CN114752187A - Preparation method of recyclable composite PET packaging box material - Google Patents
Preparation method of recyclable composite PET packaging box material Download PDFInfo
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- CN114752187A CN114752187A CN202111642877.7A CN202111642877A CN114752187A CN 114752187 A CN114752187 A CN 114752187A CN 202111642877 A CN202111642877 A CN 202111642877A CN 114752187 A CN114752187 A CN 114752187A
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- 239000000463 material Substances 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 24
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 99
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 82
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 28
- 238000001746 injection moulding Methods 0.000 claims abstract description 26
- 239000005543 nano-size silicon particle Substances 0.000 claims abstract description 25
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 21
- 238000000151 deposition Methods 0.000 claims abstract description 21
- 230000008021 deposition Effects 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000001125 extrusion Methods 0.000 claims abstract description 12
- 238000005469 granulation Methods 0.000 claims abstract description 12
- 230000003179 granulation Effects 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 4
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 40
- 230000005495 cold plasma Effects 0.000 claims description 31
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 239000004760 aramid Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 26
- 229920005604 random copolymer Polymers 0.000 claims description 22
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 20
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 20
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 20
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 claims description 20
- 238000001291 vacuum drying Methods 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 11
- 238000005886 esterification reaction Methods 0.000 claims description 11
- 239000000835 fiber Substances 0.000 claims description 11
- 238000006068 polycondensation reaction Methods 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- 239000000178 monomer Substances 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 238000002791 soaking Methods 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- UHUUYVZLXJHWDV-UHFFFAOYSA-N trimethyl(methylsilyloxy)silane Chemical compound C[SiH2]O[Si](C)(C)C UHUUYVZLXJHWDV-UHFFFAOYSA-N 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- 239000005022 packaging material Substances 0.000 claims 1
- 238000012856 packing Methods 0.000 abstract description 11
- 238000002425 crystallisation Methods 0.000 abstract description 7
- 230000008025 crystallization Effects 0.000 abstract description 7
- 230000006911 nucleation Effects 0.000 abstract description 7
- 238000010899 nucleation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004064 recycling Methods 0.000 abstract description 5
- 239000002245 particle Substances 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000000071 blow moulding Methods 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229920000554 ionomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000678 plasma activation Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
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- D06M10/00—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements
- D06M10/02—Physical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. ultrasonic, corona discharge, irradiation, electric currents, or magnetic fields; Physical treatment combined with treatment with chemical compounds or elements ultrasonic or sonic; Corona discharge
- D06M10/025—Corona discharge or low temperature plasma
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
- D06M15/273—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of unsaturated carboxylic esters having epoxy groups
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- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- D06M2101/16—Synthetic fibres, other than mineral fibres
- D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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Abstract
The invention provides a preparation method of a recyclable composite PET packaging box material, which comprises the following steps: dispersing nano silicon carbide in ethylene glycol for reaction; uniformly mixing the modified PET with terephthalic acid, and adding the mixture into a polymerization reaction kettle for reaction to obtain modified PET; drying the modified PET in vacuum, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, performing melt extrusion granulation in a double-screw extruder, and performing injection molding by using an injection molding machine to obtain a standard sample; and (3) placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film to obtain the recyclable composite PET packing box material. According to the invention, by adding the nano silicon carbide particles, a heterogeneous nucleation effect is achieved, the nucleation mechanism of PET is changed, the crystallinity and the crystallization rate of PET are improved, the thermal stability and the mechanical property of the material are improved, and meanwhile, the silicon oxide film is deposited on the surface of the PET by a magnetron sputtering method, so that the water resistance is improved, and the recycling effect is improved.
Description
Technical Field
The invention relates to the field of plastic materials, in particular to a preparation method of a recyclable composite PET packaging box material.
