CN114752187B - 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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- CN114752187B CN114752187B CN202111642877.7A CN202111642877A CN114752187B CN 114752187 B CN114752187 B CN 114752187B CN 202111642877 A CN202111642877 A CN 202111642877A CN 114752187 B CN114752187 B CN 114752187B
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- 239000000463 material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 22
- 238000004806 packaging method and process Methods 0.000 title claims abstract description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 88
- 229920006231 aramid fiber Polymers 0.000 claims abstract description 77
- 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
- 238000001746 injection moulding Methods 0.000 claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 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
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 25
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 24
- 238000002156 mixing Methods 0.000 claims abstract description 24
- 238000006116 polymerization 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 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 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
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims description 51
- 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 32
- 239000000243 solution Substances 0.000 claims description 31
- 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 30
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 229920005604 random copolymer Polymers 0.000 claims description 22
- 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
- 238000001035 drying Methods 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
- 238000007599 discharging Methods 0.000 claims description 12
- 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
- CNNKNWHLJIMTLF-UHFFFAOYSA-N C(C)(=O)OCC.C(CCCCCCCCCCC)S Chemical compound C(C)(=O)OCC.C(CCCCCCCCCCC)S CNNKNWHLJIMTLF-UHFFFAOYSA-N 0.000 claims description 10
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000011049 filling 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
- 238000002425 crystallisation Methods 0.000 abstract description 8
- 230000008025 crystallization Effects 0.000 abstract description 8
- 230000006911 nucleation Effects 0.000 abstract description 7
- 238000010899 nucleation Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004064 recycling Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 229920006351 engineering plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 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
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer 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
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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
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- 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
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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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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 glycol for reaction; uniformly mixing with terephthalic acid, and then adding the mixture into a polymerization reaction kettle to react to obtain modified PET; vacuum drying the modified PET, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, carrying out melt extrusion granulation in a double-screw extruder, and carrying out injection molding by using an injection molding machine to obtain a standard sample; and (3) taking a modified PET sample, and 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 packaging box material. According to the invention, by adding the nano silicon carbide particles, heterogeneous nucleation is achieved, the nucleation mechanism of PET is changed, the crystallinity and crystallization rate of PET are improved, meanwhile, the thermal stability and mechanical property of the material are improved, and meanwhile, the silicon oxide film is deposited on the surface of 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 performances such as wear resistance, heat resistance, electrical insulation, chemical resistance and the like, and is widely used in the fields of synthetic polyester fiber, film manufacturing, civil blow molding and the like. The PET has the defects of slow crystallization rate, high temperature of a forming die, long forming period, poor impact performance, large water absorption and the like, so that the PET is limited in application in the field of engineering plastics. In addition, PET flows easily in the injection molding process, and normal injection molding of PET resin can be realized only by improving the crystallization rate of PET. At present, only a few large companies such as Dupont and ICI have the technology, and mainly the chemical nucleation of organic carboxylate or high polymer ionomer is utilized to improve the crystallization rate of PET, but the crystallization rate can break the molecular chain of PET and locally degrade the PET. In addition, the selling price of PET engineering plastics of the companies in China is very high, so that the consumption of the domestic PET engineering plastics cannot be greatly increased to a great extent. On the other hand, PET, as a non-degradable material, is recycled with the development of "plastic restriction", which is one of the problems to be solved.
Disclosure of Invention
The technical problems to be solved are as follows: aiming at the technical problems that the existing PET material is low in crystallization rate and difficult to recycle, the nano silicon carbide particles are added, so that heterogeneous nucleation is achieved, the nucleation mechanism of PET is changed, the crystallinity and crystallization rate of PET are improved, meanwhile, the thermal stability and mechanical property of the PET material are improved, and meanwhile, a silicon oxide film is deposited on the surface of PET through a magnetron sputtering method, so that the water resistance is improved, and the recycling effect is improved.
