行活性化；Step A: Add 2ml of p-chlorobenzoyl chloride, 1ml of 4-bromobutyryl chloride, and 1ml of phosphorus trichloride to 10g of nano-silica, stir and react at 20-30°C for 10-15 hours, Silicon for activation;
    步骤B：反应完成后对混合物进行离心，依次使用三氯甲烷、乙二醇、丙酮进行清洗，进行干燥，得到活化纳米二氧化硅；Step B: After the reaction is completed, the mixture is centrifuged, washed with chloroform, ethylene glycol, and acetone in sequence, and dried to obtain activated nano-silica;
    步骤C：在活化纳米二氧化硅中加入7g聚乙烯亚胺、2g二(三 甲基硅基)碳酰二亚胺、1g聚碳化二亚胺，加入0.1gKOH，在85℃的条件下搅拌15～20小时；Step C: Add 7g of polyethyleneimine, 2g of bis(trimethylsilyl)carbodiimide, 1g of polycarbodiimide to activated nano-silica, add 0.1g of KOH, and stir at 85°C 15-20 hours;
    步骤D：反应结束后经过离心，并用甲醇进行充分洗涤，进行干燥；Step D: Centrifuge after the reaction, fully wash with methanol, and dry;
    步骤E：将风干后的纳米二氧化硅粉末装入到20ml的异丁醇中，之后加入2ml的1，2-二溴乙烷、6ml的溴己烷、0.1g溴乙酰溴、1ml的1-溴-3-甲基丁烷，再70～80℃条件下搅拌15～25小时；Step E: Put the air-dried nano silicon dioxide powder into 20ml of isobutanol, then add 2ml of 1,2-dibromoethane, 6ml of bromohexane, 0.1g of bromoacetyl bromide, 1ml of 1 -Bromo-3-methylbutane, then stirred at 70-80°C for 15-25 hours;
    步骤F：反应完成后降温到30～45℃，再向其中加入5ml碘化钾，搅拌8～12小时，经过离心，用甲醇充分洗涤，然后干燥得到抗菌剂。Step F: After the reaction is completed, cool down to 30-45° C., add 5 ml of potassium iodide therein, stir for 8-12 hours, centrifuge, fully wash with methanol, and then dry to obtain an antibacterial agent.
  5. 根据权利要求2或3或4所述的一种用于薄膜的热塑性聚酯的制备方法，其特征在于：A kind of preparation method for the thermoplastic polyester of film according to claim 2 or 3 or 4, it is characterized in that:
    所述步骤五中，先加入对苯二甲酸50份、之后加入乙二醇100份，剩余的150份对苯二甲酸分成三份，每隔10分钟加入50份对苯二甲酸，最后加入2，2-二甲基-1，3-丙二醇10份。In the step five, first add 50 parts of terephthalic acid, then add 100 parts of ethylene glycol, and divide the remaining 150 parts of terephthalic acid into three parts, add 50 parts of terephthalic acid every 10 minutes, and finally add 2 , 10 parts of 2-dimethyl-1,3-propanediol.
  6. 根据权利要求5所述的一种用于薄膜的热塑性聚酯的制备方法，其特征在于：所述步骤一中，在加入原料前，先在反应容器中加入2，6-二叔丁基-4-甲基苯酚，加入200份乙二醇，搅拌5～15分钟，再加入剩余的600份乙二醇和400份对苯二甲酸，升温至40℃进行预备混合。A kind of preparation method for the thermoplastic polyester that is used for film according to claim 5, it is characterized in that: in described step 1, before adding raw material, add 2,6-di-tert-butyl- For 4-methylphenol, add 200 parts of ethylene glycol, stir for 5-15 minutes, then add the remaining 600 parts of ethylene glycol and 400 parts of terephthalic acid, and heat up to 40°C for preliminary mixing.
  7. 根据权利要求5所述的一种用于薄膜的热塑性聚酯的制备方法，其特征在于：所述步骤二、步骤四、步骤六中加入Ti/Si系催化剂时，先将Ti/Si系催化剂用50ml乙二醇稀释，在加入到反应容器中。A kind of preparation method for the thermoplastic polyester of film according to claim 5, it is characterized in that: when adding Ti/Si series catalyst in described step 2, step 4, step 6, first Ti/Si series catalyst Dilute with 50ml of ethylene glycol and add to the reaction vessel.
PCT/CN2021/120055 2021-09-24 2021-09-24 Thermoplastic polyester used for thin film, and preparation method therefor WO2023044692A1 (en)

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US4264745A (en) * 1979-09-14 1981-04-28 Owens-Corning Fiberglas Corporation Fire-retardant polyurethane foam based on a bromine-containing polyester
US20060160986A1 (en) * 2005-01-18 2006-07-20 Hazen Benjamin R Low viscosity unsaturated polyester resin with reduced VOC emission levels
CN102634174A (en) * 2012-03-31 2012-08-15 四川东方绝缘材料股份有限公司 Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine
CN102660010A (en) * 2012-04-05 2012-09-12 四川东材绝缘技术有限公司 Preparation method of reactive polyester flame-retardant additive
CN105175701A (en) * 2015-09-09 2015-12-23 济南大学 Preparation method and application of PET-based multi-component synergetic polyol
CN105860043A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for antibacterial film and preparation method of thermoplastic polyester
CN105860044A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for films and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4264745A (en) * 1979-09-14 1981-04-28 Owens-Corning Fiberglas Corporation Fire-retardant polyurethane foam based on a bromine-containing polyester
US20060160986A1 (en) * 2005-01-18 2006-07-20 Hazen Benjamin R Low viscosity unsaturated polyester resin with reduced VOC emission levels
CN102634174A (en) * 2012-03-31 2012-08-15 四川东方绝缘材料股份有限公司 Preparation method of flame-retardant copolyester film of phosphorus, silicon and fluorine
CN102660010A (en) * 2012-04-05 2012-09-12 四川东材绝缘技术有限公司 Preparation method of reactive polyester flame-retardant additive
CN105175701A (en) * 2015-09-09 2015-12-23 济南大学 Preparation method and application of PET-based multi-component synergetic polyol
CN105860043A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for antibacterial film and preparation method of thermoplastic polyester
CN105860044A (en) * 2016-06-17 2016-08-17 苍南县宝丰印业有限公司 Thermoplastic polyester for films and preparation method thereof

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