WO2022068621A1 - 一种无卤阻燃增强pet复合材料及其制备方法 - Google Patents

一种无卤阻燃增强pet复合材料及其制备方法 Download PDF

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WO2022068621A1
WO2022068621A1 PCT/CN2021/119219 CN2021119219W WO2022068621A1 WO 2022068621 A1 WO2022068621 A1 WO 2022068621A1 CN 2021119219 W CN2021119219 W CN 2021119219W WO 2022068621 A1 WO2022068621 A1 WO 2022068621A1
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modified
flame retardant
halogen
parts
free flame
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PCT/CN2021/119219
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English (en)
French (fr)
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陈婷
张青海
吕明旭
林鸿裕
汪扬涛
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黎明职业大学
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    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/22—Halogen free composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to the technical field of polymer materials, in particular to a halogen-free flame-retardant reinforced PET composite material and a preparation method thereof.
  • PET Polyethylene terephthalate
  • PET as an automotive device material has good application prospects, but its flame retardancy, strength, and toughness needs to be solved.
  • the purpose of the present invention is to provide a halogen-free flame retardant reinforced PET composite material and a preparation method thereof, so as to obtain a PET composite material with good flame retardancy, improved rigidity and enhanced toughness, and the PET composite material has better comprehensive performance and wider application range. wide.
  • the solution of the present invention is: a halogen-free flame retardant reinforced PET composite material, comprising the following raw materials by weight: PET, 70-80 parts; toughening agent, 20-30 parts; modified halogen-free Flame retardant, 15 ⁇ 20 parts; Modified flame retardant synergist, 3 ⁇ 8 parts; Modified carbon fiber, 5 ⁇ 10 parts; Antioxidant, 0.1 ⁇ 0.5 parts; Lubricant, 0.2 ⁇ 1 part; Anti-hydrolysis agent, 0.1 to 0.5 servings.
  • the modified halogen-free flame retardant is a compound of melamine phosphate and an organic carbon source, and the modified flame retardant synergist is PGMA (polyglycidyl methacrylate) graft-modified montmorillonite , the modified carbon fiber is an oxidized carbon fiber.
  • PGMA polyglycidyl methacrylate
  • the toughening agent is ethylene-octene grafted glycidyl methacrylate copolymer (POE-g-GMA), polyethylene grafted glycidyl methacrylate copolymer (PE-g-GMA), styrene At least one of grafted glycidyl methacrylate copolymer (SGMA) and ethylene octene grafted maleic anhydride copolymer (POE-g-MAH).
  • POE-g-GMA ethylene-octene grafted glycidyl methacrylate copolymer
  • PE-g-GMA polyethylene grafted glycidyl methacrylate copolymer
  • SGMA grafted glycidyl methacrylate copolymer
  • POE-g-MAH ethylene octene grafted maleic anhydride copolymer
  • melamine phosphate and an organic carbon source are compounded in a mass ratio of 2:3 to 3:4, and the organic carbon source is at least one of pentaerythritol, ethylene glycol and phenolic resin .
  • the antioxidants are tetrakis[beta-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid]pentaerythritol ester (antioxidant 1010), tris(nonylphenyl) phosphite, tris(nonylphenyl) phosphite, At least one of [2,4-di-tert-butylphenyl]phosphite (Antioxidant 168) and 2,5-di-tert-butylhydroquinone.
  • the lubricant is at least one of natural paraffin, pentaerythritol stearate (PETS), polyethylene wax, liquid paraffin and microcrystalline stone.
  • the anti-hydrolysis agent is at least one of carbon black, N , N' -bis(2,6-diisopropylphenyl)carbodiimide and polycarbodiimide.
  • a preparation method of halogen-free flame retardant reinforced PET composite material comprising the following steps: step 1, firstly preparing the modified halogen-free flame retardant; step 2, then preparing the modified flame retardant synergist; step 3 , and then prepare the modified carbon fiber; step 4, according to the formula ratio, then combine PET, toughening agent, modified carbon fiber, modified halogen-free flame retardant, modified flame retardant synergist, antioxidant, lubricant Place the anti-hydrolysis agent in a high-speed mixer and mix evenly to obtain a mixed material; step 5, then add the mixed material into a torque rheometer for melting, the melting temperature is 260 ⁇ 265 °C, and the rotor speed is 50 ⁇ 60 r/min, the melting time is 10 ⁇ 15min; in step 6, finally, the molten mixture is hot-pressed, the hot-pressing temperature is 260 ⁇ 265°C, and the melting time is 5 ⁇ 7 min, the hot pressing time is 10 ⁇ 15 min, and the holding time is 10 ⁇ 15 min min
  • step 1 the preparation method of the modified halogen-free flame retardant is as follows: (1) Synthesis of melamine phosphate: weigh 25-35 parts of phenethyl phosphoric acid, add to 200-300 parts Parts of deionized water, heated to 95 ⁇ 100°C, then added 18 ⁇ 25 parts of melamine, kept for 1.5 ⁇ 2 h under magnetic stirring, and then cooled, filtered and dried to obtain the melamine phosphate; (2) described Compounding of modified halogen-free flame retardants: According to the mass ratio of 2:3 ⁇ 3:4, the prepared melamine phosphate (MP) is compounded with the organic carbon source.
  • MP prepared melamine phosphate
  • step 2 the preparation method of the modified flame retardant synergist is: (1) Treatment of montmorillonite: put 15-25 parts of montmorillonite in 400-500 parts of deionized water, and ultrasonically vibrate 1-1.5 parts of montmorillonite; h to expand the interlayer spacing of montmorillonite, after repeated washing and filtration with deionized water, drying in a 90-100 °C oven for 10-12 h to obtain the montmorillonite for use; (2) PGMA grafting Preparation of modified montmorillonite: 5 ⁇ 10g of montmorillonite obtained in step (1) was added to 200 ⁇ 300 parts of deionized water, mechanically stirred at 30 ⁇ 40 rpm for 10 ⁇ 12 h, and then added to the reaction system Bubble N 2 in the middle to form a N 2 atmosphere, continue stirring for 1 ⁇ 2h, add 8 ⁇ 15 parts of glycidyl methacrylate monomer and 5 ⁇ 10 parts of quaternary ammonium salt emulsifier to the reaction system,
  • the reaction was carried out for 40-50 min. After the reaction, the reaction solution was cooled to room temperature, transferred to a centrifuge tube and centrifuged for 1-1.5 h. The centrifuged precipitate was dissolved in tetrahydrofuran, and then centrifuged for 40-50 min. Repeat this for 3 times. , in order to remove the residual glycidyl methacrylate monomer, quaternary ammonium salt emulsifier and PGMA not grafted on the surface of montmorillonite. After drying at ⁇ 100°C for 10 ⁇ 12 h, the PGMA graft-modified montmorillonite was obtained, which was used as the modified flame retardant synergist for later use.
  • the quaternary ammonium salt emulsifier is double dodecyl dimethyl- ⁇ -diquaternary ammonium salt, octadecyl trimethyl ammonium chloride (quaternary ammonium salt 1831), dodecyl dimethyl benzyl At least one of ammonium chloride (quaternary ammonium salt 1227) and octadecyldimethylbenzyl ammonium chloride (quaternary ammonium salt 1827), and the initiator is at least one of potassium persulfate and ammonium persulfate A sort of.