Background
PET has excellent properties such as abrasion resistance, heat resistance, electrical insulation, and chemical resistance, and is widely used in the fields of synthetic polyester fibers, film manufacturing, and civil blow molding. Because of the defects of slow crystallization rate, high temperature of a forming die, long forming period, poor impact property, large water absorption and the like, the application of the PET in the field of engineering plastics is limited. In addition, PET is easy to flow in the injection molding process, and normal injection molding of PET resin can be realized only by improving the crystallization rate of the PET. At present, only a few major companies such as Dupont and ICI have the technology, which mainly utilizes the chemical nucleation of organic carboxylate or high-molecular ionomer to improve the crystallization rate of PET, but the molecular chain of PET is broken, and the molecules are locally degraded. In addition, the PET engineering plastics of the companies have very high selling price in China, and the consumption of the domestic PET engineering plastics cannot be greatly increased to a great extent. On the other hand, as the PET is used as a non-degradable material, with the development of the plastic-limiting ream, the recycling of the PET also becomes one of the problems to be solved.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the technical problems of low crystallization rate and difficult recycling of the existing PET material, the invention has the advantages that through adding the nano silicon carbide particles, the heterogeneous nucleation effect is realized, the nucleation mechanism of PET is changed, the crystallinity and the crystallization rate of PET are improved, the thermal stability and the mechanical property of the material are improved, and meanwhile, the silicon oxide film is deposited on the surface of the PET by a magnetron sputtering method, so that the waterproofness is improved, and the recycling effect is improved.
The technical scheme is as follows: a preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 1-2 h;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 250-260 ℃, and carrying out esterification reaction for 1-2 hours;
and step 3: starting a vacuum pump for pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 270-280 ℃, and reacting for 1-2 hours;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, performing melt extrusion granulation in a double-screw extruder, and performing injection molding by using an injection molding machine to obtain a standard sample, wherein the mold temperature is 70 ℃;
step 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the power of the microwave plasma chemical vapor deposition device adopts 500-5000W of power supply, and tetramethyldisiloxane and O 2The flow ratio of (1) to (120) and the working pressure of 20-60 Pa.
Further, the molar ratio of terephthalic acid to ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.05-0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol.
Further, the ratio of the modified PET to the modified aramid fiber in the step 5 is 8 (1-2).
Further, the preparation method of the modified aramid fiber in the step 5 comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid;
(2) pouring the solution into a normal hexane solution for washing, removing upper-layer liquid, repeating for 2-3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) putting the aramid fiber into a cold plasma cavity, heating the aramid fiber to 90 ℃ in the cavity, and keeping the temperature at N2Carrying out cold plasma pretreatment on aramid fibers in the atmosphere;
(4) After the pretreatment is finished, soaking aramid fibers in 0.5-3% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the grafting time is 10 min.
Furthermore, the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2.
Further, the cold plasma pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow rate is 35mL/min, the power is 50W, and the time is 30 min.
Further, in the step 5, the temperatures of all sections of the cylinder of the twin-screw extruder are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm.
Further, the vacuum degree of the magnetron sputtering background in the step 6 is 5.0 multiplied by 10-3Pa, power supply power of 100-400W, working air pressure of 1 × 10-2～5×10-2Pa, and the deposition time is 10-120 min.
Further, the thickness of the silicon oxide film in the step 6 is 50-300 nm.
Has the advantages that:
1. the invention has the advantages that the nano silicon carbide particles are added, the heterogeneous nucleation effect is realized, the nucleation mechanism of PET is changed, the crystallinity and the crystallization rate of PET are improved, and the thermal stability and the mechanical property of the material are improved.
2. According to the invention, the surface of aramid fiber is firstly subjected to plasma activation, active groups such as free radicals are introduced on the surface by adopting a ternary random copolymer product, the aramid fiber is taken out and then immediately immersed in a ternary random copolymer product solution for post-graft polymerization when the vacuum is relieved, and a flexible interface layer is formed between the aramid fiber and a PET material, so that the interface performance between the aramid fiber and the PET material is improved.
3. According to the invention, the silicon oxide film is deposited on the surface of the PET by a magnetron sputtering method, so that the waterproofness is improved, and the recycling effect is improved.
