CN116478533B - Nylon 66 modified based on transition metal and rare earth complex and method thereof - Google Patents
Nylon 66 modified based on transition metal and rare earth complex and method thereof Download PDFInfo
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- 229920002302 Nylon 6,6 Polymers 0.000 title claims abstract description 54
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 20
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 27
- 238000001035 drying Methods 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000000945 filler Substances 0.000 claims abstract description 14
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000004594 Masterbatch (MB) Substances 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract description 6
- -1 transition metal salt Chemical class 0.000 claims abstract description 5
- 239000008187 granular material Substances 0.000 claims abstract description 3
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- 238000010907 mechanical stirring Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 239000011572 manganese Substances 0.000 claims description 27
- 239000002048 multi walled nanotube Substances 0.000 claims description 20
- 238000001125 extrusion Methods 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 7
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 7
- 229940099607 manganese chloride Drugs 0.000 claims description 7
- 235000002867 manganese chloride Nutrition 0.000 claims description 7
- 239000011565 manganese chloride Substances 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 5
- 239000006185 dispersion Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000000155 melt Substances 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 238000004873 anchoring Methods 0.000 claims description 3
- 230000007547 defect Effects 0.000 claims description 3
- 239000003446 ligand Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 239000007800 oxidant agent Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims 1
- TXBBUSUXYMIVOS-UHFFFAOYSA-N thenoyltrifluoroacetone Chemical compound FC(F)(F)C(=O)CC(=O)C1=CC=CS1 TXBBUSUXYMIVOS-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 14
- 230000004048 modification Effects 0.000 abstract description 6
- 238000012986 modification Methods 0.000 abstract description 6
- 238000004154 testing of material Methods 0.000 abstract description 2
- 238000001746 injection moulding Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 14
- 238000001291 vacuum drying Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- 229910052693 Europium Inorganic materials 0.000 description 6
- 239000011347 resin Substances 0.000 description 6
- 229920005989 resin Polymers 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000011363 dried mixture Substances 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 229910001437 manganese ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 239000012153 distilled water Substances 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2477/06—Polyamides derived from polyamines and polycarboxylic acids
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- 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
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
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- 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
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- 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
- C08K5/00—Use of organic ingredients
- C08K5/0091—Complexes with metal-heteroatom-bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
- Y02B20/00—Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps
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Abstract
The invention discloses a preparation method of nylon 66 based on modification of transition metal and rare earth complex, which comprises the steps of mixing prepared unzipped carbon nano-tubes with transition metal salt to obtain a transition metal anchored unzipped carbon nano-tube nano-filler; uniformly mixing the transition metal anchored and unzipped carbon nano tube nano filler with the rare earth ion organic ligand solution, stirring, washing, filtering, drying and collecting to obtain the fluorescent hybrid luminescent material; uniformly mixing the fluorescent hybridized luminescent material and nylon 66 granules by a mechanical stirring method, uniformly adding the uniformly mixed mixture into a double-screw extruder, melting and heating, and extruding through a thin-caliber die to obtain the nylon 66 master batch modified by the complex of transition metal and rare earth. The mechanical properties of the prepared composite material are tested by a universal material testing machine, and the ultimate tensile strength is improved by about 75 percent compared with that of pure nylon 66. The fluorescent property of the composite material is tested by an ultraviolet spectrophotometer, and the fluorescent intensity can reach 3.0 multiplied by 10 5 candela。
Description
Technical Field
The invention belongs to the field of composite material interface modification, and in particular relates to a nylon 66 nanocomposite modified by a transition metal and rare earth complex carried by a zipper-releasing carbon nanotube and a preparation method thereof.
Background
Nylon 66 resin (PA 66) is an excellent thermoplastic engineering material, and has more hydrogen bonds than other nylon series nylon 66, so that the nylon 66 has excellent mechanical properties, high friction resistance, scratch resistance and solvent resistance, self-lubricating property, shock absorption and sound absorption performance, and becomes engineering plastic with highest demand, and has been widely applied to electronic, electric and automobile industries, household appliances, sports goods and the like. However, the low strength of the virgin nylon 66 greatly limits its further applications. To compensate for these drawbacks, nylon 66 resins are modified.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide nylon 66 modified based on transition metal and rare earth complex and a method thereof.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
the preparation method of nylon 66 based on transition metal and rare earth complex modification comprises the steps of mixing prepared unzipped carbon nano-tubes with transition metal salt to obtain a transition metal anchored unzipped carbon nano-tube nano-filler; uniformly mixing the transition metal anchored and unzipped carbon nano tube nano filler with the rare earth ion organic ligand solution, stirring, washing, filtering, drying and collecting to obtain the fluorescent hybrid luminescent material; uniformly mixing the fluorescent hybridized luminescent material and nylon 66 granules by a mechanical stirring method, uniformly adding the uniformly mixed mixture into a double-screw extruder, melting and heating, and extruding through a thin-caliber die to obtain the nylon 66 master batch modified by the complex of transition metal and rare earth.