  • the preparation method of the modified carbon fiber includes the following steps: (1) Pretreatment of the carbon fiber: soak the carbon fiber in a solvent of 35-40° C. for 20-24 h, washed repeatedly with deionized water for several times, and dried at 70 ⁇ 80 °C for 4 ⁇ 5 h to obtain pretreated carbon fibers; (2) Oxidation treatment of carbon fibers: the pretreated carbon fibers were heated at 80 ⁇ 110 °C The reaction is carried out in a strong oxidant for 2-5 hours, and after the reaction is completed, the oxidized carbon fibers on the surface are washed with deionized water to a pH value of 6-7, and dried at 70-80° C.
  • Described strong oxidant is one or more in concentrated sulfuric acid, concentrated nitric acid, hypochlorous acid and potassium permanganate mixed with any mixing ratio, and described solvent is one or more in acetone, toluene and xylene. The species are mixed in any mixing ratio.
  • a halogen-free flame retardant reinforced PET composite material of the present invention has the following beneficial effects: firstly, by adding a compound of melamine phosphate (MP) and an organic carbon source as a modified halogen-free flame retardant , adding PGMA graft-modified montmorillonite as a modified flame retardant synergist.
  • MP melamine phosphate
  • organic carbon source an organic carbon source
  • PGMA graft-modified montmorillonite as a modified flame retardant synergist.
  • MP acts as an acid source and a gas source in the flame retardant system to dehydrate and carbonize the PET polymer during combustion and finally cover the polymer surface, thereby hindering the contact of oxygen and heat with the internal polymer; through MP and organic carbon source
  • the compounding can effectively improve the problem of high hygroscopicity of MP; adding the modified montmorillonite graft as a modified flame retardant synergist can promote the formation of a more stable and dense carbon layer when the system is burned, and improve the composite material. flame retardant and flame retardant and smoke suppression properties.
  • the selected compound flame retardant contains phenethyl group
  • the PET molecular chain also contains phenethyl group, which can improve the compatibility between the flame retardant and the PET molecular chain.
  • the flame retardant synergist contains GMA functional group. It can react with terminal carboxyl groups and terminal hydrocarbon groups on PET, and also solves the problem of poor compatibility between flame retardant synergists and PBT, and improves the interaction force between PET substrate and flame retardant, thereby improving the resistance of the material. While improving the flammability, it also improves the compatibility of the flame retardant and the material. In addition, due to the good interfacial force between the flame retardant and the polymer, the composite material still maintains good mechanical properties.
  • the mechanical properties of the PET composite material are further improved, and at the same time, the wick effect is prevented when the PET composite material is used as a flame retardant.
  • the halogen-free flame retardant reinforced PET composite material obtained by the present invention not only has good flame retardant performance, but also has strong strength and toughness. domain usage requirements.
  • the present invention provides a method for preparing a halogen-free flame retardant reinforced PET composite material, which is simple and convenient, easy to implement, and has important practical application value.
  • the molecular chain of the toughening agent used in the present invention contains functional groups that can react with PET.
  • the toughening agent is a grafted glycidyl methacrylate copolymer
  • the epoxy group in the toughening agent can react with PET.
  • the terminal carboxyl groups and terminal hydrocarbon groups on the PET react;
  • the toughening agent is a grafted maleic anhydride copolymer
  • the maleic anhydride groups in the toughening agent can react with the hydrocarbon groups on the PET. Therefore, the selected toughening agent can not only play a toughening role, but also improve the problem of insufficient compatibility between the toughening agent and PET, so as to maximize the toughening effect.
  • Example 1 a halogen-free flame retardant reinforced PET composite material, comprising the following raw materials by weight: PET, 80 parts; POE-g-GMA, 20 parts; modified halogen-free flame retardant, 17 parts; Combustion synergist, 4 parts; modified carbon fiber, 5 parts; antioxidant 1010, 0.2 part; polyethylene wax, 0.2 part; polycarbodiimide, 0.1 part.
  • the modified halogen-free flame retardant is a compound of melamine phosphate and pentaerythritol
  • the modified flame retardant synergist is PGMA graft-modified montmorillonite
  • the modified carbon fiber is oxidized carbon fiber.
  • the preparation method of the halogen-free flame retardant reinforced PET composite material includes the following steps: Step 1.
  • reaction solution After the reaction is over, cool the reaction solution to room temperature, transfer it to a centrifuge tube and centrifuge for 1 hour, dissolve the centrifuged precipitate in tetrahydrofuran, and then centrifuge for 40 min. Repeat this 3 times to remove residual methacrylic acid.
  • the oxidized carbon fibers on the surface are washed with deionized water to pH 6-7, and dried at 70 °C for 5 h to obtain modified carbon fibers; step 4, according to the formula ratio, and then Vacuum-dried PET, POE-g-GMA, modified carbon fiber, modified halogen-free flame retardant, modified flame retardant synergist and antioxidant 1010, lubricant polyethylene wax and anti-hydrolysis agent polycarbodioxide
  • the amine is placed in a high-speed mixer and mixed uniformly to obtain a mixture; step 5, then the mixture is added to a torque rheometer for melting, the melting temperature is 260 ° C, and the rotor speed is 5 0 r/min, the melting time is 10 min; in step 6, finally, the molten mixture is hot-pressed, the hot-pressing temperature is 265 °C, the melting time is 5 min, the hot-pressing time is 10 min, and the heat preservation is carried out. The time was 15 min, and the
  • Embodiment 2 a halogen-free flame retardant reinforced PET composite material, comprising the following raw materials by weight: PET, 70 parts; PE-g-GMA, 30 parts; modified halogen-free flame retardant, 15 parts; Combustion synergist, 3 parts; modified carbon fiber, 6 parts; antioxidant 168, 0.2 parts; liquid paraffin, 0.3 parts; polycarbodiimide, 0.3 parts.
  • the modified halogen-free flame retardant is a compound of melamine phosphate and ethylene glycol
  • the modified flame retardant synergist is PGMA (polyglycidyl methacrylate) graft-modified montmorillonite.
  • Carbon fiber is oxidized carbon fiber.
  • the preparation method of the halogen-free flame retardant reinforced PET composite material includes the following steps: Step 1. Prepare a modified halogen-free flame retardant: (1) Synthesis of melamine phosphate: weigh 28 parts of phenethyl phosphoric acid and place it in 500 mL 250 parts of deionized water was added to the round-bottomed flask, the temperature was raised to 95°C, 18 parts of melamine were added, and the temperature was kept under magnetic stirring for 1.5 h, and then cooled, filtered, and dried to obtain melamine phosphate; (2) Modification Compounding of halogen-free flame retardant: according to the mass ratio of 2:3, the prepared melamine phosphate (MP) is compounded with ethylene glycol; step 2, then prepare the modified flame retardant synergist: (1) Treatment of montmorillonite: 18 parts of montmorillonite were placed in 400 parts of deionized water, ultrasonically vibrated for 1.5 h to expand the interlayer spacing of montmorillonite, washe
  • modified carbon fibers (1) Pretreatment of carbon fibers: soak the carbon fibers in toluene at 40 °C for 24 h , and then repeatedly washed with deionized water for several times, and dried at 70 °C for 5 h to obtain pretreated carbon fibers; (2) Oxidation treatment of carbon fibers: the pretreated carbon fibers were reacted in concentrated nitric acid at 100 °C for 4 h, The amount of concentrated nitric acid is suitable to completely submerge the carbon fibers.
