CN115353722B - Glass fiber reinforced PET material and preparation method thereof - Google Patents
Glass fiber reinforced PET material and preparation method thereof Download PDFInfo
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- CN115353722B CN115353722B CN202210861012.8A CN202210861012A CN115353722B CN 115353722 B CN115353722 B CN 115353722B CN 202210861012 A CN202210861012 A CN 202210861012A CN 115353722 B CN115353722 B CN 115353722B
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- 239000003365 glass fiber Substances 0.000 title claims abstract description 146
- 239000000463 material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 83
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 38
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 26
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 25
- 239000007822 coupling agent Substances 0.000 claims abstract description 21
- 210000002381 plasma Anatomy 0.000 claims abstract description 20
- 239000004970 Chain extender Substances 0.000 claims abstract description 18
- 239000002667 nucleating agent Substances 0.000 claims abstract description 18
- 239000000314 lubricant Substances 0.000 claims abstract description 16
- 238000005303 weighing Methods 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000001125 extrusion Methods 0.000 claims description 9
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 235000019441 ethanol Nutrition 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 230000010355 oscillation Effects 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000004580 weight loss Effects 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- -1 methacryloxy group Chemical group 0.000 claims description 6
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- 230000007935 neutral effect Effects 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 5
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 4
- 238000010079 rubber tapping Methods 0.000 claims description 4
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical group [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims description 4
- 239000004299 sodium benzoate Substances 0.000 claims description 4
- 235000010234 sodium benzoate Nutrition 0.000 claims description 4
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 3
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 3
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 2
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- 125000003277 amino group Chemical group 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 125000003700 epoxy group Chemical group 0.000 claims 1
- 230000003014 reinforcing effect Effects 0.000 claims 1
- 125000003396 thiol group Chemical group [H]S* 0.000 claims 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 13
- 239000011159 matrix material Substances 0.000 abstract description 13
- 230000002195 synergetic effect Effects 0.000 abstract description 4
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 description 58
- 239000005020 polyethylene terephthalate Substances 0.000 description 58
- 239000002131 composite material Substances 0.000 description 18
- 238000012545 processing Methods 0.000 description 11
- 238000009832 plasma treatment Methods 0.000 description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000005516 engineering process Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 5
- 238000005530 etching Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
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- 150000002500 ions Chemical class 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000004594 Masterbatch (MB) Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 229920006351 engineering plastic Polymers 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
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- 230000003746 surface roughness Effects 0.000 description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 description 1
- 229920002748 Basalt fiber Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004593 Epoxy Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 229920003182 Surlyn® Polymers 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 238000012289 standard assay Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000012745 toughening agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
- C08J5/08—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials glass fibres
-
- 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
-
- 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
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Nanotechnology (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention discloses a glass fiber reinforced PET material, which is characterized in that: comprises 70 to 85 parts of PET resin, 10 to 25 parts of glass fiber, 1.0 to 5.0 parts of multi-wall carbon nano tube, 0.5 to 1.0 part of chain extender, 0.5 to 1.5 parts of nucleating agent, 0.1 to 0.5 part of lubricant, 0.3 to 0.6 part of antioxidant and 0.1 to 0.5 part of coupling agent. The invention also discloses a preparation method of the glass fiber reinforced PET material, which utilizes the characteristic of high ionization of plasmas to treat glass fibers, improves electrostatic adsorption of the multi-wall carbon nanotubes on the surfaces of the glass fibers, enhances the combination effect of the modified glass fibers and the modified multi-wall carbon nanotubes, promotes the synergistic effect between the modified glass fibers and the modified multi-wall carbon nanotubes, improves the interface bonding strength of the glass fibers and a PET resin matrix through the multi-wall carbon nanotubes on the surfaces of the glass fibers, improves the compatibility of the glass fibers and the PET matrix, and enhances the strength and toughness of the PET material.
Description
Technical Field
The invention relates to a method for modifying and processing PET (polyethylene terephthalate) material, in particular to a glass fiber reinforced PET material and a preparation method thereof, belonging to the technical field of polymer composite material processing.
