CN116574370A - Durable antistatic high-strength polyamide engineering plastic and preparation method thereof - Google Patents
Durable antistatic high-strength polyamide engineering plastic and preparation method thereof Download PDFInfo
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- 229920006351 engineering plastic Polymers 0.000 title claims abstract description 21
- 239000004952 Polyamide Substances 0.000 title claims abstract description 19
- 229920002647 polyamide Polymers 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000000843 powder Substances 0.000 claims abstract description 73
- 239000000919 ceramic Substances 0.000 claims abstract description 56
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 45
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000011258 core-shell material Substances 0.000 claims abstract description 30
- 229960003638 dopamine Drugs 0.000 claims abstract description 19
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims abstract description 16
- 239000007853 buffer solution Substances 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920001690 polydopamine Polymers 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052802 copper Inorganic materials 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims abstract description 7
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003381 stabilizer Substances 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 12
- 235000021355 Stearic acid Nutrition 0.000 claims description 11
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 11
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 11
- 239000008117 stearic acid Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 230000033444 hydroxylation Effects 0.000 claims description 9
- 238000005805 hydroxylation reaction Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 8
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 7
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 239000012792 core layer Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 238000002490 spark plasma sintering Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 150000001879 copper Chemical class 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 239000012760 heat stabilizer Substances 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000011812 mixed powder Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000002216 antistatic agent Substances 0.000 abstract description 11
- 238000005452 bending Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 229910000365 copper sulfate Inorganic materials 0.000 abstract description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 3
- 239000007771 core particle Substances 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010420 shell particle Substances 0.000 abstract description 2
- 229920002292 Nylon 6 Polymers 0.000 description 23
- 125000004429 atom Chemical group 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000011159 matrix material Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910010293 ceramic material Inorganic materials 0.000 description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000011231 conductive filler Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910011208 Ti—N Inorganic materials 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- -1 ester imide Chemical class 0.000 description 1
- WCHFOOKTKZYYAE-UHFFFAOYSA-N ethoxyperoxyethane Chemical compound CCOOOCC WCHFOOKTKZYYAE-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920006146 polyetheresteramide block copolymer Polymers 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
- C08L77/02—Polyamides derived from omega-amino carboxylic acids or from lactams thereof
-
- 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
- C08K2201/017—Additives being an antistatic agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/04—Antistatic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention relates to the technical field of modified engineering plastics, and provides a durable antistatic high-strength polyamide engineering plastic and a preparation method thereof. The invention prepares Ti by taking TiN powder, YN powder, ybN powder, ti powder and Al powder as raw materials (2‑m‑n) Y m Yb n AlN laminar ceramic powder, treating the surface of the ceramic powder with sodium hydroxide solution, loading dopamine, and promoting dopamine polymerization with Tris-HCl buffer solution containing copper sulfate and hydrogen peroxide to form Ti (2‑m‑n) Y m Yb n AlN ceramic powder is a core and shell particle which takes copper doped polydopamine as a shell. The core-shell particles are used as antistatic agents, and not only can endow PA6 material with good resistanceElectrostatic properties, and can improve the tensile strength and bending strength of the PA6 material.
Description
Technical Field
The invention relates to the technical field of modified engineering plastics, and provides a durable antistatic high-strength polyamide engineering plastic and a preparation method thereof.
Background
Polyamide 6 (PA 6) is an important thermoplastic engineering plastic with high mechanical strength, good toughness, good fatigue resistance, smooth surface, small friction coefficient, corrosion resistance, no toxicity and no odor, and self-extinguishing property. PA6 is not only commonly used in the traditional textile chemical fiber industry, but also increasingly used in the fields of automobiles, machinery, electronics, electrical appliances, aerospace and the like. PA6 has the defects of easy water absorption, poor antistatic performance and poor heat resistance, and has certain limit on the application range.
For antistatic modification of PA6, inorganic conductive fillers such as conductive metals or metal oxides, conductive carbon materials, and the like may be added, and organic antistatic agents such as surfactant type antistatic agents and polymer type antistatic agents may also be added.
The antistatic performance of inorganic conductive fillers (such as copper, silver, nickel, iron, zinc oxide, graphite, graphene, carbon black, carbon nano tubes, carbon fibers and the like) is obviously improved, but the interface compatibility between the inorganic fillers and a PA6 matrix is poor, the fillers are easy to agglomerate, the antistatic performance is reduced after the agglomeration, the mechanical property of PA6 is obviously influenced, and the tensile strength and the bending strength are obviously reduced.