  • Step 4 According to the formula ratio, then vacuum-dried PET, PE-g-GMA, modified carbon fiber, modified halogen-free flame retardant, modified flame retardant synergist and antioxidant 168, lubricant liquid paraffin and The anti-hydrolysis agent polycarbodiimide is placed in a high-speed mixer and mixed uniformly to obtain a mixture; step 5, then the mixture is added to a torque rheometer for melting, and the melting temperature is 260 ° C , the rotor speed is 55 r/min, the melting time is 10 min; step 6, finally, the molten mixture is hot-pressed, the hot-pressing temperature is 260 °C, the melting time is 7 min, and the hot-pressing time is 15 min, the heat preservation time is 10 min, and the halogen-free flame retardant reinforced
  • Embodiment 3 a halogen-free flame retardant reinforced PET composite material, comprising the following raw materials by weight: PET, 75 parts; SGMA, 25 parts; modified halogen-free flame retardant, 20 parts; modified flame retardant synergist , 8 parts; modified carbon fiber, 10 parts; tris(nonylphenyl) phosphite, 0.5 parts; PET, 0.8 parts; N , N '-bis(2,6-diisopropylphenyl) carbon two Imine, 0.5 part.
  • the modified halogen-free flame retardant is a compound of melamine phosphate and pentaerythritol
  • the modified flame retardant synergist is PGMA (polyglycidyl methacrylate) graft-modified montmorillonite
  • modified carbon fiber Oxidized carbon fiber is a compound of melamine phosphate and pentaerythritol
  • the preparation method of the halogen-free flame retardant reinforced PET composite material includes the following steps: Step 1. Preparation of modified halogen-free flame retardant: (1) Synthesis of melamine phosphate: Weigh 33 parts of phenethyl phosphoric acid and place it in 500 mL Add 300 parts of deionized water to the round-bottomed flask, raise the temperature to 100°C, add 23 parts of melamine, keep the temperature under magnetic stirring for 1.5h, then cool, filter, and dry to obtain melamine phosphate; (2) Modification Compounding of halogen-free flame retardants: according to the mass ratio of 3:4, the prepared melamine phosphate (MP) is compounded with pentaerythritol; step 2, then prepare the modified flame retardant synergist: (1) montmorillonite Soil treatment: put 15 parts of montmorillonite in 400 parts of deionized water, ultrasonically vibrate for 1.5 hours to expand the interlayer spacing of montmorillonite, and after repeated washing and
  • the reaction was continued for 40 min. After the reaction was completed, the reaction solution was cooled to room temperature, and then transferred to a centrifuge tube for centrifugation for 1 h. The centrifugal precipitate was dissolved in tetrahydrofuran, and then centrifuged for 40 min. This was repeated 3 times to remove the remaining residues. Glycidyl methacrylate monomer, quaternary ammonium salt 1827 and PGMA ungrafted on the surface of montmorillonite. Finally, the centrifugal precipitate was washed 5 times with absolute ethanol, and dried at 100 °C for 12 h to obtain PGMA grafting.
  • the branch-modified montmorillonite is used as a modified flame retardant synergist for use; Step 3, then prepare modified carbon fibers: (1) Pretreatment of carbon fibers: soak the carbon fibers in acetone at 35 °C for 20 h, and then use Ionized water was repeatedly washed for several times and dried at 80 °C for 4 hours to obtain pretreated carbon fibers; (2) Oxidation treatment of carbon fibers: the pretreated carbon fibers were reacted in concentrated sulfuric acid at 90 °C for 3 hours, and the amount of concentrated sulfuric acid was It is advisable to completely submerge the carbon fibers.
  • the melted mixture was hot-pressed, and the hot-pressing temperature was 263 °C.
  • the melting time is 7 min
  • the hot pressing time is 12 min
  • the heat preservation time is 12 min to obtain a halogen-free flame retardant reinforced PET composite material.
  • Embodiment 4 a halogen-free flame retardant reinforced PET composite material, comprising the following raw materials by weight: PET, 75 parts; POE-g-MAH, 25 parts; modified halogen-free flame retardant, 15 parts; Combustion synergist, 5 parts; modified carbon fiber, 8 parts; antioxidant 168, 0.3 parts; polyethylene wax, 0.5 parts; polycarbodiimide, 0.3 parts.
  • the modified halogen-free flame retardant is a compound of melamine phosphate and pentaerythritol
  • the modified flame retardant synergist is PGMA (polyglycidyl methacrylate) graft-modified montmorillonite
  • modified carbon fiber Oxidized carbon fiber is a compound of melamine phosphate and pentaerythritol
  • the preparation method of the halogen-free flame retardant reinforced PET composite material includes the following steps: Step 1. Preparation of modified halogen-free flame retardant: (1) Synthesis of melamine phosphate: Weigh 35 parts of phenethyl phosphoric acid and place it in 500 mL Add 300 parts of deionized water to the round-bottomed flask, raise the temperature to 100°C, add 25 parts of melamine, keep the temperature for 1.5h under magnetic stirring, and then cool, filter, and dry to obtain melamine phosphate; (2) Modification Compounding of halogen-free flame retardants: according to the mass ratio of 2:3, the prepared melamine phosphate (MP) is compounded with pentaerythritol; step 2, then prepare the modified flame retardant synergist: (1) montmorillonite Soil treatment: put 25 parts of montmorillonite in 500 parts of deionized water, ultrasonically vibrate for 1 hour to expand the interlayer spacing of montmorillonite, and after repeated washing
  • the modified montmorillonite is used as a modified flame retardant synergist for use; Step 3, then prepare the modified carbon fiber: (1) Pretreatment of carbon fiber: soak the carbon fiber in xylene at 35 °C for 24 h, and then deionize the carbon fiber. (2) Oxidation treatment of carbon fibers: the pretreated carbon fibers were reacted in concentrated nitric acid at 110°C for 5 hours, and the amount of concentrated nitric acid was It is advisable to completely submerge the carbon fibers.
  • the oxidized carbon fibers on the surface are washed with deionized water to a pH value of 6-7, and dried at 70 °C for 5 h to obtain modified carbon fibers; step 4, according to the formula ratio, Then the vacuum-dried PET, POE-g-MAH, modified carbon fiber, modified halogen-free flame retardant, modified flame retardant synergist and antioxidant 168, lubricant polyethylene wax and anti-hydrolysis agent were polymerized
  • the carbodiimide is placed in a high-speed mixer and mixed evenly to obtain a mixture; step 5, then the mixture is added to a torque rheometer for melting, the melting temperature is 265 ° C, and the The sub-speed is 55 r/min, and the melting time is 12 min; step 6, finally, the molten mixture is hot-pressed, the hot-pressing temperature is 265 °C, the melting time is 5 min, and the hot-pressing time is 12 min , the heat preservation time is 12 min, and the halogen
  • Embodiment 5 a halogen-free flame retardant reinforced PET composite material, comprising the following raw materials by weight: PET, 70 parts; SGMA, 30 parts; modified halogen-free flame retardant, 20 parts; modified flame retardant synergist , 8 parts; modified carbon fiber, 8 parts; antioxidant 1010, 0.5 part; PETS, 1 part; N , N '-bis(2,6-diisopropylphenyl)carbodiimide, 0.5 part.
  • the modified halogen-free flame retardant is a compound of melamine phosphate and phenolic resin
  • the modified flame retardant synergist is PGMA (polyglycidyl methacrylate) graft-modified montmorillonite.
  • Carbon fiber is oxidized carbon fiber.
  • the preparation method of the halogen-free flame retardant reinforced PET composite material includes the following steps: Step 1. Preparation of a modified halogen-free flame retardant: (1) Synthesis of melamine phosphate: weigh 30 parts of phenethyl phosphoric acid and place it in 500 mL In the round-bottomed flask, add 300 parts of deionized water, raise the temperature to 95°C, add 20 parts of melamine, keep the temperature for 1.5h under magnetic stirring, then cool, filter, and dry to obtain melamine phosphate; (2) Modification Compounding of halogen-free flame retardants: according to the mass ratio of 3:4, the prepared melamine phosphate (MP) is compounded with phenolic resin; step 2, then prepare the modified flame retardant synergist: (1) Mongolia Treatment of de-soil: put 21 parts of montmorillonite in 500 parts of deionized water, ultrasonically vibrate for 1.5h to expand the interlayer spacing of montmorillonite, repeatedly wash and filter with deion
  • reaction solution was cooled to room temperature, and then transferred to a centrifuge tube for centrifugation for 1 h.