Background
Micrometer fibers such as glass fibers, carbon fibers, basalt fibers and the like have the excellent characteristics of light weight, high strength and good temperature resistance, so that the micrometer fibers are widely applied to various fields, wherein the application of the glass fibers is mainly used for enhancing and modifying the performance of engineering materials. At present, although the properties of the composite material are improved compared with those of a pure polymer material, the properties of the composite material are far lower than those of glass fiber fibers, in particular to the strength of the material. The reasons are as follows: 1. the compatibility of the glass fiber and the matrix resin is poor, so that the stress transmission between the glass fiber and the matrix resin is influenced; 2. there is usually a certain free volume between the glass fibers and the matrix resin where stresses cannot be transferred; 3. micron sized glass fibers have limited collective reinforcement areas. It is therefore important to increase the compatibility of the glass fibers with the matrix resin and to increase the contact area between the glass fibers and the matrix resin in the preparation of the composite.
Chinese patent CN109721958a discloses a high-performance PET engineering plastic, comprising the following components in parts by weight: 52.75-88.25 parts of PET resin, 10-40 parts of glass fiber, 1.0-4.0 parts of nucleating agent, 0-0.25 part of hydrolysis resistance agent, 0.75-3.0 parts of antioxidant, 1.6 parts of KH550 treated talcum powder and 0.8 part of surlyn resin, and the obtained composite material improves the crystallization rate of PET, shortens the molding cycle and has the tensile strength of only 110MPa from the embodiment.
Chinese patent CN106810829B discloses a modified glass fiber reinforced PET composite material, comprising the following components in parts by weight: 30-60 parts of PET resin, 0-10 parts of PBT resin, 25-45 parts of glass fiber, 5-15 parts of hollow glass microsphere, 0-5 parts of toughening agent, 5-10 parts of nucleating agent and 5-10 parts of surface improver, and the prepared material improves the compatibility of glass fiber and resin and reduces the exposed proportion of glass fiber, but in the examples, the tensile strength and bending strength of the sample are only 111MPa and 171MPa.
Chinese patent CN103275468B discloses an environment-friendly flame-retardant glass fiber reinforced PET material, comprising the following components in parts by weight: 40-70 parts of recycled PET resin, 15-45 parts of modified glass fiber, 8-30 parts of flame retardant, 0.3-2 parts of crystallization nucleating agent, 0.3-2 parts of lubricant, 0.3-1 part of antioxidant and 0.1-1 part of chain extender, and the prepared composite material uses recycled PET as a matrix material, is environment-friendly, but in the embodiment, the tensile strength of a sample is only 125MPa, and the bending strength is 179MPa.
The PET composite material disclosed in the patent is obviously improved in other use performances after being modified, but various strengths of the prepared relative product are not improved. Therefore, there is a need for improvements in the existing methods of producing PET materials to improve the performance of PET materials.
Disclosure of Invention
The invention aims to solve the problems and provide a glass fiber reinforced PET material and a preparation method thereof, so as to conveniently improve the tensile strength and the shock resistance of the PET material and improve the stability.
The technical scheme of the invention is as follows:
A glass fiber reinforced PET material is characterized in that: the PET material comprises the following components in parts by weight: 70 to 85 parts of PET resin, 10 to 25 parts of modified glass fiber, 1.0 to 5.0 parts of modified multi-wall carbon nano tube, 0.5 to 1.0 part of chain extender, 0.5 to 1.5 parts of nucleating agent, 0.1 to 0.5 part of lubricant, 0.3 to 0.6 part of antioxidant and 0.1 to 0.5 part of coupling agent; among the above components, the PET resin may be virgin PET resin or recycled PET resin, and has an intrinsic viscosity of 0.45 to 1.1dl/g, preferably 0.6 to 0.8dl/g.
Further, the glass fiber reinforced PET material described above, wherein: the lubricant is at least one of saturated hydrocarbon, metal soap, aliphatic phenol, fatty acid, fatty alcohol and silicone powder.
Preferably, the lubricant is compounded by silicone master batch and pentaerythritol stearate, and the weight ratio of the silicone master batch to the pentaerythritol stearate is 2:3.
Further, the glass fiber reinforced PET material described above, wherein: the chain extender is one of the Pasteur chain extender ADR-4370S, ADR-4370F and ADR-4468.
Further, the glass fiber reinforced PET material described above, wherein: the nucleating agent is sodium benzoate.
Further, the glass fiber reinforced PET material described above, wherein: the antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 126, antioxidant 225 and antioxidant 215.
Further, the glass fiber reinforced PET material described above, wherein: the coupling agent is a silane coupling agent, and the general formula is RSiX3; wherein R represents amino, mercapto, vinyl, epoxy, cyano or methacryloxy, X represents hydrolyzable alkoxy, can improve the adhesive properties of glass fibers and resins, greatly improve the strength, electrical, water resistance, weather resistance and other properties of glass fiber reinforced composites, and has remarkable effect on improving the mechanical properties of the composites even in a wet state, can improve the processing technology, increase the elongation and tear strength of the products, and improve the impact properties.