The surfactant type antistatic agent (such as quaternary ammonium salt, alkyl amino acid salt, alkyl sulfonate, fatty amine ethoxy ether, etc.) can be an external coating method or an internal blending method, which has little influence on the mechanical properties of the PA6 matrix, but as small organic molecules, is easy to gradually lose in the water washing or friction process, and is difficult to provide a durable antistatic effect. And, since it leaks charges mainly by adsorbing moisture in the air to form a conductive water layer, its antistatic effect has a great relationship with ambient humidity.
The high molecular antistatic agent (such as polyethylene oxide, polyether ester amide, polyether ester imide, etc.) is not affected by friction, water washing, etc., and can provide lasting antistatic effect. Since the charge is leaked mainly by forming a conductive network structure in the matrix, the adsorption to form a water layer only plays a secondary auxiliary role, so that the antistatic effect has little dependence on the environmental humidity. However, the polymer antistatic agent needs to form a conductive network structure, and generally needs a higher addition amount, which can affect the mechanical properties of the matrix, especially the hydrophilic soft segment has a larger influence on the mechanical strength of the matrix.
Disclosure of Invention
The invention prepares a novel antistatic agent which has a core-shell structure, and the antistatic agent is added into a PA6 matrix to prepare the modified PA6 plastic, so that the antistatic agent not only can endow the PA6 material with good antistatic performance, but also can improve the tensile strength and the bending strength of the PA6 material.
The specific technical scheme related by the invention is as follows:
the durable antistatic high-strength polyamide engineering plastic comprises PA6, core-shell antistatic particles, a stabilizer, stearic acid and white oil.
Preferably, the stabilizer is an organic copper salt heat stabilizer.
Further preferably, the mass ratio of the PA6 to the core-shell antistatic particles to the stabilizer to the stearic acid to the white oil is 100:4-10:0.2-0.5:0.3-1:0.2-0.5.
The core layer of the core-shell antistatic particle is Y/Yb co-doped Ti 2 AlN layered ceramic powder, i.e. Ti (2-m-n) Y m Yb n AlN layered ceramic powder, wherein the shell layer is copper doped polydopamine.
The preparation process of the core-shell antistatic particle comprises the following steps:
step1, uniformly mixing TiN powder, YN powder, ybN powder, ti powder and Al powder by adopting a mixer under the protection of argon, putting into a die, sintering to obtain a block material, crushing and grinding, and sieving with a 400-800-mesh sieve to obtain Ti (2-m-n) Y m Yb n AlN layered ceramic powder;
step2, heating a sodium hydroxide solution to 60-80 ℃, atomizing and spraying the sodium hydroxide solution onto the surface of the layered ceramic powder, and washing the layered ceramic powder with deionized water after 10-20min to obtain surface hydroxylation ceramic powder;
step3, adding dopamine hydrochloride into deionized water, uniformly stirring, and spraying and depositing on the surface of the surface hydroxylation ceramic powder to obtain dopamine-loaded ceramic powder;
step4, preparing Tris-HCl buffer solution with pH of 8.5, adding copper sulfate pentahydrate, mixing, adding hydrogen peroxide, mixing to obtain mixed solution, spraying the mixed solution on the surface of the dopamine-loaded ceramic powder in an atomized manner, washing with deionized water after 4-6 hours, and drying to obtain the core-shell antistatic particles.
In Step1, the molar ratio of TiN, YN, ybN, ti, al is 2-m-n: m: n:1:1, wherein m=0.02-0.1, n=0.02-0.1. Preferably, m=0.04-0.08, n=0.04-0.08. Further preferably, m=0.06, n=0.06.
Preferably, in Step1, spark plasma sintering is adopted for sintering, and the specific process is that the mixed powder is placed into a spark plasma sintering furnace, vacuum is pumped firstly, heating is started when the vacuum degree reaches 10Pa, the temperature is increased to 900 ℃ at 90 ℃/min, the temperature is kept for 1min, then the pressure is increased to 30Pa, the temperature is increased to 1200 ℃ at 60 ℃/min, the temperature is kept for 5min, the pressure is removed, and the furnace is cooled.