The preparation method prepares the multiwall carbon nano tube for unzipping by using the modified Hummers technology, and uses two strong acids of HCl and HNO 3 Treating the original multiwall carbon nanotubes to remove impurities, and using a strong oxidant KMnO 4 And oxidizing and tearing the original carbon nano tube to obtain the zipped multi-wall carbon nano tube similar to the graphene lamellar structure.
The preparation method comprises the steps of respectively weighing manganese chloride with equal mass and unzipped carbon nano tubes, respectively dissolving the manganese chloride and the unzipped carbon nano tubes in absolute ethyl alcohol, mixing the dispersion solution after the manganese chloride and the unzipped carbon nano tubes are completely dissolved through magnetic stirring, carrying out ultrasonic treatment for 2-4 hours, and drying to obtain the transition metal anchored unzipped carbon nano tube nano filler uMWCNTS-Mn.
The preparation method comprises the steps of anchoring rare earth complex to the nano-pore defect of transition metal nano-filler carried by the unzipped carbon nano-tube, uniformly dispersing the transition metal anchored unzipped carbon nano-tube nano-filler in DMF by ultrasonic, and adding Eu with the same amount 3+ And (3) fully and uniformly stirring the rare earth complex organic ligand solution, filtering and washing with DMF, and drying and collecting to obtain Eu-uMWCNTs-Mn.
The preparation method prepares ligand solution, the used ligand comprises TTA (2-thiophenoyltrifluoroacetone) and Phen (phenanthroline), and EuCl is dripped in 3 ·6H 2 Fully and uniformly stirring the solution in O at 45 ℃ and at a stirring speed of 200r/min to obtain Eu 3+ (TTA) 3 Ternary complexes of Phen.
According to the preparation method, when the Hummers technology is used for preparing the zippers, the diameter of the MWCNTs of the multi-wall carbon nano tube is 50nm, the length of the MWCNTs is 10 mu m, the ultrasonic stirring and dispersing time is 24 hours, the number of times of adding potassium permanganate is 3, the dosage of the potassium permanganate is 1.5g, the mass of the corresponding multi-wall carbon nano tube is 0.2g, and the heat preservation time is 4 hours after the potassium permanganate is added.
The preparation method adopts a double-screw extruder to melt and extrude at the temperature of 260-280 ℃ and the extrusion speed of 20-60rpm.
Nylon 66 hybrid material prepared according to any of the preparation methods.
The invention adopts the methodAfter the technical scheme, the method has the following beneficial effects: (1) The existence of the transition metal ion and the rare earth complex effectively transfers the stress applied to the nylon 66 resin matrix, and improves the mechanical property of the nylon 66 resin; (2) The existence of the transition metal ion and the rare earth complex effectively improves the luminous performance of the nylon 66 resin. (3) The mechanical properties of the prepared composite material are tested by a universal material testing machine, and the ultimate tensile strength is improved by about 75 percent compared with that of pure nylon 66. The fluorescent property of the composite material is tested by an ultraviolet spectrophotometer, and the fluorescent intensity can reach 3.0 multiplied by 10 5 candela。
Drawings
FIG. 1 is a flow chart of a method for preparing the Eu-uMWCNTs-Mn modified nylon 66 resin of the present invention.
FIG. 2 shows TEM images of MWCNTs (a) and uMWCNTs (b).
FIG. 3 is an infrared spectrum of Eu-uMWCNTs-Mn.
Fig. 4 is a fluorescence emission spectrum of the composite material.
FIG. 5 is a tensile stress strain curve of the Eu-uMWCNTs-Mn/PA66 composite.
FIG. 6 is a Young's modulus curve of Eu-uMWCNTs-TM/PA66 composite.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
S1, preparing the unzipped carbon nano tube by adopting a modified Hummers technology.