The invention also provides a preparation method of the glass fiber reinforced PET material, which comprises the following steps:
(1) Weighing each component according to the weight ratio, putting a proper amount of sample into a dry and clean weighing bottle, sleeving a clean small paper strip on the weighing bottle, putting the weighing bottle on a balance weighing disc to weigh the mass ml of the weighing bottle, taking out the weighing bottle, taking the bottle cap above a sample container, tilting the weighing bottle, tapping the bottle cap, slowly dropping the sample into the container, tapping the bottle cap when the required weight is approached, dropping the sample adhered to the bottle cap, slowly standing the weighing bottle, covering the bottle cap, and weighing the mass m2 of the weighing bottle. The difference between the two qualities is the quality of a first sample poured into a container, multiple samples can be weighed continuously by the same method, and the materials which are easy to absorb water, easy to oxidize or easy to react with carbon dioxide are weighed by adopting the decreasing weighing method, so that inaccurate weighing is avoided.
(2) Adding the multi-wall carbon nano tube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall and grafting hydroxyl functional groups, performing ultrasonic dispersion for 10min, stirring at 80 ℃ for 24h, wherein the concentration range of the multi-wall carbon nano tube is 2% -10%, performing filtration treatment, washing the obtained filtrate with 0.1-0.3 mol/L NaOH solution for multiple times, washing with deionized water to be neutral, and performing vacuum drying at 80 ℃ for 48 h.
(3) Placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 5-10 min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: 40% N 2 +60% Ar, the vacuum degree is 0.6Pa, the power is 100W, the weight loss rate of the glass fiber after treatment is controlled to be 0.1% -0.5%, and the modified glass fiber with the length of 2-5 mm and the diameter of 5-13 μm is obtained by chopping the glass fiber after plasma treatment.
(4) Dispersing the modified multi-wall carbon nano tube processed in the step (2) in ethanol solution with the volume fraction of 40-60%, adding the modified glass fiber processed by the plasmas obtained in the step (3), carrying out reaction by stirring, keeping the ratio of the modified glass fiber to the modified multi-wall carbon nano tube within the range of 2-25, putting the mixture in an environment with the temperature of 0-4 ℃ for refrigerating for 24 hours, and then freeze-drying to obtain the glass fiber composite coated by the multi-wall carbon nano tube.
(5) And (3) sequentially placing the PET resin, the glass fiber compound in the step (4), the antioxidant, the chain extender, the nucleating agent, the lubricant and the coupling agent into a high-speed mixer, mixing at a high speed for 5-20 min, then putting into a double-screw extruder, controlling the screw rotating speed at 150-300 rpm, and finally obtaining the multi-wall carbon nano tube glass fiber modified reinforced PET material through melt extrusion and granulation.
Further, the preparation method of the glass fiber reinforced PET material comprises the following steps: the double-screw extruder is provided with 10 temperature control areas, and the temperature control range is 220-260 ℃.
Further, the preparation method of the glass fiber reinforced PET material comprises the following steps: the double-screw extruder is provided with two vacuumizing ports in total, the first vacuumizing port is arranged at the beginning of the melting section, and the second vacuumizing port is arranged at the metering section.
Therefore, by adopting the technical scheme of the invention, the polarity of the glass fiber is improved, the etching degree of the surface of the glass fiber can be controlled by adjusting the treatment time, and the carboxyl and hydroxyl groups are introduced to be dispersed in the solution, so that the integral electronegativity ensures that the modified multi-wall carbon nano tube can be uniformly dispersed in the solution, namely, the multi-wall carbon nano tube can be uniformly coated on the surface of the modified glass fiber by utilizing the electrostatic effect, and the carboxyl and hydroxyl groups on the surface of the multi-wall carbon nano tube can also react with the hydroxyl and carboxyl groups in the PET resin matrix to form a more stable structure, thereby enhancing the strength and toughness of the PET material.