Preferably, in Step2, the concentration of the sodium hydroxide solution is 2mol/L, and the mass ratio of the sodium hydroxide solution to the layered ceramic powder is 0.5:1, a step of; in Step3, the mass ratio of dopamine hydrochloride to the surface hydroxylation ceramic powder is 0.1:1, a step of; in Step4, the mass ratio of the buffer solution to the hydrogen peroxide to the copper sulfate pentahydrate is 1:0.18:0.12; the mass ratio of the mixed solution to the dopamine-loaded ceramic powder is 0.2:1.
the invention also provides a preparation method of the polyamide engineering plastic, which comprises the following steps: uniformly mixing PA6, core-shell antistatic particles, a stabilizer, stearic acid and white oil, extruding and granulating by using an extruder, cooling and drying. Preferably, a twin screw extruder is used, the barrel temperature in each section is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 235 ℃ and the head temperature is 240 ℃.
Known Ti 2 AlN is a ternary layered ceramic material (MAX phase ceramic material) having a close-packed hexagonal structure in which close-packed Ti atomic layers are periodically separated by Al atomic layers, ti atoms and N atoms form an octahedron therebetween, and N atoms are located at the center of the octahedron. The bonding force between Ti atoms and N atoms is a strong covalent bond; the Ti atoms and the Al atomic layers are in weak combination of Van der Waals force, so that the Al atoms are easier to break loose from the constraint of the Ti-N sheet layers; the Ti atoms are bonded by metal bonds. Thus Ti is 2 AlN has the excellent performance of binary ceramic, and can conduct electricity and heat. In view of this, the present invention prepares Ti 2 AlN laminar ceramic powder is taken as a core, dopamine is adsorbed on the surface of the AlN laminar ceramic powder, copper sulfate and hydrogen peroxide are added into a buffer solution, and the mixture is sprayed on the surface of the powder to promote the polymerization of the dopamine to form a copper doped polydopamine shell layer. In the core-shell particle, the ceramic powder of the core layer and the copper doped polydopamine of the shell layer jointly play a role in charge transfer, so that the core-shell particle can play a role in PA6Desired antistatic effect.
The invention also adopts yttrium/ytterbium to Ti 2 AlN is co-doped, so that the mechanical strength of the material can be further improved. It is known that well dispersed ceramic particles can strengthen the matrix material, while poorly dispersed ceramic particles can affect the mechanical strength of the material due to agglomeration. In the invention, the polydopamine shell layer is formed on the surface of the ceramic particles, so that the interface combination between the ceramic particles and the organic matrix can be obviously improved, and the uniform dispersion of the ceramic particles in the PA6 is promoted, and therefore, the mechanical strength of the PA6 is not reduced by the core-shell particles within a reasonable addition range. Further, the ternary layered ceramic is doped and modified, and part of M-site atoms (Ti is replaced by other transition metals 2 Ti in AlN), or substitution of part of the a-site atoms (Ti with other main group elements 2 Al in AlN) may improve certain properties of the ceramic material, possibly due to changes in lattice constant caused by doping, or to change the propensity for interlayer slip. Experiments show that compared with undoped material, the method uses Y atoms and Yb atoms to replace part of Ti atoms to obtain Ti (2-m-n) Y m Yb n AlN and the core-shell particles prepared by the method can further improve the tensile strength and the bending strength of the PA6 material.
In the preparation process of the core-shell particles, the surface of the layered ceramic powder is firstly treated by sodium hydroxide solution, then dopamine is loaded, and further the oxidation polymerization of the dopamine is promoted. Through sodium hydroxide solution treatment, more hydroxyl groups can be formed on the surface of the ceramic powder, the dopamine monomer is favorably loaded on the surface of the ceramic powder through hydrogen bond action, and the polymerized polydopamine can also form hydrogen bonds with the hydroxyl groups on the surface of the ceramic, so that the uniformity and firmness of loading of a shell layer can be improved, and the core-shell particles are favorable for playing good antistatic and mechanical strength improving roles.
Compared with the prior art, the invention has the outstanding characteristics and excellent effects that: the invention prepares Ti by taking TiN powder, YN powder, ybN powder, ti powder and Al powder as raw materials (2-m-n) Y m Yb n AlN layered ceramicCeramic powder is treated by sodium hydroxide solution, dopamine is loaded on the surface of the ceramic powder, and Tris-HCl buffer solution containing copper sulfate and hydrogen peroxide is used for promoting dopamine polymerization to form Ti (2-m-n) Y m Yb n AlN ceramic powder is a core and shell particle which takes copper doped polydopamine as a shell. The core-shell particles are used as antistatic agents, so that the PA6 material can be endowed with good antistatic performance, and the tensile strength and the bending strength of the PA6 material can be improved.