The technical scheme is as follows: a preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 1-2 h;
step 2: uniformly mixing with terephthalic acid, adding 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 h;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 270-280 ℃, and reacting for 1-2 h;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, carrying out melt extrusion granulation in a double-screw extruder, and carrying out injection molding by an injection molding machine to obtain a standard sample, wherein the temperature of a mold is 70 ℃;
step 6: taking a modified PET sample, placing the modified PET sample into a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the microwave plasma chemical vapor deposition adopts power supply with the power of 500-5000W, and tetramethyl disiloxane and O 2 The flow ratio of (2) is 1:120, and the working pressure is 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 to 0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol.
Further, in the step 5, the ratio of the modified PET to the modified aramid fiber 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-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 2-3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere;
(4) After pretreatment, placing the aramid fiber into 0.5-3% of ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Further, the molar ratio of the glycidyl methacrylate, the n-butyl methacrylate, the maleic anhydride, the azobisisobutyronitrile and the dodecyl mercaptan is 1:3:1:0.02:0.2.
Further, the conditions of the cold plasma pretreatment are as follows: vacuum degree of 10.33Pa, N 2 The flow rate was 35mL/min, the power was 50W, and the time was 30min.
Further, in the step 5, the temperatures of the sections of the barrel of the twin-screw extruder are set as follows: 240 ℃, 260 ℃, 250 ℃, and the screw rotation speed is 100rpm.
Further, the magnetron sputtering background vacuum degree in the step 6 is 5.0x10 -3 Pa, 100-400W of power supply and 1X 10 working air pressure -2 ～5×10 -2 Pa, deposition time is 10-120 min.
Further, the thickness of the silicon oxide film in the step 6 is 50-300 nm.
The beneficial effects are that:
1. according to the invention, by adding the nano silicon carbide particles, heterogeneous nucleation is achieved, the nucleation mechanism of PET is changed, the crystallinity and crystallization rate of PET are improved, and the thermal stability and mechanical properties of the material are improved.
2. According to the invention, plasma activation is firstly carried out on the surface of the aramid fiber, active groups such as free radicals are introduced on the surface by adopting a ternary random copolymer product, the aramid fiber is immediately immersed into a ternary random copolymer product solution for post graft polymerization after being taken out when vacuum is released, and a flexible interface layer is formed between the aramid fiber and the 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 PET surface by a magnetron sputtering method, so that the water resistance is improved, and the recycling effect is improved.
Detailed Description
Example 1
A preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 1h;
step 2: uniformly mixing with terephthalic acid, adding into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 250 ℃, and carrying out esterification reaction for 1h; the molar ratio of terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.05 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 270 ℃, and reacting for 1h;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:1, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 50nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 100W of power supply, 1X 10 working air pressure -2 Pa, deposition time 10min; the microwave plasma chemical vapor deposition adopts the power supply with the power of 500W, and the tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 20Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 2 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into a 0.5% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain a modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Example 2
A preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 1.5h;
step 2: uniformly mixing with terephthalic acid, adding into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 255 ℃, and carrying out esterification reaction for 1.5h; the molar ratio of terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.1 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, enabling the vacuum degree to rise to 20Pa, controlling the temperature to 275 ℃, and reacting for 1.5h;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and 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, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 100nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 200W of power supply, 2X 10 of working air pressure -2 Pa, deposition time 30min; the microwave plasma chemical vapor deposition adopts the power supply with the power of 1000W, and the tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 30Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into a 1% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain a modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Example 3
A preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 1.5h;
step 2: uniformly mixing with terephthalic acid, adding into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 255 ℃, and carrying out esterification reaction for 1.5h; the molar ratio of terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.15 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, enabling the vacuum degree to rise to 20Pa, controlling the temperature to 275 ℃, and reacting for 1.5h;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and 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, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 150nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 300W of power supply, 3X 10 working air pressure -2 Pa, deposition time 50min; the microwave plasma chemical vapor deposition adopts the power of 2000W, tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 40Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into 1.5% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Example 4
A preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 1h;