Compared with the prior art, after the technical scheme is adopted, positive ions are introduced by utilizing plasma modification, and then the combination is carried out by utilizing the principle of electrostatic adsorption, so that on one hand, the combination effect of the modified glass fiber and the modified multi-wall carbon nano tube is enhanced, and on the other hand, the modified multi-wall carbon nano tube can be uniformly distributed on the surface of the modified glass fiber by utilizing the principle of electrostatic adsorption, the defect that the original multi-wall carbon nano tube is not easy to disperse is overcome, the synergistic effect between the modified glass fiber and the modified multi-wall carbon nano tube is promoted, and the effect of 1+1>2 is realized; and after the glass fiber is treated by the plasma treatment method, electron, ion and plasma can be utilized to generate collision reaction with the surface of the glass fiber to generate super desorption, so that the etching effect of the surface of the glass fiber is enhanced, the surface roughness of the glass fiber is effectively improved, the surface geometry of the glass fiber is changed, the surface area of the glass fiber is further enlarged, the contact area of the glass fiber and a substrate is enhanced, the adhesiveness is improved, the good dispersibility of the multi-wall carbon nano tube is ensured, and the compatibility of the glass fiber and a PET matrix is improved.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments in order to make the objects, technical solutions and advantages of the present invention more apparent, but it should not be construed that the scope of the above subject matter of the present invention is limited to only the following examples.
Wherein, the raw materials used in the following examples are all commercial or self-made, and the specific implementation cases adopt the following raw materials: the PET resin is preferably regenerated PET resin with an intrinsic viscosity of 0.68dl/g, and rPET-PCR78AP produced by Ningbo fast new material company is selected; the glass fiber is 303H produced by Chongqing International composite material Co., ltd, the fiber length is 3mm, and the monofilament diameter is 10 μm; the multi-wall carbon nano tube is XFQ041 industrial multi-wall carbon nano tube produced by Nanjing Xianfeng nano company; the chain extender is JoncrylADR-4468 produced by Basoff company, has nine active groups and can be subjected to a linking reaction with the engineering plastic reaction groups to form a branched molecular structure, so that the mechanical property of the material is improved, and the processing stability and mechanical property of the return material are improved; the nucleating agent is sodium benzoate produced by Nanjing pine crown biotechnology limited company; the antioxidant is selected from antioxidant Irganox1010 and antioxidant Irgafos168 produced by Basff company of Germany, and the proportion of the synergistic effect of main and auxiliary antioxidants is adopted; the coupling agent is CG-902 produced by Nanjing Chen industrial organic silicon, which is totally called aminopropyl methyl diethoxy silane.
Example 1
(1) Weighing the components according to the weight: 5 parts of multi-wall carbon nano tube, 10 parts of glass fiber and 0.5 part of aminosilane coupling agent CG-902.
(2) Adding the multiwall carbon nanotube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall and grafting carboxyl hydroxyl functional groups, dispersing for 10min by ultrasonic, stirring for 24h at 80 ℃, filtering, washing the obtained filtrate for multiple times by using 0.1-0.3 mol/L NaOH solution, washing to be neutral by using deionized water, and vacuum drying for 48h at 80 ℃ to obtain the modified multiwall carbon nanotube.
(3) Placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 5-10 min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: n 2 (40%) +Ar (60%), the reaction time is 4min, and the weight loss rate of the glass fiber after treatment is controlled to be 0.1% -0.5%, so that the glass fiber after plasma treatment is obtained.
(4) Dispersing the modified multi-wall carbon nano tube obtained in the step (2) in ethanol solution with the volume fraction of 40-60%, adding the glass fiber treated by the plasmas obtained in the step (3), stirring for reaction, placing in an environment with the temperature of 0-4 ℃ for refrigerating for 24 hours, and freeze-drying to obtain the multi-wall carbon nano tube coated glass fiber compound.
(5) Weighing the components according to the weight: 85 parts of recovered PET resin, 15 parts of glass fiber compound coated by the multi-wall carbon nano tube in (4), 0.5 part of antioxidant 225, 0.5 part of chain extender ADR-4468, 1 part of nucleating agent sodium benzoate, 0.5 part of lubricant and coupling agent CG-9020.5 parts, mixing in a high-speed mixer for 5-20 min, then putting into a double-screw extruder, controlling the screw rotating speed to be 150-300 rpm, and carrying out melt extrusion and granulation to obtain the multi-wall carbon nano tube modified reinforced PET compound.
The processing technology of the double-screw extruder is as follows: the twin-screw extruder has 10 temperature control areas, and the temperature control range is 220-260 ℃.
Example 2
(1) Weighing the components according to the weight: 1 part of multi-wall carbon nano tube, 25 parts of glass fiber and 0.5 part of aminosilane coupling agent CG-902.