  • the centrifugal precipitate was dissolved in tetrahydrofuran, and then centrifuged for 40 min.
  • step 3 prepare the modified carbon fiber: (1) Pretreatment of carbon fiber: soak the carbon fiber in toluene at 35 ⁇ 40°C for 20 ⁇ 24 h, washed repeatedly with deionized water for several times, and dried at 70 °C for 5 h to obtain pretreated carbon fibers; (2) Oxidation treatment of carbon fibers: the pretreated carbon fibers were immersed in concentrated nitric acid at 80-110 °C The reaction was carried out for 2 ⁇ 5 h, and the amount of concentrated nitric acid was suitable to completely submerge the carbon fibers
  • Step 4 according to the formula ratio, then vacuum-dried PET, SGMA, modified carbon fiber, modified halogen-free flame retardant, modified flame retardant synergist and antioxidant 1010, lubricant PETS and the anti-hydrolysis agent N , N' -bis(2,6-diisopropylphenyl)carbodiimide is placed in a high-speed mixer and mixed uniformly to obtain a mixture; step 5, then the The mixture was added to the torque rheometer for melting, the melting temperature was 265 °C, the rotor speed was 60 r/min, and the melting time was 15 min; step 6, finally, the melted mixture was hot-pressed to form, hot-pressed The temperature is 265 °C, the melting time is 5 min, the hot pressing time is 15 min, and the heat preservation time is
  • common PET composite material including the following raw materials by weight: PET, 70 parts; toughening agent ABS, 30 parts; antioxidant 1010, 0.3 parts; liquid paraffin, 0.5 parts; polycarbodiimide, 0.3 parts .
  • the preparation method of the common PET composite material includes the following steps: Step 1. According to the formula ratio, then vacuum-dried PET, toughening agent ABS and antioxidant 1010, lubricant liquid paraffin and anti-hydrolysis agent polycarbide The imine is placed in a high-speed mixer and mixed evenly to obtain a mixture; step 2, then the mixture is added to a torque rheometer for melting, the melting temperature is 265 ° C, and the rotor speed is 60 r/min, the melting time is 15 min; in step 3, the molten mixture is finally hot-pressed, the hot-pressing temperature is 260 ° C, the melting time is 5 min, the hot-pressing time is 15 min, and the holding time is For 10 min, the ordinary PET composite material of the comparative example was obtained.
  • the halogen-free flame retardant reinforced PET composite materials prepared in Examples 1 to 5 and the common PET composite materials prepared in the comparative example were cut out to obtain dumbbell-shaped tensile samples and long-shaped impact samples.
  • the samples obtained in each example and comparative example were respectively subjected to tensile property test (GB/T1040.2-2006), impact property test (GB/T1043.1-2008), vertical combustion and limiting oxygen index test, and the test results See Table 1.
  • the halogen-free flame retardant reinforced PET composite material prepared by the present invention not only has good flame retardant performance, reaching the UL94V-0 level, but also has strong impact strength and tensile strength.
  • the PET composite material is non-toxic and smoke-free, and meets the requirements of the flame retardant field.

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Abstract

一种无卤阻燃增强PET复合材料，包括如下重量份的原料：70～80份PET、20～30份增韧剂、15～20份改性无卤阻燃剂、3～8份改性阻燃协效剂、5～10份改性碳纤维、0.1～0.5份抗氧剂、0.2～1份润滑剂和0.1～0.5份抗水解剂，改性无卤阻燃剂为三聚氰胺磷酸盐与有机碳源的复配物，改性阻燃协效剂为PGMA接枝改性的蒙脱土，改性碳纤维为经过氧化处理的碳纤维。还公开一种无卤阻燃增强PET复合材料的制备方法，制备方法简单方便，易于实现。

Description

一种无卤阻燃增强PET复合材料及其制备方法 技术领域