Specifically, 20ml of nitric acid (HNO) 3 ) And 20ml of concentrated sulfuric acid (98% H) were measured 2 SO 4 ) Adding into 250ml three-neck flask, weighing 0.20g carbon nanotube, adding into three-neck flask, mechanically stirring the mixed solution in a stirrer for 1 hr, then performing ultrasonic dispersion for 24 hr, and adding 1.50g potassium permanganate (KMnO) 4 ) The addition was performed in 3 portions, each at 30 minute intervals. Then the temperature of the water bath is raised to 45 ℃, and the reaction is kept for 4 hours. 40ml of pure water was measured, and 1ml of hydrogen peroxide (30% H) was added 2 O 2 ) Is prepared into hydrogen peroxide solution and frozen into ice cubes. Putting the ice cubes into a beaker, adding the mixed solution, stirring with a glass rod,this process was performed in an ice-water bath. Then, H is added dropwise 2 O 2 (30%) to prevent insoluble MnO 2 Until no bubbles appear, to obtain the unzipped carbon nanotube dispersion. After the first centrifugation, the supernatant is removed, and during the second centrifugation, a HCl solution (distilled water to concentrated sulfuric acid ratio 3:1) is used to clean the residual product. And centrifuging the product obtained after the secondary centrifugation for multiple times by using pure water until the pH value of the supernatant is 7, after centrifugal washing, freeze-drying the washed multi-wall carbon nano tube dispersion liquid for unzipping, and collecting to obtain the carbon nano tube powder for unzipping. FIG. 2 shows TEM images of MWCNTs (a) and uMWCNTs (b). The original multi-wall carbon nano tube structure with a regular structure can be obviously seen to be torn, and a lamellar graphite structure is formed.
S2, preparing the uMWCNTs modified nylon 66 hybrid material.
Dispersing 0.04g of uMWCNTs in an absolute ethyl alcohol solvent, adding 20g of nylon 66 master batch, mechanically stirring, placing into a vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, adding the dried mixture into a double screw for melt extrusion at a constant speed, wherein the melt extrusion temperature is 260-280 ℃, the extrusion speed is 40rpm, extruding and modifying, slicing, placing into the vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, and performing injection molding by an injection molding machine, wherein the injection molding melting temperature is 260-280 ℃, the injection molding pressure is 3MPa, and the mold temperature is 100 ℃. The sample uMWCNTs (0.2%)/PA 66 was obtained.
Example 2
S1, preparation of europium complex
Into a conical flask, 5ml of 0.1mol/LPhen solution was added, stirred for 4h, and then 5ml of 0.1M EuCl was added 3 ·6H 2 O solution and 5ml of 0.3M TTA, stirring for 30min, regulating pH to 7 with 2mol/L dilute ammonia water, and stirring for 2 hr to obtain Eu3+ -organic ligand solution. And freeze-drying to obtain europium complex powder.
S2, preparing the europium complex modified nylon 66 hybrid material.
Dispersing 0.04g of solid europium complex powder in an absolute ethyl alcohol solvent, adding 20g of nylon 66 master batch, mechanically stirring, placing into a vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, adding the dried mixture into a double screw for melt extrusion at a constant speed, wherein the melt extrusion temperature is 260-280 ℃, the extrusion speed is 40rpm, extruding and modifying, slicing, placing into the vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, performing injection molding by an injection molding machine, wherein the injection molding melting temperature is 260-280 ℃, the injection molding pressure is 3MPa, and the mold temperature is 100 ℃. The sample Eu (0.2%)/PA 66 was obtained. FIG. 4 shows the fluorescence emission spectrum of the composite material, and the fluorescence intensity of the Eu/PA66 material is obviously improved. FIG. 5 shows the mechanical property curve of the composite material, wherein the Eu/PA66 material has a mechanical property improved by 56% compared with the original nylon 66 material.
Example 2
Preparation of S1, uMWCNTs-Mn
Weighing 1g of manganese chloride solid and 1g of unzipped multiwall carbon nanotube powder, respectively placing the manganese chloride solid and the 1g of unzipped multiwall carbon nanotube powder in a conical flask, adding 10ml of absolute ethyl alcohol, magnetically stirring for 2 hours, after the manganese chloride solid and the powder are completely dispersed, mixing the two solutions, magnetically stirring the mixed solution for 2 hours, then carrying out ultrasonic treatment for 4 hours, and drying to obtain manganese anchored unzipped carbon nanotube nano filler powder uMWCNTs-Mn.