(2) Adding the multiwall carbon nanotube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall, grafting hydroxyl functional groups and the like, dispersing for 10min by ultrasonic, stirring for 24h at 80 ℃, filtering, washing the obtained filtrate with 0.1-0.3 mol/L NaOH solution for multiple times, washing to be neutral by deionized water, and vacuum drying at 80 ℃ for 48h to obtain the modified multiwall carbon nanotube.
(3) Placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 5-10 min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: n 2 (40%) +Ar (60%), the reaction time is 4min, and the weight loss rate of the glass fiber after treatment is controlled to be 0.1% -0.5%, so that the glass fiber after plasma treatment is obtained.
(4) Dispersing the modified multi-wall carbon nano tube obtained in the step (2) in ethanol solution with the volume fraction of 40-60%, adding the glass fiber treated by the plasmas obtained in the step (3), stirring for reaction, placing in an environment with the temperature of 0-4 ℃ for refrigerating for 24 hours, and freeze-drying to obtain the multi-wall carbon nano tube coated glass fiber compound.
(5) Weighing the components according to the weight: 74 parts of recovered PET resin, 26 parts of glass fiber composite coated by multi-wall carbon nano tubes in (4), 0.5 part of antioxidant, 0.5 part of chain extender, 1 part of nucleating agent, 0.5 part of lubricant and 0.5 part of coupling agent, mixing for 5-20 min in a high-speed mixer, then putting into a double-screw extruder, controlling the screw rotating speed to be 150-300 rpm, and performing melt extrusion and granulation to obtain the multi-wall carbon nano tube modified reinforced PET composite.
The processing technology of the double-screw extruder is as follows: the double-screw extruder is provided with 10 temperature control areas, and the temperature control range is 220-260 DEG C
Example 3
(1) Weighing the components according to the weight: 2.5 parts of multi-wall carbon nano tube, 20 parts of glass fiber and 0.5 part of aminosilane coupling agent CG-902.
(2) Adding the multiwall carbon nanotube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall, grafting hydroxyl functional groups and the like, dispersing for 10min by ultrasonic, stirring for 24h at 80 ℃, washing the mixture subjected to filtration treatment for multiple times by using 0.1-0.3 mol/L NaOH solution, washing to be neutral by using deionized water, and placing the mixture in 80 ℃ for vacuum drying for 48h to obtain the modified multiwall carbon nanotube.
(3) Placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 10min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: n 2 (40%) +Ar (60%), the reaction time is 4min, and the weight loss rate of the glass fiber after treatment is controlled to be 0.1% -0.5%, so that the glass fiber after plasma treatment is obtained.
(4) Dispersing the modified multi-wall carbon nano tube obtained in the step (2) in ethanol solution with the volume fraction of 40-60%, adding the glass fiber treated by the plasmas obtained in the step (3), stirring for reaction, placing in an environment with the temperature of 0-4 ℃ for refrigerating for 24 hours, and freeze-drying to obtain a multi-wall carbon nano tube coated glass fiber compound;
(5) Weighing the components according to the weight: 77.5 parts of recycled PET resin, 22.5 parts of glass fiber compound coated by the multi-wall carbon nano tube in (4), 0.5 part of antioxidant, 0.5 part of chain extender, 1 part of nucleating agent, 0.5 part of lubricant and 0.5 part of coupling agent are mixed in a high-speed mixer for 5-20 min, then the mixture is put into a double-screw extruder, the screw rotating speed is controlled at 150-300 rpm, and the multi-wall carbon nano tube modified reinforced PET compound is obtained through melt extrusion and granulation.
The processing technology of the double-screw extruder is as follows: the twin-screw extruder has 10 temperature control areas, and the temperature control range is 220-260 ℃.
Example 4
(1) Weighing the components according to the weight: 5 parts of multi-wall carbon nano tube, 25 parts of glass fiber and 0.5 part of aminosilane coupling agent CG-902.
(2) Adding the multiwall carbon nanotube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall, grafting hydroxyl functional groups, dispersing by ultrasonic for 10min, stirring for 24h at 80 ℃, filtering, washing the obtained filtrate with 0.1-0.3 mol/L NaOH solution for multiple times, washing with deionized water to neutrality, and vacuum drying at 80 ℃ for 48h to obtain the modified multiwall carbon nanotube.
(3) Placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 5-10 min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: n 2 (40%) +Ar (60%), the reaction time was 4min, and the weight loss rate of the glass fiber after the treatment was controlled to be 0.1% -0.5%, to obtain a plasma-treated glass fiber.