Detailed Description
Example 1
A preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 1 h;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 250 ℃, and carrying out esterification reaction for 1 h; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.05 per mill of the total mass of the terephthalic acid and the ethylene glycol;
and step 3: starting a vacuum pump, carrying out pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 270 ℃, and reacting for 1 h;
And 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET; and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:1, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of the mold is 70 ℃;
step 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 50 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 100W, working air pressure 1X 10-2Pa, deposition time 10 min; the microwave plasma chemical vapor deposition adopts 500W of power supply power, tetramethyldisiloxane and O2The flow ratio of (1) to (120) and the working pressure of 20 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) Pouring the solution into a normal hexane solution for washing, removing upper-layer liquid, repeating for 2 times, and performing vacuum drying to constant weight to obtain a ternary random copolymer product;
(3) putting the aramid fiber into a cold plasma cavity, heating the aramid fiber to 90 ℃ in the cavity, and keeping the temperature at N2Carrying out cold plasma pretreatment on aramid fibers under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 0.5% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Example 2
A preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 1.5 h;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 255 ℃, and carrying out esterification reaction for 1.5 h; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.1 per mill of the total mass of the terephthalic acid and the ethylene glycol;
And 3, step 3: starting a vacuum pump, performing pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 275 ℃, and reacting for 1.5 hours;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:1.5, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and 100rpm of screw rotation speed; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of a mold is 70 ℃;
and 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 100 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 200W, working air pressure 2X 10-2Pa, deposition time 30 min; the microwave plasma chemical vapor deposition adopts 1000W of power supply power, tetramethyldisiloxane and O 2The flow ratio of (1) to (120) and the working pressure of 30 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) pouring the solution into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying to constant weight to obtain a ternary random copolymer product;
(3) putting aramid fiber into cold plasma cavity, heating to 90 deg.C in N2Carrying out cold plasma pretreatment on aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 1% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Example 3
A preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 1.5 h;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 255 ℃, and carrying out esterification reaction for 1.5 h; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.15 per mill of the total mass of the terephthalic acid and the ethylene glycol;
and step 3: starting a vacuum pump, carrying out pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 275 ℃, and reacting for 1.5 h;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:1.5, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of the mold is 70 ℃;
Step 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 150 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 300W, working air pressure 3X 10-2Pa, deposition time 50 min; the microwave plasma chemical vapor deposition adopts 2000W of power supply power, tetramethyldisiloxane and O2The flow ratio of (1) to (120) and the working pressure of 40 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) pouring the mixture into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying until the weight is constant to obtain a ternary random copolymer product;
(3) Putting aramid fiber into cold plasma cavity, heating to 90 deg.C in N2Carrying out cold plasma pretreatment on aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 1.5% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Example 4
A preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 1 h;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 250 ℃, and carrying out esterification reaction for 1 h; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.15 per mill of the total mass of the terephthalic acid and the ethylene glycol;
and step 3: starting a vacuum pump, carrying out pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 270 ℃, and reacting for 1 h;
And 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening the kettle bottom for dischargingDischarging through a valve, cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:1, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of the mold is 70 ℃;
step 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 200 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 200W, working air pressure 4X 10-2Pa, depositing for 80 min; the microwave plasma chemical vapor deposition adopts 3000W of power supply power, tetramethyldisiloxane and O2The flow ratio of (1) to (120) and the working pressure of 50 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) Pouring the solution into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying to constant weight to obtain a ternary random copolymer product;
(3) putting the aramid fiber into a cold plasma cavity, heating the aramid fiber to 90 ℃ in the cavity, and keeping the temperature at N2Carrying out cold plasma pretreatment on aramid fibers under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow rate is 35mL/min, the power is 50W, and the time is 30min；
(4) After the pretreatment is finished, soaking aramid fibers in a 2% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Example 5
A preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 2 hours;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 260 ℃, and carrying out esterification reaction for 2 hours; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.15 per mill of the total mass of the terephthalic acid and the ethylene glycol;
And 3, step 3: starting a vacuum pump, performing pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 280 ℃, and reacting for 2 hours;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and 100rpm of screw rotation speed; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of a mold is 70 ℃;