S2, preparing the uMWCNTs-Mn modified nylon 66 hybrid material.
Dispersing 0.04g of uMWCNTs-Mn in an absolute ethyl alcohol solvent, adding 20g of nylon 66 master batch, mechanically stirring, placing into a vacuum drying oven, drying at 80 ℃ for 12h and 120 ℃ for 4h, adding the dried mixture into a double screw for melt extrusion at a constant speed, wherein the temperature of melt extrusion is 260-280 ℃, the extrusion speed is 40rpm, slicing after extrusion modification, placing into the vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, performing injection molding by an injection molding machine, the injection molding melting temperature is 260-280 ℃, the injection molding pressure is 3MPa, and the mold temperature is 100 ℃. The sample uMWCNTs-Mn (0.2%)/PA 66 was obtained. FIG. 5 is a tensile stress strain curve of the composite material, with a 74% improvement in mechanical strength of the uMWCNTs-Mn/PA66 material over the original nylon 66. FIG. 6 is a Young's modulus curve of the composite material, with a 100% improvement in the uMWCNTs-Mn/PA66 material over the original nylon 66.
Example 4
Preparation of S1, eu-uMWCNTs-Mn
Into a conical flask, 5ml of 0.1mol/LPhen solution was added, stirred for 4h, and then 5ml of 0.1M EuCl was added 3 ·6H 2 Mixing O solution and 5ml of 0.3M TTA, stirring for 30min, regulating pH to 7 with 2mol/L diluted ammonia water, and stirring for 2 hr to obtain Eu 3+ -an organic ligand solution.
Dispersing 0.1g uMWCNTs-Mn in 20ml DMF, ultrasonic dispersing uniformly, adding prepared Eu 3+ -organic ligand solution, stirred for 4h. Washing and suction filtering with a large amount of DMF, and drying and collecting Eu-uMWCNTs-Mn. FIG. 3 shows an infrared spectrum of Eu-uMWCNTs-Mn. It was found that the Eu-uMWCNTs-Mn had a phen located 844cm -1 Infrared characteristic peak of (2) and at 581cm -1 The characteristic peak of (2) shows that the rare earth complex is combined with uMWCNTs-Mn to generate a novel fluorescent hybrid material.
FIG. 4 (a) shows the fluorescence emission spectrum of Eu-uMWCNTs-Mn, and it can be seen that the fluorescence intensity of the zipped multiwall carbon nanotube carrying the manganese ion for anchoring the europium ion is higher than that of the mixed nano-filler of the europium complex and the manganese ion.
S2, preparing Eu-uMWCNTs-Mn modified nylon 66 hybrid materials.
Dispersing 0.04g Eu-uMWCNTs-Mn in an absolute ethyl alcohol solvent, adding 20g nylon 66 master batch, mechanically stirring, placing into a vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, adding the dried mixture into a double screw for melt extrusion at a constant speed, wherein the melt extrusion temperature is 260-280 ℃, the extrusion speed is 40rpm, extruding and modifying, slicing, placing into the vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, performing injection molding by an injection molding machine, the injection molding melting temperature is 260-280 ℃, the injection molding pressure is 3MPa, and the mold temperature is 100 ℃. The Eu-uMWCNTs-Mn (0.2%)/PA 66 sample was obtained. FIG. 4 shows the fluorescence emission spectrum of the composite material, wherein the fluorescence intensity of the Eu-uMWCNTs-Mn/PA66 material is obviously improved. FIG. 6 is a Young's modulus curve of the composite material, wherein the Eu-uMWCNTs-Mn/PA66 material has a modulus improved by 70% relative to the original nylon 66 material.
Comparative example 1:
s1, preparing an original nylon 66 material.
Taking 20g of nylon 66 master batch, mechanically stirring, putting into a vacuum drying oven, drying at 80 ℃ for 12h, drying at 120 ℃ for 4h, performing injection molding by an injection molding machine, wherein the injection melting temperature is 260-280 ℃, the injection molding pressure is 3MPa, and the mold temperature is 100 ℃. Sample PA66 was obtained.
It will be understood that modifications and variations will be apparent to those skilled in the art from the foregoing description, and it is intended that all such modifications and variations be included within the scope of the following claims.