(4) Dispersing the modified multi-wall carbon nano tube obtained in the step (2) in ethanol solution with the volume fraction of 40-60%, adding the glass fiber treated by the plasmas obtained in the step (3), stirring for reaction, placing in an environment with the temperature of 0-4 ℃ for refrigerating for 24 hours, and freeze-drying to obtain the multi-wall carbon nano tube coated glass fiber compound.
(5) Weighing the components according to the weight: 70 parts of recovered PET resin, 20 parts of glass fiber composite coated by the multi-wall carbon nano tube in (4), 0.5 part of antioxidant, 0.5 part of chain extender, 1 part of nucleating agent, 0.5 part of lubricant and 0.5 part of coupling agent, mixing for 5-20 min in a high-speed mixer, then putting into a double-screw extruder, controlling the screw rotating speed to be 150-300 rpm, and performing melt extrusion and granulation to obtain the multi-wall carbon nano tube modified reinforced PET composite.
The processing technology of the double-screw extruder is as follows: the twin-screw extruder has 10 temperature control areas, and the temperature control range is 220-260 ℃.
Comparative example 1
(1) Weighing the components according to the weight: 5 parts of multi-wall carbon nano tube, 10 parts of glass fiber and 0.5 part of aminosilane coupling agent CG-902.
(2) Adding the multiwall carbon nanotube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall, grafting carboxyl and other functional groups, dispersing for 10min by ultrasonic, stirring for 24h at 80 ℃, filtering, washing the filtrate with 0.1-0.3 mol/L NaOH solution for multiple times, washing with deionized water to be neutral, and vacuum drying at 80 ℃ for 48h to obtain the modified multiwall carbon nanotube.
(3) Weighing the components according to the weight: 85 parts of recovered PET resin, 10 parts of glass fiber, 5 parts of multi-wall carbon nano tubes in (2), 0.5 part of antioxidant, 0.5 part of chain extender, 1 part of nucleating agent, 0.5 part of lubricant and 0.5 part of coupling agent are mixed in a high-speed mixer for 5-20 min, then the mixture is put into a double-screw extruder, the screw rotating speed is controlled at 150-300 rpm, and the multi-wall carbon nano tube modified glass fiber reinforced PET compound is obtained through melt extrusion and granulation.
The processing technology of the double-screw extruder is as follows: the twin-screw extruder has 10 temperature control areas, and the temperature control range is 220-260 ℃.
Comparative example 2
(1) Weighing the components according to the weight: 5 parts of multi-wall carbon nano tube, 10 parts of glass fiber and 0.5 part of aminosilane coupling agent CG-902.
(2) Placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 5-10 min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: n 2 (40%) +Ar (60%), the reaction time is 4min, and the weight loss rate of the glass fiber after treatment is controlled to be 0.1% -0.5%, so that the glass fiber after plasma treatment is obtained.
(3) Dispersing the multi-wall carbon nano tube in an ethanol solution with the volume fraction of 40-60%, adding the glass fiber treated by the plasmas obtained in the step (2), stirring for reaction, refrigerating for 24 hours in an environment with the temperature of 0-4 ℃, and freeze-drying to obtain the glass fiber composite coated by the multi-wall carbon nano tube.
(4) Weighing the components according to the weight: 85 parts of recovered PET resin, 15 parts of glass fiber composite coated by the multi-wall carbon nano tube in (3), 0.5 part of antioxidant, 0.5 part of chain extender, 1 part of nucleating agent, 0.5 part of lubricant and 0.5 part of coupling agent, mixing for 5-20 min in a high-speed mixer, then putting into a double-screw extruder, controlling the screw rotating speed to be 150-300 rpm, and carrying out melt extrusion and granulation to obtain the multi-wall carbon nano tube modified reinforced PET composite.
The processing technology of the double-screw extruder is as follows: the twin-screw extruder has 10 temperature control areas, and the temperature control range is 220-260 ℃.
Comparative example 3
Weighing the components according to the weight: 85 parts of recovered PET resin, 10 parts of glass fiber, 5 parts of multi-wall carbon nano tube, 0.5 part of antioxidant, 0.5 part of chain extender, 1 part of nucleating agent, 0.5 part of lubricant and 0.5 part of coupling agent are mixed in a high-speed mixer for 5-20 min, then the mixture is put into a double-screw extruder, the screw speed is controlled at 150-300 rpm, and the multi-wall carbon nano tube modified reinforced PET compound is obtained through melt extrusion and granulation.