and 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 250 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 400W, working air pressure 4X 10-2Pa, deposition time 100 min; the microwave plasma chemical vapor deposition adopts power supply power of 4000W, tetramethyldisiloxane and O 2The flow ratio of (1) to (120) and the working pressure of 50 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) pouring the mixture into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying until the weight is constant to obtain a ternary random copolymer product;
(3) putting aramid fiber into cold plasma cavity, heating to 90 deg.C in N2Carrying out cold plasma pretreatment on aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 2.5% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Example 6
A preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 2 hours;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 260 ℃, and carrying out esterification reaction for 2 hours; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol;
and step 3: starting a vacuum pump, carrying out pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 280 ℃, and reacting for 2 hours;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of the mold is 70 ℃;
And 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 300 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 400W, working air pressure 5X 10-2Pa, deposition time 120 min; the microwave plasma chemical vapor deposition adopts the power supply with 5000W, the tetramethyldisiloxane and O2The flow ratio of (1) to (120) and the working pressure of 60 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) pouring the mixture into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying until the weight is constant to obtain a ternary random copolymer product;
(3) Putting aramid fiber into cold plasmaIn the chamber, the temperature in the chamber is heated to 90 ℃ in N2Carrying out cold plasma pretreatment on aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 3% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Comparative example 1
The comparative example differs from example 6 in that unmodified aramid fibers were used, as follows:
a preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 2 hours;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the polymerization reaction kettle to 0.25MPa and 260 ℃, and carrying out esterification reaction for 2 hours; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol;
and step 3: starting a vacuum pump, performing pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 280 ℃, and reacting for 2 hours;
And 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with aramid fibers in a high-speed mixer, wherein the ratio of the modified PET to the aramid fibers is 8:2, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and 100rpm of screw rotation speed; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of a mold is 70 ℃;
and 6: taking a modified PET sample, and placing the modified PET sample in a microwave plasma chemical vapor deposition deviceCarrying out magnetron sputtering deposition on a silicon oxide film with the thickness of 300 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 400W, working air pressure 5X 10-2Pa, deposition time 120 min; the microwave plasma chemical vapor deposition adopts the power supply with 5000W, the tetramethyldisiloxane and O2The flow ratio of (1) to (120) and the working pressure of 60 Pa.
Comparative example 2
This comparative example differs from example 6 in that no silicon oxide film was deposited, as follows:
a preparation method of a recyclable composite PET packing box material comprises the following steps:
Step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 2 hours;
and 2, step: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating the mixture to 0.25MPa and 260 ℃, and carrying out esterification reaction for 2 hours; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol;
and 3, step 3: starting a vacuum pump, performing pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 280 ℃, and reacting for 2 hours;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm; and then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of the mold is 70 ℃.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) pouring the mixture into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying until the weight is constant to obtain a ternary random copolymer product;
(3) putting aramid fiber into cold plasma cavity, heating to 90 deg.C in N2Carrying out cold plasma pretreatment on aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 3% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
Comparative example 3
The comparative example is different from example 6 in that the nano silicon carbide is not doped, and the specific steps are as follows:
a preparation method of a recyclable composite PET packing box material comprises the following steps:
step 1: uniformly mixing terephthalic acid and ethylene glycol, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 260 ℃, and carrying out esterification reaction for 2 hours; the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7;
step 2: starting a vacuum pump, carrying out pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 280 ℃, and reacting for 2 hours;
and step 3: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 4, step 4: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, performing melt extrusion granulation in a double-screw extruder, and sequentially setting the temperature of each section of a cylinder of the double-screw extruder as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm; then injection molding is carried out by an injection molding machine to obtain a standard sample, and the temperature of the mold is 70 ℃;
And 5: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the thickness of the silicon oxide film is 300 nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10-3Pa, power supply power 400W, working air pressure 5X 10-2Pa, deposition time 120 min; the microwave plasma chemical vapor deposition adopts the power supply with 5000W, the tetramethyldisiloxane and O2The flow ratio of (1) to (120) and the working pressure of 60 Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2;
(2) pouring the mixture into a normal hexane solution for washing, removing upper-layer liquid, repeating for 3 times, and performing vacuum drying until the weight is constant to obtain a ternary random copolymer product;
(3) Putting the aramid fiber into a cold plasma cavity, heating the aramid fiber to 90 ℃ in the cavity, and keeping the temperature at N2Carrying out cold plasma pretreatment on aramid fibers under the atmosphere, wherein the pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow is 35mL/min, the power is 50W, and the time is 30 min;
(4) after the pretreatment is finished, soaking aramid fibers in a 3% ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min. And (3) testing and analyzing the mechanical properties of the material by adopting an electronic universal tester, and preparing and testing samples according to the standard GB/T1040-2018.