本发明涉及高分子材料技术领域，具体涉及的是一种无卤阻燃增强PET复合材料及其制备方法。
 背景技术
聚对苯二甲酸乙二醇酯( PET) 有着其他工程材料不可比拟的诸多优势，如很好的抗腐蚀性、较好的耐疲劳性和较好的力学性能等，因而被广泛应用在汽车器件领域，但PET本身易燃、性脆，而汽车器件对材料的阻燃性能、强度、韧性等提出了很高的要求。
因此，采用PET作为汽车器件材料具有很好的应用前景，但还需解决其阻燃性、强度、韧性不足等问题。
 技术问题
本发明的目的在于提供一种无卤阻燃增强PET复合材料及其制备方法，获得阻燃性好、刚性提高、韧性增强的PET复合材料，该PET复合材料的综合性能更好、应用范围更广。
 技术解决方案
为了达成上述目的，本发明的解决方案是：一种无卤阻燃增强PET复合材料，包括如下重量份的原料：PET，70~80份；增韧剂，20~30份；改性无卤阻燃剂，15~20份；改性阻燃协效剂，3~8份；改性碳纤维，5~10份；抗氧剂，0.1~0.5份；润滑剂，0.2~1份；抗水解剂，0.1~0.5份。
所述改性无卤阻燃剂为三聚氰胺磷酸盐与有机碳源的复配物，所述改性阻燃协效剂为PGMA（聚甲基丙烯酸缩水甘油酯）接枝改性的蒙脱土，所述改性碳纤维为经过氧化处理的碳纤维。
所述增韧剂为乙烯-辛烯接枝甲基丙烯酸缩水甘油酯共聚物（POE-g-GMA）、聚乙烯接枝甲基丙烯酸缩水甘油酯共聚物（PE-g-GMA）、苯乙烯接枝甲基丙烯酸缩水甘油酯共聚物（SGMA）和乙烯辛烯接枝马来酸酐共聚物（POE-g-MAH）中的至少一种。
所述改性无卤阻燃剂中三聚氰胺磷酸盐与有机碳源按质量比2:3~3:4复配而成，所述有机碳源为季戊四醇、乙二醇和酚醛树脂中的至少一种。
所述抗氧剂为四[β-（3,5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯（抗氧剂1010）、三(壬基苯基)亚磷酸酯、三[2,4-二叔丁基苯基]亚磷酸酯（抗氧剂168）和2,5-二特丁基对苯二酚中的至少一种。
所述润滑剂为天然石蜡、季戊四醇硬脂酸酯（PETS）、聚乙烯蜡、液体石蜡和微晶石中的至少一种。
所述抗水解剂为炭黑、 N, N'-二(2,6-二异丙基苯基)碳二亚胺和聚碳化二亚胺中的至少一种。
一种无卤阻燃增强PET复合材料的制备方法，包括以下步骤：步骤1、先制备所述改性无卤阻燃剂；步骤2、然后制备所述改性阻燃协效剂；步骤3、然后制备所述改性碳纤维；步骤4、按照配方比例，然后将PET、增韧剂、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂、抗氧剂、润滑剂和抗水解剂置于高速混合机中混合均匀，得到混合料；步骤5、然后将所述混合料加入转矩流变仪中进行熔融，熔融的温度为260~265℃，转子转速为50~60 r/min，熔融的时间为10~15min；步骤6、最后将熔融后的混合料热压成型，热压温度为260~265℃，熔融的时间为5~7 min，热压的时间为10~15 min，保温的时间为10~15 min，得到所述无卤阻燃增强PET复合材料。
步骤1中，所述改性无卤阻燃剂的制备方法为：（1）三聚氰胺磷酸盐的合成：称取25~35份苯乙基磷酸，加入到200~300 份去离子水中，升温至95~100℃，再加入18~25份三聚氰胺，在磁力搅拌下保温1.5~2 h，然后经过冷却、过滤，干燥，得所述三聚氰胺磷酸盐；（2）所述改性无卤阻燃剂的复配：按质量比2:3~3:4，将制得的三聚氰胺磷酸盐（MP）与有机碳源复配备用。
步骤2中，所述改性阻燃协效剂的制备方法为：（1）蒙脱土的处理：将15~25份蒙脱土置于400~500份去离子水中，超声振动1~1.5h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在90~100℃烘箱中干燥10~12 h，得到所述蒙脱土，备用；（2）PGMA接枝改性的蒙脱土制备：将5~10ｇ步骤（1）得到的蒙脱土加入到200~300 份去离子水中，在30~40 rpm的转速下机械搅拌10~12 h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌1~2ｈ后在反应体系中加入8~15份甲基丙烯酸缩水甘油酯单体和5~10 份季铵盐类乳化剂，持续搅拌1h，然后在70~80℃下加入0.06~0.09 份引发剂，反应1~2 h后，继续缓慢匀速滴入18 ~23 份甲基丙烯酸缩水甘油酯单体，2~3 h内滴完后，继续反应40~50 min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1~1.5 h，将离心沉淀物溶于四氢呋喃中，再离心分离40~50 min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐类乳化剂和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤3~5次，在90~100℃下干燥10~12 h，即得到PGMA接枝改性的蒙脱土，作为所述改性阻燃协效剂备用。
所述季铵盐类乳化剂为双十二烷基二甲基-γ-双季铵盐、十八烷基三甲基氯化铵（季铵盐1831）、十二烷基二甲基苄基氯化铵（季铵盐1227）和十八烷基二甲基苄基氯化铵（季铵盐1827）中的至少一种，所述引发剂为过硫酸钾和过硫酸铵中的至少一种。
步骤3中，所述改性碳纤维的制备方法，包括以下步骤：（1）碳纤维的预处理：将碳纤维在35~40℃的溶剂中浸泡20~24 h，再用去离子水反复洗涤多次，于70~80℃下干燥4~5h，得到预处理后的碳纤维；（2）碳纤维的氧化处理：将预处理后的碳纤维在80~110℃的强氧化剂中反应2~5 h，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于70~80℃下干燥4~5h，得到所述改性碳纤维；所述强氧化剂为浓硫酸、浓硝酸、次氯酸和高锰酸钾中的一种或多种以任意混合比混合而成，所述溶剂为丙酮、甲苯和二甲苯中的一种或多种以任意混合比混合而成。
 有益效果
采用上述技术方案后，本发明一种无卤阻燃增强PET复合材料，具有以下有益效果：一是通过添加三聚氰胺磷酸盐（MP）与有机碳源的复配物作为改性无卤阻燃剂，添加PGMA接枝改性的蒙脱土作为改性阻燃协效剂。
MP在该阻燃体系中作为酸源、气源，使PET聚合物在燃烧中脱水炭化并最终覆盖在聚合物表面，从而阻碍氧气和热量与内部的聚合物的接触；通过MP和有机碳源的复配可有效改善MP吸湿性大的问题；加入改性后的蒙脱土接枝物作为改性阻燃协效剂，可以促进体系燃烧时形成更加稳定和致密的炭层，提高复合材料的阻燃和阻燃抑烟性能。另外，选用的复配阻燃剂中含有苯乙基，PET分子链中也含有苯乙基，能提高阻燃剂与PET分子链的相容性，同时阻燃协效剂中含有GMA官能团，能与PET上的端羧基和端烃基反应，也解决了阻燃协效剂与PBT相容性较差的问题，提高了PET基材与阻燃剂间的相互作用力，从而在提高材料阻燃性能的同时，也改善了阻燃剂与材料的相容性问题。此外，由于阻燃剂与聚合物间具有较好的界面作用力，使得复合材料仍保持着较好的力学性能。
二是通过添加与PET相容性较好的改性碳纤维，使PET复合材料的力学性能得到进一步提升，同时防止该PET复合材料作为阻燃剂使用时出现灯芯效应。     三是最终本发明制得的无卤阻燃增强PET复合材料，不仅具有良好的阻燃性能，还具有较强的强度和韧性，所制得的PET复合材料无毒、无烟，满足阻燃领域的使用要求。
进一步，本发明一种无卤阻燃增强PET复合材料的制备方法，制备方法简单方便，易于实现，具有重要的实际应用价值。
进一步，本发明采用的增韧剂的分子链中含有可与PET反应的官能团，当增韧剂为接枝甲基丙烯酸缩水甘油酯共聚物时，增韧剂中的环氧基团可与PET上的端羧基和端烃基反应；当增韧剂为接枝马来酸酐共聚物时，增韧剂中的马来酸酐基团可与PET上的烃基反应。因此，选用的增韧剂不仅能起到增韧作用，也能同时改善增韧剂与PET相容性不足的问题，从而最大限度地起到增韧效果。
 本发明的实施方式
为了进一步解释本发明的技术方案，下面通过具体实施例来对本发明进行详细阐述。
实施例1，一种无卤阻燃增强PET复合材料，包括如下重量份的原料：PET，80份；POE-g-GMA，20份；改性无卤阻燃剂，17份；改性阻燃协效剂，4份；改性碳纤维，5份；抗氧剂1010，0.2份；聚乙烯蜡，0.2份；聚碳化二亚胺，0.1份。