The processing technology of the double-screw extruder is as follows: the twin-screw extruder has 10 temperature control areas, and the temperature control range is 220-260 ℃.
Table 1 gives the tensile strength, flexural strength and notched impact strength test data for samples of the multiwall carbon nanotube-modified glass fiber reinforced PET materials of examples 1 to 4 and comparative examples 1 to 3.
Tensile strength: according to GB/T1040-2006 standard
Flexural strength: wherein the flexural modulus of elasticity is determined according to GB/T9341-2008 standard
IZOD notched impact Strength: GB/T1843-2008 standard assay
Table 1: physical properties comparison table of comparison cases and implementation cases
| Experimental sample | Tensile Strength (MPa) | Flexural Strength (MPa) | Notched impact (KJ/m 2) |
| Example 1 | 138 | 251 | 16 |
| Example 2 | 135 | 250 | 15.5 |
| Example 3 | 142 | 253 | 17 |
| Example 4 | 150 | 265 | 15.3 |
| Comparative example 1 | 120 | 235 | 15 |
| Comparative example 2 | 116 | 220 | 15.3 |
| Comparative example 3 | 115 | 175 | 7.7 |
As can be seen from table 1: the notched impact strength of examples 1-4 is above 15kJ/m 2, and the tensile strength and bending strength are superior to those of the corresponding comparative examples 1-3, which shows that the formula of the invention can enhance the mechanical properties of PET materials through the combination effect of modified glass fibers and modified multi-wall carbon nanotubes, and can be widely applied to products with higher requirements on strength.
In the technical scheme of the invention, the multi-wall carbon nano tube is oxidized by strong acid, and then the glass fiber is subjected to plasma treatment, so that the surfaces of the glass fiber and the multi-wall carbon nano tube respectively form electropositivity and electronegativity, the combination effect of the modified glass fiber and the modified multi-wall carbon nano tube is enhanced, the defect that the original multi-wall carbon nano tube is difficult to disperse is overcome, and the synergistic effect between the glass fiber and the multi-wall carbon nano tube is promoted. In the state of solution dispersion, stable combination is formed between the two by utilizing electrostatic action, and simultaneously, hydroxyl and carboxyl introduced on the surface of the multi-wall carbon nano tube react with the resin matrix, so that generated acting force can perform good stress transfer among the PET resin, the multi-wall carbon nano tube and the glass fiber.
Thus, by adopting the technical scheme of the invention, on one hand, positive nitrogen ions N + are introduced into the surface of the glass fiber after plasma treatment, so that the surface activity of the glass fiber is increased, the polarity of the glass fiber is improved, and the treatment time can be further adjusted to control the etching degree of the surface of the glass fiber; on the other hand, after the surface of the multi-wall carbon nano tube is cleaned and functionalized by using strong acid, carboxyl and hydroxyl are introduced and dispersed in the solution, so that the surface of the multi-wall carbon nano tube subjected to the strong acid treatment presents electronegativity, the whole electronegativity ensures that the modified multi-wall carbon nano tube can be uniformly dispersed in the solution and is not agglomerated, the multi-wall carbon nano tube can be uniformly coated on the surface of the modified glass fiber by using the electrostatic effect, and the carboxyl and hydroxyl on the surface of the multi-wall carbon nano tube can also react with hydroxyl and carboxyl in a PET resin matrix to form more stable combination, thereby enhancing the strength and toughness of the PET material.
Compared with the prior art, the technical scheme of the invention has the advantages that after the glass fiber is treated by the plasma treatment method, electron, ion and plasma can be utilized to generate a super-desorption effect with the collision reaction of the surface of the glass fiber, so that the etching effect of the surface of the glass fiber is enhanced, the surface roughness of the glass fiber is effectively improved, the surface geometry of the glass fiber is changed, the surface area of the glass fiber is further enlarged, the contact area of the glass fiber and a substrate is enhanced, the adhesiveness is improved, the good dispersibility of the multi-wall carbon nano tube is ensured, and the compatibility of the glass fiber and a PET matrix is improved.
The technical scheme, the working process and the implementation effect of the invention are described in detail, and it is to be noted that the description is only a typical example of the invention, and besides, the invention can also have other various specific embodiments, and all the technical schemes formed by adopting equivalent substitution or equivalent transformation fall within the scope of the invention claimed.