step 2: uniformly mixing with terephthalic acid, adding into a polymerization reaction kettle, sealing the polymerization reaction kettle, pressurizing and heating to 0.25MPa and 250 ℃, and carrying out esterification reaction for 1h; the molar ratio of terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.15 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 270 ℃, and reacting for 1h;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharging valve at the bottom of the kettle for discharging, and cooling to manufactureGranulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:1, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 200nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 200W of power supply, 4X 10 working air pressure -2 Pa, deposition time 80min; microwave plasma chemical vapor deposition adopts power supply with power of 3000W, tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 50Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow rate is 35mL/min, the power is 50W, and the time is30min；
(4) After pretreatment, placing the aramid fiber into 2% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Example 5
A preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 2h;
step 2: uniformly mixing with terephthalic acid, adding 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 terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.15 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 280 ℃, and reacting for 2 hours;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 250nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 400W of power supply, 4X 10 working air pressure -2 Pa, deposition time 100min; the microwave plasma chemical vapor deposition adopts the power of 4000W,tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 50Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into 2.5% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Example 6
A preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 2h;
step 2: uniformly mixing with terephthalic acid, adding 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 terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.2 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 280 ℃, and reacting for 2 hours;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 300nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 400W of power supply, 5X 10 of working air pressure -2 Pa, deposition time 120min; microwave plasma chemical vapor deposition adopts power supply with power of 5000W, tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 60Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into a 3% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain a modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Comparative example 1
The comparative example differs from example 6 in that unmodified aramid fibers are used, specifically as follows:
a preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 2h;
step 2: uniformly mixing with terephthalic acid, adding 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 terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.2 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 280 ℃, and reacting for 2 hours;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the aramid fiber is 8:2, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 6: taking a modified PET sample, and 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 300nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 400W of power supply, 5X 10 of working air pressure -2 Pa, deposition time 120min; microwave plasma chemical vapor deposition adopts power supply with power of 5000W, tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 60Pa.
Comparative example 2
This comparative example differs from example 6 in that no silicon oxide film was deposited, specifically as follows:
a preparation method of a recyclable composite PET packaging box material comprises the following steps:
step 1: dispersing nano silicon carbide in glycol, and reacting for 2h;
step 2: uniformly mixing with terephthalic acid, adding 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 terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.2 per mill of the total mass of terephthalic acid and ethylene glycol;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 280 ℃, and reacting for 2 hours;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; and then injection molding is carried out on the standard sample by an injection molding machine, wherein 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-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into a 3% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain a modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
Comparative example 3
The difference between this comparative example and example 6 is that no nano silicon carbide is doped, specifically as follows:
a preparation method of a recyclable composite PET packaging 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 terephthalic acid to ethylene glycol is 1:1.7;
step 2: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, increasing the vacuum degree to 20Pa, controlling the temperature to 280 ℃, and reacting for 2 hours;
step 3: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 4: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET and the modified aramid fiber in a high-speed mixer, wherein the ratio of the modified PET to the modified aramid fiber is 8:2, and carrying out melt extrusion granulation in a double-screw extruder, wherein the temperatures of each section of a double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃ and the screw rotation speed is 100rpm; then an injection molding machine is used for injection molding to form a standard sample, and the temperature of the mold is 70 ℃;
step 5: taking a modified PET sample, and 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 300nm; wherein the vacuum degree of the magnetron sputtering background is 5.0 multiplied by 10 -3 Pa, 400W of power supply, 5X 10 of working air pressure -2 Pa, deposition time 120min; microwave plasma chemical vapor deposition adopts power supply with power of 5000W, tetramethyl disiloxane and O 2 The flow ratio of (2) was 1:120, and the operating pressure was 60Pa.
The preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid; the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecyl mercaptan is 1:3:1:0.02:0.2;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere, wherein the pretreatment conditions are as follows: vacuum degree of 10.33Pa, N 2 The flow is 35mL/min, the power is 50W, and the time is 30min;
(4) After pretreatment, placing the aramid fiber into a 3% ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain a modified aramid fiber; wherein, the grafting power is 100W and the time is 10min. And (3) testing and analyzing the mechanical properties of the material by adopting an electronic universal testing machine, and preparing and testing samples according to the standard GB/T1040-2018.