其中，改性无卤阻燃剂为三聚氰胺磷酸盐与季戊四醇的复配物，改性阻燃协效剂为PGMA接枝改性的蒙脱土，改性碳纤维为经过氧化处理的碳纤维。
该无卤阻燃增强PET复合材料的制备方法，包括如下步骤：步骤1、制备改性无卤阻燃剂：（1）三聚氰胺磷酸盐的合成：称取31份苯乙基磷酸置于500 mL圆底烧瓶中，再加入200份去离子水，升温至100℃，再加入21份三聚氰胺，在磁力搅拌下保温2h，然后经过冷却、过滤，干燥，得三聚氰胺磷酸盐；（2）改性无卤阻燃剂的复配：按质量比2:3，将制得的三聚氰胺磷酸盐（MP）与季戊四醇复配备用；步骤2、然后制备改性阻燃协效剂：（1）蒙脱土的处理：将20份蒙脱土置于500份去离子水中，超声振动1h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在90℃烘箱中干燥12h，得到蒙脱土，备用；（2）PGMA接枝改性的蒙脱土制备：在500mL四口烧瓶中加入5份步骤（1）得到的蒙脱土和200 份去离子水，在30rpm的转速下机械搅拌12h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌1h后在反应体系中加入10份甲基丙烯酸缩水甘油酯单体和5份季铵盐1831，持续搅拌1h，然后在70℃下加入0.06份过硫酸钾，反应1h后，在四口烧瓶上的恒压滴液漏斗中继续缓慢匀速滴入20份甲基丙烯酸缩水甘油酯单体，3h内滴完后，继续反应40min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1h，将离心沉淀物溶于四氢呋喃中，再离心分离40min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐1831和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤5次，在100℃下干燥12h，即得到PGMA接枝改性的蒙脱土，作为改性阻燃协效剂备用；步骤3、然后制备改性碳纤维：（1）碳纤维的预处理：将碳纤维在35℃的丙酮中浸泡20 h，再用去离子水反复洗涤多次，于70℃下干燥5h，得到预处理后的碳纤维；（2）碳纤维的氧化处理：将预处理后的碳纤维在80℃的浓硫酸中反应2h，浓硫酸的用量以将碳纤维完全淹没为宜，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于70℃下干燥5 h，得到改性碳纤维；步骤4、按照配方比例，然后将经过真空干燥后的PET、POE-g-GMA、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂与抗氧剂1010、润滑剂聚乙烯蜡和抗水解剂聚碳化二亚胺置于高速混合机中混合均匀，得到混合料；步骤5、然后将混合料加入转矩流变仪中进行熔融，熔融的温度为260℃，转子转速为50 r/min，熔融的时间为10 min；步骤6、最后将熔融后的混合料热压成型，热压温度为265℃，熔融的时间为5 min，热压的时间为10 min，保温的时间为15 min，得到无卤阻燃增强PET复合材料。
实施例2，一种无卤阻燃增强PET复合材料，包括如下重量份的原料：PET，70份；PE-g-GMA，30份；改性无卤阻燃剂，15份；改性阻燃协效剂，3份；改性碳纤维，6份；抗氧剂168，0.2份；液体石蜡，0.3份；聚碳化二亚胺，0.3份。
其中，改性无卤阻燃剂为三聚氰胺磷酸盐与乙二醇的复配物，改性阻燃协效剂为PGMA（聚甲基丙烯酸缩水甘油酯）接枝改性的蒙脱土，改性碳纤维为经过氧化处理的碳纤维。
该无卤阻燃增强PET复合材料的制备方法，包括如下步骤：步骤1、制备改性无卤阻燃剂：（1）三聚氰胺磷酸盐的合成：称取28份苯乙基磷酸置于500 mL圆底烧瓶中，再加入250份去离子水，升温至95℃，再加入18份三聚氰胺，在磁力搅拌下保温1.5 h，然后经过冷却、过滤，干燥，得三聚氰胺磷酸盐；（2）改性无卤阻燃剂的复配：按质量比2:3，将制得的三聚氰胺磷酸盐（MP）与乙二醇复配备用；步骤2、然后制备改性阻燃协效剂：（1）蒙脱土的处理：将18份蒙脱土置于400份去离子水中，超声振动1.5 h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在95℃烘箱中干燥10 h，得到蒙脱土，备用；（2）PGMA接枝改性的蒙脱土制备：在500mL四口烧瓶中加入7份步骤（1）得到的蒙脱土和250 份去离子水，在35rpm的转速下机械搅拌12h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌1.5h后在反应体系中加入10份甲基丙烯酸缩水甘油酯单体和5份季铵盐1227，持续搅拌1h，然后在70℃下加入0.07份过硫酸铵，反应1h后，在四口烧瓶上的恒压滴液漏斗中继续缓慢匀速滴入20份甲基丙烯酸缩水甘油酯单体，3h内滴完后，继续反应40min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1 h，将离心沉淀物溶于四氢呋喃中，再离心分离40min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐1227和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤5次，在90℃下干燥10h，即得到PGMA接枝改性的蒙脱土，作为改性阻燃协效剂备用；步骤3、然后制备改性碳纤维：（1）碳纤维的预处理：将碳纤维在40℃的甲苯中浸泡24 h，再用去离子水反复洗涤多次，于70℃下干燥5h，得到预处理后的碳纤维；（2）碳纤维的氧化处理：将预处理后的碳纤维在100℃的浓硝酸中反应4 h，浓硝酸的用量以将碳纤维完全淹没为宜，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于70℃下干燥5 h，得到改性碳纤维；步骤4、按照配方比例，然后将经过真空干燥后的PET、PE-g-GMA、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂与抗氧剂168、润滑剂液体石蜡和抗水解剂聚碳化二亚胺置于高速混合机中混合均匀，得到混合料；步骤5、然后将混合料加入转矩流变仪中进行熔融，熔融的温度为260℃，转子转速为55 r/min，熔融的时间为10 min；步骤6、最后将熔融后的混合料热压成型，热压温度为260℃，熔融的时间为7 min，热压的时间为15 min，保温的时间为10 min，得到无卤阻燃增强PET复合材料。
实施例3，一种无卤阻燃增强PET复合材料，包括如下重量份的原料：PET，75份；SGMA，25份；改性无卤阻燃剂，20份；改性阻燃协效剂，8份；改性碳纤维，10份；三(壬基苯基)亚磷酸酯，0.5份；PET，0.8份； N, N'-二(2,6-二异丙基苯基)碳二亚胺，0.5份。
其中，改性无卤阻燃剂为三聚氰胺磷酸盐与季戊四醇的复配物，改性阻燃协效剂为PGMA（聚甲基丙烯酸缩水甘油酯）接枝改性的蒙脱土，改性碳纤维为经过氧化处理的碳纤维。