Claims (4)
1. The utility model provides a glass fiber reinforcing PET material which characterized in that: the PET material comprises the following components in parts by weight:
70-85 parts of PET resin;
10-25 parts of modified glass fiber;
1.0 to 5.0 portions of modified multiwall carbon nano tube;
0.5 to 1.0 part of chain extender;
0.5 to 1.5 portions of nucleating agent;
0.1 to 0.5 part of lubricant;
0.3 to 0.6 part of antioxidant;
0.1 to 0.5 part of coupling agent;
The PET resin is virgin PET resin or reclaimed PET resin, and the intrinsic viscosity of the PET resin is 0.45-1.1 dl/g;
The chain extender is one of a Pasteur chain extender ADR-4370S, ADR-4370F and ADR-4468;
The nucleating agent is sodium benzoate;
The antioxidant is at least one of antioxidant 1010, antioxidant 168, antioxidant 126, antioxidant 225 and antioxidant 215;
The lubricant is formed by compounding silicone master batches and pentaerythritol stearate, and the weight ratio of the silicone master batches to the pentaerythritol stearate is 2:3;
The preparation method of the PET material comprises the following steps:
weighing the components according to the weight ratio, putting a proper amount of sample into a dry and clean weighing bottle, sleeving a clean small paper strip on the weighing bottle, putting the weighing bottle on a balance weighing disc to weigh the mass ml of the weighing bottle, taking out the weighing bottle, taking a bottle cap above a sample container, tilting the weighing bottle, tapping a bottle mouth with the bottle cap, slowly dropping the sample into the container, tapping the bottle mouth with the bottle cap when the required weight is approached, enabling the sample adhered to the bottle mouth to drop, slowly standing the weighing bottle, then capping the bottle cap, and weighing the mass m2 of the weighing bottle;
Adding the multiwall carbon nanotube into 85% concentrated sulfuric acid, removing amorphous carbon remained on the side wall and grafting hydroxyl functional groups, performing ultrasonic dispersion for 10min, stirring at 80 ℃ for 24h, wherein the concentration range of the multiwall carbon nanotube is 2% -10%, performing filtration treatment, washing the obtained filtrate with 0.1-0.3 mol/L NaOH solution for multiple times, washing with deionized water to be neutral, and performing vacuum drying at 80 ℃ for 48h to obtain the treated modified multiwall carbon nanotube;
Step (3), placing the glass fiber in absolute ethyl alcohol for ultrasonic oscillation cleaning for 5-10 min, drying, placing the glass fiber into a plasma reaction chamber, and introducing carrier gas: 40% of N 2 plus 60% of Ar, the vacuum degree is 0.6Pa, the power is 100W, the weight loss rate of the glass fiber after being treated is controlled to be 0.1% -0.5%, and the modified glass fiber with the length of 2-5 mm and the diameter of 5-13 mu m is obtained by chopping the glass fiber after being treated by plasma;
Dispersing the modified multi-wall carbon nano tube treated in the step (2) in an ethanol solution with the volume fraction of 40-60%, adding the modified glass fiber treated by the plasmas obtained in the step (3), carrying out a reaction by stirring, keeping the ratio of the modified glass fiber to the modified multi-wall carbon nano tube in a range of 2-25, putting the mixture in an environment with the temperature of 0-4 ℃ for refrigerating for 24 hours, and then freeze-drying to obtain a glass fiber compound coated by the multi-wall carbon nano tube;
And (5) sequentially placing the PET resin, the glass fiber compound in the step (4), the antioxidant, the chain extender, the nucleating agent, the lubricant and the coupling agent into a high-speed mixer, mixing at a high speed for 5-20 min, then putting into a double-screw extruder, controlling the screw rotating speed at 150-300 rpm, and finally obtaining the glass fiber reinforced PET material through melt extrusion and granulation.
2. The glass fiber reinforced PET material of claim 1, wherein: the coupling agent is a silane coupling agent, and the general formula is RSiX 3; wherein R represents an amino group, a mercapto group, a vinyl group, an epoxy group, a cyano group or a methacryloxy group, and X represents an alkoxy group capable of hydrolysis.
3. The glass fiber reinforced PET material of claim 1, wherein: the twin-screw extruder is provided with 10 temperature control areas, and the corresponding temperature control range is 220-260 ℃.
4. The glass fiber reinforced PET material of claim 1, wherein: the double-screw extruder is provided with two vacuumizing ports in total, the first vacuumizing port is arranged at the beginning of the melting section, and the second vacuumizing port is arranged at the metering section.
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