And (3) 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 various embodiments
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Claims (7)
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 glycol, and reacting for 1-2 h;
step 2: uniformly mixing with terephthalic acid, adding 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 h;
step 3: starting a vacuum pump to perform pre-polycondensation, opening a large vacuum valve after the vacuum degree reaches 300Pa, raising the vacuum degree to 20Pa, controlling the temperature to 270-280 ℃, and reacting for 1-2 h;
step 4: after the reaction is finished, vacuum defoamation is carried out, N 2 Pressurizing, opening a discharge valve at the bottom of the kettle for discharging, and cooling and granulating to obtain modified PET;
step 5: vacuum drying the modified PET at 120 ℃, uniformly mixing the modified PET with the modified aramid fiber in a high-speed mixer, carrying out melt extrusion granulation in a double-screw extruder, and carrying out injection molding by an injection molding machine to obtain a standard sample, wherein the temperature of a mold is 70 ℃;
step 6: taking a modified PET sample, placing the modified PET sample into a microwave plasma chemical vapor deposition device for magnetron sputtering deposition of a silicon oxide film, wherein the microwave plasma chemical vapor deposition adopts power supply with power of 500-5000W, and tetramethyl disiloxane and O 2 The flow ratio of (2) is 1:120, and the working pressure is 20-60 Pa;
the preparation method of the modified aramid fiber comprises the following steps:
(1) Adding ethyl acetate into a four-neck flask, filling nitrogen for protection, heating to about 50 ℃ in a water bath, magnetically stirring, adding three monomer glycidyl methacrylate, n-butyl methacrylate, maleic anhydride, azodiisobutyronitrile and dodecyl mercaptan ethyl acetate solutions into the four-neck flask from a constant pressure dropping funnel, stirring for 0.5h, heating to 60 ℃ and stirring for 3h, and stopping reacting to obtain viscous liquid;
(2) Pouring the mixture into normal hexane solution for washing, removing upper liquid, repeating for 2-3 times, and drying in vacuum to constant weight to obtain a ternary random copolymer product;
(3) Placing aramid fiber into cold plasma cavity, heating to 90deg.C, and heating to N 2 Carrying out cold plasma pretreatment on the aramid fiber under the atmosphere;
(4) After pretreatment, placing the aramid fiber into 0.5-3% of ternary random copolymer product/acetone solution for soaking, drying the solvent, and then carrying out cold plasma grafting on the fiber to obtain modified aramid fiber; wherein, the grafting power is 100W and the time is 10min.
2. The method for preparing the recyclable composite PET packaging box material, as set forth in claim 1, is characterized in that: the molar ratio of terephthalic acid to ethylene glycol is 1:1.7; the mass of the nano silicon carbide accounts for 0.05 to 0.2 per mill of the total mass of the terephthalic acid and the ethylene glycol.
3. The method for preparing the recyclable composite PET packaging box material, as set forth in claim 1, is characterized in that: the molar ratio of the glycidyl methacrylate to the n-butyl methacrylate to the maleic anhydride to the azobisisobutyronitrile to the dodecylmercaptan is 1:3:1:0.02:0.2.
4. The method for preparing the recyclable composite PET packaging box material, as set forth in claim 1, is characterized in that: the conditions of the cold plasma pretreatment are as follows: vacuum degree of 10.33Pa, N 2 The flow rate was 35mL/min, the power was 50W, and the time was 30min.
5. The method for preparing the recyclable composite PET packaging box material, as set forth in claim 1, is characterized in that: in the step 5, the temperatures of the sections of the double-screw extruder barrel are sequentially set as follows: 240 ℃, 260 ℃, 250 ℃, and the screw rotation speed is 100rpm.
6. The method for preparing the recyclable composite PET packaging box material, as set forth in claim 1, is characterized in that: the vacuum degree of the magnetron sputtering background in the step 6 is 5.0 multiplied by 10 -3 Pa, 100-400 of power supply power W, working air pressure 1 x 10 -2 ～5×10 -2 Pa, deposition time is 10-120 min.
7. The method for preparing the recyclable composite PET packaging box material, as set forth in claim 1, is characterized in that: the thickness of the silicon oxide film in the step 6 is 50-300 nm.
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