该无卤阻燃增强PET复合材料的制备方法，包括如下步骤：步骤1、制备改性无卤阻燃剂：（1）三聚氰胺磷酸盐的合成：称取33份苯乙基磷酸置于500 mL圆底烧瓶中，再加入300份去离子水，升温至100℃，再加入23份三聚氰胺，在磁力搅拌下保温1.5h，然后经过冷却、过滤，干燥，得三聚氰胺磷酸盐；（2）改性无卤阻燃剂的复配：按质量比3:4，将制得的三聚氰胺磷酸盐（MP）与季戊四醇复配备用；步骤2、然后制备改性阻燃协效剂：（1）蒙脱土的处理：将15份蒙脱土置于400份去离子水中，超声振动1.5h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在90℃烘箱中干燥10h，得到蒙脱土，备用；（2）PGMA接枝改性的蒙脱土制备：在500mL四口烧瓶中加入6份步骤（1）得到的蒙脱土和250 份去离子水，在35rpm的转速下机械搅拌11h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌1.5h后在反应体系中加入10份甲基丙烯酸缩水甘油酯单体和5份季铵盐1827，持续搅拌1h，然后在70℃下加入0.07份过硫酸钾，反应1h后，在四口烧瓶上的恒压滴液漏斗中继续缓慢匀速滴入20份甲基丙烯酸缩水甘油酯单体，3h内滴完后，继续反应40min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1h，将离心沉淀物溶于四氢呋喃中，再离心分离40min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐1827和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤5次，在100℃下干燥12h，即得到PGMA接枝改性的蒙脱土，作为改性阻燃协效剂备用；步骤3、然后制备改性碳纤维：（1）碳纤维的预处理：将碳纤维在35℃的丙酮中浸泡20 h，再用去离子水反复洗涤多次，于80℃下干燥4h，得到预处理后的碳纤维；（2）碳纤维的氧化处理：将预处理后的碳纤维在90℃的浓硫酸中反应3h，浓硫酸的用量以将碳纤维完全淹没为宜，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于80℃下干燥4h，得到改性碳纤维；步骤4、按照配方比例，然后将经过真空干燥后的PET、SGMA、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂与抗氧剂三(壬基苯基)亚磷酸酯、润滑剂PETS和抗水解剂 N, N'-二(2,6-二异丙基苯基)碳二亚胺置于高速混合机中混合均匀，得到混合料；步骤5、然后将混合料加入转矩流变仪中进行熔融，熔融的温度为260℃，转子转速为60 r/min，熔融的时间为10 min；步骤6、最后将熔融后的混合料热压成型，热压温度为263℃，熔融的时间为7 min，热压的时间为12 min，保温的时间为12 min，得到无卤阻燃增强PET复合材料。
实施例4，一种无卤阻燃增强PET复合材料，包括如下重量份的原料：PET，75份；POE-g-MAH，25份；改性无卤阻燃剂，15份；改性阻燃协效剂，5份；改性碳纤维，8份；抗氧剂168，0.3份；聚乙烯蜡，0.5份；聚碳化二亚胺，0.3份。
其中，改性无卤阻燃剂为三聚氰胺磷酸盐与季戊四醇的复配物，改性阻燃协效剂为PGMA（聚甲基丙烯酸缩水甘油酯）接枝改性的蒙脱土，改性碳纤维为氧化处理的碳纤维。
该无卤阻燃增强PET复合材料的制备方法，包括如下步骤：步骤1、制备改性无卤阻燃剂：（1）三聚氰胺磷酸盐的合成：称取35份苯乙基磷酸置于500 mL圆底烧瓶中，再加入300份去离子水，升温至100℃，再加入25份三聚氰胺，在磁力搅拌下保温1.5h，然后经过冷却、过滤，干燥，得三聚氰胺磷酸盐；（2）改性无卤阻燃剂的复配：按质量比2:3，将制得的三聚氰胺磷酸盐（MP）与季戊四醇复配备用；步骤2、然后制备改性阻燃协效剂：（1）蒙脱土的处理：将25份蒙脱土置于500份去离子水中，超声振动1h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在100℃烘箱中干燥12h，得到蒙脱土，备用；（2）PGMA接枝改性的蒙脱土制备：在500mL四口烧瓶中加入8份步骤（1）得到的蒙脱土和300 份去离子水，在40rpm的转速下机械搅拌11h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌2h后在反应体系中加入10份甲基丙烯酸缩水甘油酯单体和5份季铵盐1227，持续搅拌1h，然后在80℃下加入0.08份过硫酸铵，反应1h后，在四口烧瓶上的恒压滴液漏斗中继续缓慢匀速滴入23份甲基丙烯酸缩水甘油酯单体，3h内滴完后，继续反应40min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1h，将离心沉淀物溶于四氢呋喃中，再离心分离40min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐1227和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤5次，在100℃下干燥12h，即得到PGMA接枝改性的蒙脱土，作为改性阻燃协效剂备用；步骤3、然后制备改性碳纤维：（1）碳纤维的预处理：将碳纤维在35℃的二甲苯中浸泡24 h，再用去离子水反复洗涤多次，于70℃下干燥5h，得到预处理后的碳纤维；（2）碳纤维的氧化处理：将预处理后的碳纤维在110℃的浓硝酸中反应5 h，浓硝酸的用量以将碳纤维完全淹没为宜，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于70℃下干燥5 h，得到改性碳纤维；步骤4、按照配方比例，然后将经过真空干燥后的PET、POE-g-MAH、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂与抗氧剂168、润滑剂聚乙烯蜡和抗水解剂聚碳化二亚胺置于高速混合机中混合均匀，得到混合料；步骤5、然后将混合料加入转矩流变仪中进行熔融，熔融的温度为265℃，转子转速为55 r/min，熔融的时间为12 min；步骤6、最后将熔融后的混合料热压成型，热压温度为265℃，熔融的时间为5 min，热压的时间为12 min，保温的时间为12 min，得到无卤阻燃增强PET复合材料。
实施例5，一种无卤阻燃增强PET复合材料，包括如下重量份的原料：PET，70份；SGMA，30份；改性无卤阻燃剂，20份；改性阻燃协效剂，8份；改性碳纤维，8份；抗氧剂1010，0.5份；PETS，1份； N, N'-二(2,6-二异丙基苯基)碳二亚胺，0.5份。
其中，改性无卤阻燃剂为三聚氰胺磷酸盐与酚醛树脂的复配物，改性阻燃协效剂为PGMA（聚甲基丙烯酸缩水甘油酯）接枝改性的蒙脱土，改性碳纤维为经过氧化处理的碳纤维。
该无卤阻燃增强PET复合材料的制备方法，包括如下步骤：步骤1、制备改性无卤阻燃剂：（1）三聚氰胺磷酸盐的合成：称取30份苯乙基磷酸置于500 mL圆底烧瓶中，再加入300份去离子水，升温至95℃，再加入20份三聚氰胺，在磁力搅拌下保温1.5h，然后经过冷却、过滤，干燥，得三聚氰胺磷酸盐；（2）改性无卤阻燃剂的复配：按质量比3:4，将制得的三聚氰胺磷酸盐（MP）与酚醛树脂复配备用；步骤2、然后制备改性阻燃协效剂：（1）蒙脱土的处理：将21份蒙脱土置于500份去离子水中，超声振动1.5h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在100℃烘箱中干燥10 h，得到蒙脱土，备用；（2）PGMA接枝改性的蒙脱土制备：在500mL四口烧瓶中加入6份步骤（1）得到的蒙脱土和230份去离子水，在30rpm的转速下机械搅拌11h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌1.5h后在反应体系中加入10份甲基丙烯酸缩水甘油酯单体和5份季铵盐1827，持续搅拌1h，然后在70℃下加入0.06份过硫酸钾，反应1h后，在四口烧瓶上的恒压滴液漏斗中继续缓慢匀速滴入20份甲基丙烯酸缩水甘油酯单体，3h内滴完后，继续反应40min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1h，将离心沉淀物溶于四氢呋喃中，再离心分离40min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐1827和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤5次，在100℃下干燥12h，即得到PGMA接枝改性的蒙脱土，作为改性阻燃协效剂备用；步骤3、然后制备改性碳纤维：（1）碳纤维的预处理：将碳纤维在35~40℃的甲苯中浸泡20~24 h，再用去离子水反复洗涤多次，于70℃下干燥5h，得到预处理后的碳纤维；（2）碳纤维的氧化处理：将预处理后的碳纤维在80~110℃的浓硝酸中反应2~5 h，浓硝酸的用量以将碳纤维完全淹没为宜，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于70℃下干燥5 h，得到改性碳纤维；步骤4、按照配方比例，然后将经过真空干燥后的PET、SGMA、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂与抗氧剂1010、润滑剂PETS和抗水解剂 N, N'-二(2,6-二异丙基苯基)碳二亚胺置于高速混合机中混合均匀，得到混合料；步骤5、然后将混合料加入转矩流变仪中进行熔融，熔融的温度为265℃，转子转速为60 r/min，熔融的时间为15 min；步骤6、最后将熔融后的混合料热压成型，热压温度为265℃，熔融的时间为5 min，热压的时间为15 min，保温的时间为10 min，得到无卤阻燃增强PET复合材料。