And testing and analyzing the impact strength of the material by adopting a digital display impact tester, and preparing and testing samples according to the standard GB/T1843-2008.
TABLE 1 Performance testing of the examples
Claims (9)
1. A preparation method of a recyclable composite PET packaging box material is characterized by comprising the following steps: the method comprises the following steps:
step 1: dispersing nano silicon carbide in ethylene glycol, and reacting for 1-2 h;
step 2: uniformly mixing the mixture with terephthalic acid, adding the mixture into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 250-260 ℃, and carrying out esterification reaction for 1-2 hours;
And step 3: starting a vacuum pump for pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to be 270-280 ℃, and reacting for 1-2 hours;
and 4, step 4: after the reaction is finished, vacuum defoaming, N2Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
and 5: placing the modified PET at 120 ℃ for vacuum drying, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, performing melt extrusion granulation in a double-screw extruder, and performing injection molding by using an injection molding machine to obtain a standard sample, wherein the mold temperature is 70 ℃;
step 6: placing the modified PET sample in a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the power supply power of the microwave plasma chemical vapor deposition device is 500-5000W, and tetramethyldisiloxane is adoptedAnd O2The flow ratio of (1: 120) and the working pressure of 20-60 Pa.
2. A recyclable composite PET packaging box material as claimed in claim 1, characterized in that: the molar ratio of the terephthalic acid to the ethylene glycol is 1: 1.7; the mass of the nano silicon carbide accounts for 0.05-0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol.
3. A recyclable composite PET packaging box material as claimed in claim 1, characterized in that: the proportion of the modified PET to the modified aramid fiber in the step 5 is 8 (1-2).
4. A recyclable composite PET packaging material according to claim 1, characterized in that: the preparation method of the modified aramid fiber in the step 5 comprises the following steps:
(1) adding ethyl acetate into a four-mouth flask, introducing nitrogen for protection, heating in a water bath to about 50 ℃, magnetically stirring, adding three monomers of glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan into the four-mouth flask from a constant-pressure dropping funnel, stirring for 0.5h, raising the temperature to 60 ℃, stirring for 3h, and stopping reaction to obtain viscous liquid;
(2) pouring the solution into a normal hexane solution for washing, removing upper-layer liquid, repeating for 2-3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) putting aramid fiber into cold plasma cavity, heating to 90 deg.C in N2Carrying out cold plasma pretreatment on aramid fibers in the atmosphere;
(4) after the pretreatment is finished, soaking aramid fibers in 0.5-3% of ternary random copolymer product/acetone solution, drying the solvent, and then carrying out cold plasma grafting on the fibers to obtain modified aramid fibers; wherein the grafting power is 100W, and the time is 10 min.
5. A recyclable composite PET packaging box material as claimed in claim 4, characterized in that: the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azodiisobutyronitrile to the dodecanethiol is 1:3:1:0.02: 0.2.
6. A recyclable composite PET packaging box material as claimed in claim 4, characterized in that: the cold plasma pretreatment conditions are as follows: the vacuum degree is 10.33Pa, N2The flow rate is 35mL/min, the power is 50W, and the time is 30 min.
7. A recyclable composite PET packaging box material as claimed in claim 1, characterized in that: the temperature of each section of the double-screw extruder barrel in the step 5 is sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the rotation speed of the screw is 100 rpm.
8. A recyclable composite PET packaging box material as claimed in claim 1, characterized in that: the vacuum degree of the magnetron sputtering background in the step 6 is 5.0 multiplied by 10-3Pa, power supply power of 100-400W, working air pressure of 1 × 10-2～5×10- 2Pa, and the deposition time is 10-120 min.
9. A recyclable composite PET packaging box material as claimed in claim 1, characterized in that: the thickness of the silicon oxide film in the step 6 is 50-300 nm.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115613352A (en) * | 2022-10-10 | 2023-01-17 | 余翔 | Breathable down-proof fabric and preparation method thereof |
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