Claims (8)
1. The preparation method of nylon 66 modified by complex of transition metal and rare earth is characterized in that the prepared zipped carbon nano tube is mixed with transition metal salt to obtain nano filler of transition metal anchored zipped carbon nano tube; uniformly mixing the transition metal anchored and unzipped carbon nano tube nano filler with the rare earth ion organic ligand solution, stirring, washing, filtering, drying and collecting to obtain the fluorescent hybrid luminescent material; uniformly mixing the fluorescent hybridized luminescent material and nylon 66 granules by a mechanical stirring method, uniformly adding the uniformly mixed mixture into a double-screw extruder, melting and heating, and extruding through a thin-caliber die to obtain the nylon 66 master batch modified by the complex of transition metal and rare earth.
2. The method of claim 1, wherein the modified Hummers technique is used to prepare the unzipped multiwall carbon nanotubes by using two strong acids HCl, HNO 3 Treating the original multiwall carbon nanotubes to remove impurities, and using a strong oxidant KMnO 4 And oxidizing and tearing the original carbon nano tube to obtain the zipped multi-wall carbon nano tube similar to the graphene lamellar structure.
3. The preparation method of claim 1, wherein manganese chloride and unzipped carbon nano-tubes with equal mass are respectively weighed and respectively dissolved in absolute ethyl alcohol, after the dissolution is completed through magnetic stirring, the dispersion solution is mixed, the magnetic stirring is carried out, after ultrasonic treatment is carried out for 2-4 hours, the transition metal anchored unzipped carbon nano-tube nano-filler uMWCNTS-Mn is obtained after drying.
4. The preparation method of claim 1, wherein the step of anchoring the rare earth complex to the nano-pore defect of the transition metal nano-filler carried by the unzipped carbon nano-tube comprises the steps of uniformly dispersing the transition metal anchored unzipped carbon nano-tube nano-filler in DMF by ultrasonic, and adding Eu with the same amount 3+ And (3) fully and uniformly stirring the rare earth complex organic ligand solution, filtering and washing with DMF, and drying and collecting to obtain Eu-uMWCNTs-Mn.
5. The process according to claim 4, wherein the ligand solution is prepared by dropping 2-thenoyltrifluoroacetone TTA, phenanthroline Phen, and EuCl 3 ·6H 2 Fully and uniformly stirring the solution in O at 45 ℃ and at a stirring speed of 200r/min to obtain Eu 3+ (TTA) 3 Ternary complexes of Phen.
6. The preparation method according to claim 2, wherein when the Hummers technology is used for preparing the unzipped multi-walled carbon nanotubes, MWCNTs are 50nm in diameter and 10 μm in length, ultrasonic stirring and dispersing are carried out for 24 hours, the number of times of adding potassium permanganate is 3, the dosage of the potassium permanganate is 1.5g, the mass of the corresponding multi-walled carbon nanotubes is 0.2g, and the heat preservation time is 4 hours after the potassium permanganate is added.
7. The process according to claim 1, wherein the melt extrusion is carried out at a temperature of 260 to 280℃and an extrusion speed of 20 to 60rpm using a twin screw extruder.
8. A nylon 66 hybrid material prepared according to the preparation method of any one of claims 1 to 7.
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| CN104860294A (en) * | 2015-04-20 | 2015-08-26 | 复旦大学 | Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof |
| CN111423871A (en) * | 2020-04-01 | 2020-07-17 | 青岛大学 | Multi-wall carbon nanotube structure derivative and hybrid luminescent nano material and preparation method thereof |
| CN112920495A (en) * | 2021-02-27 | 2021-06-08 | 青岛大学 | Unzipped carbon nanotube reinforced high-density polyethylene hybrid material and preparation method thereof |
| CN115286895A (en) * | 2022-02-09 | 2022-11-04 | 青岛大学 | Rare earth complex modified epoxy resin composite material and preparation method thereof |
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| CN104860294A (en) * | 2015-04-20 | 2015-08-26 | 复旦大学 | Three-dimensional graphene nanoribbon/carbon nanoribbon bridged structural material, and preparation method and application thereof |
| CN111423871A (en) * | 2020-04-01 | 2020-07-17 | 青岛大学 | Multi-wall carbon nanotube structure derivative and hybrid luminescent nano material and preparation method thereof |
| CN112920495A (en) * | 2021-02-27 | 2021-06-08 | 青岛大学 | Unzipped carbon nanotube reinforced high-density polyethylene hybrid material and preparation method thereof |
| CN115286895A (en) * | 2022-02-09 | 2022-11-04 | 青岛大学 | Rare earth complex modified epoxy resin composite material and preparation method thereof |
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