对比例，普通PET复合材料，包括如下重量份的原料：PET，70份；增韧剂ABS，30份；抗氧剂1010，0.3份；液体石蜡，0.5份；聚碳化二亚胺，0.3份。
该普通PET复合材料的制备方法，包括如下步骤：步骤1、按照配方比例，然后将经过真空干燥后的PET、增韧剂ABS与抗氧剂1010、润滑剂液体石蜡和抗水解剂聚碳化二亚胺置于高速混合机中混合均匀，得到混合料；步骤2、然后将混合料加入转矩流变仪中进行熔融，熔融的温度为265℃，转子转速为60 r/min，熔融的时间为15 min；步骤3、最后将熔融后的混合料热压成型，热压温度为260℃，熔融的时间为5 min，热压的时间为15 min，保温的时间为10 min，得到对比例普通PET复合材料。
实验例，分别将实施例1~5制备得到的无卤阻燃增强PET复合材料以及对比例制备得到的普通PET复合材料进行裁样，得到哑铃型拉伸试样与长条形冲击试样，将各实施例和对比例得到的试样分别进行拉伸性能测试（GB/T1040.2-2006）、冲击性能测试（GB/T1043.1-2008）、垂直燃烧和极限氧指数测试，测试结果见表1。
表1 无卤阻燃增强PET复合材料的性能测试结果。
Figure 876660dest_path_image001
。
从表1可以看出，本发明制得的无卤阻燃增强PET复合材料，不仅具有良好的阻燃性能，达到UL94V-0级，还具有较强的冲击强度和拉伸强度，所制得的PET复合材料无毒、无烟，满足阻燃领域的使用要求。
上述实施例并非限定本发明的产品形态和式样，任何所属技术领域的普通技术人员对其所做的适当变化或修饰，皆应视为不脱离本发明的专利范畴。

Claims (10)

  1. 一种无卤阻燃增强PET复合材料，其特征在于：包括如下重量份的原料：
    PET                    70~80份
    增韧剂                  20~30份
    改性无卤阻燃剂          15~20份
    改性阻燃协效剂          3~8份
    改性碳纤维              5~10份
    抗氧剂                  0.1~0.5份
    润滑剂                  0.2~1份
    抗水解剂                0.1~0.5份
    所述改性无卤阻燃剂为三聚氰胺磷酸盐与有机碳源的复配物，所述改性阻燃协效剂为PGMA接枝改性的蒙脱土，所述改性碳纤维为经过氧化处理的碳纤维。
  2. 根据权利要求1所述的一种无卤阻燃增强PET复合材料，其特征在于：所述增韧剂为乙烯-辛烯接枝甲基丙烯酸缩水甘油酯共聚物、聚乙烯接枝甲基丙烯酸缩水甘油酯共聚物、苯乙烯接枝甲基丙烯酸缩水甘油酯共聚物和乙烯辛烯接枝马来酸酐共聚物中的至少一种。
  3. 根据权利要求1所述的一种无卤阻燃增强PET复合材料，其特征在于：所述改性无卤阻燃剂中三聚氰胺磷酸盐与有机碳源按质量比2:3~3:4复配而成，所述有机碳源为季戊四醇、乙二醇和酚醛树脂中的至少一种。
  4. 根据权利要求1所述的一种无卤阻燃增强PET复合材料，其特征在于：所述抗氧剂为四[β-（3,5-二叔丁基-4-羟基苯基）丙酸]季戊四醇酯、三(壬基苯基)亚磷酸酯、三[2,4-二叔丁基苯基]亚磷酸酯和2,5-二特丁基对苯二酚中的至少一种。
  5. 根据权利要求1所述的一种无卤阻燃增强PET复合材料，其特征在于：所述润滑剂为天然石蜡、季戊四醇硬脂酸酯、聚乙烯蜡、液体石蜡和微晶石中的至少一种。
  6. 根据权利要求1所述的一种无卤阻燃增强PET复合材料，其特征在于：所述抗水解剂为炭黑、 N, N'-二(2,6-二异丙基苯基)碳二亚胺和聚碳化二亚胺中的至少一种。
  7. 制备如权利要求1所述的一种无卤阻燃增强PET复合材料的制备方法，其特征在于：包括以下步骤：
    步骤1、先制备所述改性无卤阻燃剂；
    步骤2、然后制备所述改性阻燃协效剂；
    步骤3、然后制备所述改性碳纤维；
    步骤4、按照配方比例，然后将PET、增韧剂、改性碳纤维、改性无卤阻燃剂、改性阻燃协效剂、抗氧剂、润滑剂和抗水解剂置于高速混合机中混合均匀，得到混合料；
    步骤5、然后将所述混合料加入转矩流变仪中进行熔融，熔融的温度为260~265℃，转子转速为50~60 r/min，熔融的时间为10~15min；
    步骤6、最后将熔融后的混合料热压成型，热压温度为260~265℃，熔融的时间为5~7 min，热压的时间为10~15 min，保温的时间为10~15 min，得到所述无卤阻燃增强PET复合材料。
  8. 根据权利要求7所述的一种无卤阻燃增强PET复合材料的制备方法，其特征在于：步骤1中，所述改性无卤阻燃剂的制备方法为：
    （1）三聚氰胺磷酸盐的合成：称取25~35 份苯乙基磷酸，加入到200~300 份去离子水中，升温至95~100℃，再加入18~25 份三聚氰胺，在磁力搅拌下保温1.5~2 h，然后经过冷却、过滤，干燥，得所述三聚氰胺磷酸盐；
    （2）所述改性无卤阻燃剂的复配：按质量比2:3~3:4，将制得的三聚氰胺磷酸盐与有机碳源复配备用。
  9. 根据权利要求7所述的一种无卤阻燃增强PET复合材料的制备方法，其特征在于：步骤2中，所述改性阻燃协效剂的制备方法为：
    （1）蒙脱土的处理：将15~25 份蒙脱土置于400~500 份去离子水中，超声振动1~1.5h以扩大蒙脱土的层间距，经去离子水多次重复洗涤并过滤后，在90~100℃烘箱中干燥10~12 h，得到所述蒙脱土，备用；
    （2）PGMA接枝改性的蒙脱土制备：将5~10份步骤（1）得到的蒙脱土加入到200~300 份去离子水中，在30~40 rpm的转速下机械搅拌10~12 h，然后在反应体系中鼓入N 2以形成N 2气氛，继续搅拌1~2ｈ后在反应体系中加入8~15份甲基丙烯酸缩水甘油酯单体和5~10份季铵盐类乳化剂，持续搅拌1h，然后在70~80℃下加入0.06~0.09 份引发剂，反应1~2 h后，继续缓慢匀速滴入18 ~23 份甲基丙烯酸缩水甘油酯单体，2~3 h内滴完后，继续反应40~50 min，反应结束后，将反应液冷却至室温后，转移至离心管中离心1~1.5 h，将离心沉淀物溶于四氢呋喃中，再离心分离40~50 min，如此反复3次，以除去残余的甲基丙烯酸缩水甘油酯单体、季铵盐类乳化剂和未接枝在蒙脱土表面的PGMA，最后，将离心沉淀物用无水乙醇洗涤3~5次，在90~100℃下干燥10~12 h，即得到PGMA接枝改性的蒙脱土，作为所述改性阻燃协效剂备用；
    所述季铵盐类乳化剂为双十二烷基二甲基-γ-双季铵盐、十八烷基三甲基氯化铵、十二烷基二甲基苄基氯化铵和十八烷基二甲基苄基氯化铵中的至少一种，所述引发剂为过硫酸钾和过硫酸铵中的至少一种。
  10. 根据权利要求7所述的一种无卤阻燃增强PET复合材料的制备方法，其特征在于：步骤3中，所述改性碳纤维的制备方法，包括以下步骤：
    （1）碳纤维的预处理：将碳纤维在35~40℃的溶剂中浸泡20~24 h，再用去离子水反复洗涤多次，于70~80℃下干燥4~5h，得到预处理后的碳纤维；
    （2）碳纤维的氧化处理：将预处理后的碳纤维在80~110℃的强氧化剂中反应2~5 h，待反应结束后，用去离子水洗涤表面被氧化的碳纤维至pH值为6~7，于70~80℃下干燥4~5h，得到所述改性碳纤维；
    所述强氧化剂为硫酸、硝酸、次氯酸和高锰酸钾中的一种或多种以任意混合比混合而成，所述溶剂为丙酮、甲苯和二甲苯中的一种或多种以任意混合比混合而成。
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