Detailed Description
The following embodiments are preferred embodiments of the present invention, and the scope of the present invention should not be construed as being limited thereto. Various substitutions and alterations are also within the scope of this disclosure, as will be apparent to those of ordinary skill in the art and by routine experimentation, without departing from the spirit and scope of the invention as defined by the foregoing description.
Examples 1-4 each used the following steps to prepare core-shell antistatic particles:
step1, preparing TiN powder, YN powder, ybN powder, ti powder and Al powder according to a molar ratio of 1.88:0.06:0.06:1:1, a step of; mixing the above powder with a mixer under the protection of argon for 12h, placing into a mold, placing into a discharge plasma sintering furnace, vacuumizing to 10Pa, heating to 900 ℃ at 90 ℃/min, preserving heat for 1min, pressurizing to 30Pa, heating to 1200 ℃ at 60 ℃/min, preserving heat for 5min, removing pressure, cooling with the furnace to obtain a block material, crushing and grinding, sieving with a 600-mesh sieve to obtain Ti (2-m-n) Y m Yb n AlN layered ceramic powder;
step2, heating a 2mol/L sodium hydroxide solution to 70 ℃, atomizing and spraying the solution onto the surface of the layered ceramic powder, and washing the layered ceramic powder with deionized water after 15min to obtain surface hydroxylation ceramic powder; the mass ratio of the sodium hydroxide solution to the layered ceramic powder is 0.5:1, a step of;
step3, adding dopamine hydrochloride into deionized water, uniformly stirring, and spraying and depositing on the surface of the surface hydroxylation ceramic powder to obtain dopamine-loaded ceramic powder; the mass ratio of dopamine hydrochloride to the surface hydroxylation ceramic powder is 0.1:1, a step of;
step4, preparing Tris-HCl buffer solution with pH of 8.5, adding copper sulfate pentahydrate, mixing, adding hydrogen peroxide, mixing to obtain mixed solution (the mass ratio of the buffer solution to the hydrogen peroxide to the copper sulfate pentahydrate is 1:0.18:0.12), spraying the mixed solution on the surface of the dopamine-loaded ceramic powder in an atomized manner, washing the surface of the dopamine-loaded ceramic powder with deionized water after 5 hours, and drying to obtain core-shell antistatic particles; the mass ratio of the mixed solution to the dopamine-loaded ceramic powder is 0.2:1.
then preparing modified polyamide engineering plastics:
uniformly mixing PA6, core-shell antistatic particles, a stabilizer, stearic acid and white oil, extruding and granulating by using an extruder, cooling and drying to obtain the durable antistatic high-strength polyamide engineering plastic. Wherein the stabilizer is organic copper salt heat stabilizer Finner-336, the extruder is a double screw extruder, the temperature of each section of the machine barrel is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 235 ℃, the temperature of the machine head is 240 ℃, and the screw rotating speed is 60r/min.
In example 1, the mass ratio of PA6, core-shell antistatic particles, stabilizer, stearic acid, white oil is 100:4:0.3:0.5:0.3.
in example 2, the mass ratio of PA6, core-shell antistatic particles, stabilizer, stearic acid, white oil is 100:6:0.3:0.5:0.3.
in example 3, the mass ratio of PA6, core-shell antistatic particles, stabilizer, stearic acid, white oil was 100:8:0.3:0.5:0.3.
in example 4, the mass ratio of PA6, core-shell antistatic particles, stabilizer, stearic acid, white oil was 100:10:0.3:0.5:0.3.
comparative example 1 in preparing core-shell antistatic particles, Y, yb was not used for doping, but TiN powder, ti powder, al powder in a molar ratio of 2:1:1 preparation of Ti 2 The AlN layered ceramic powder serves as a core layer of the antistatic particles. Other preparation conditions were the same as in example 4.
Comparative example 2 in the preparation of core-shell antistatic particles, the surface of layered ceramic powder was not treated with sodium hydroxide solution, but dopamine hydrochloride was directly spray-deposited. Other preparation conditions were the same as in example 4.
The prepared modified polyamide engineering plasticInjecting into 100mm×100mm×2mm test sample plate by injection molding machine, injection molding at 250deg.C under 4.5MPa for 4.5s, cooling for 10s, testing surface resistivity of sample plate by resistance tester, and averaging 5 times of each sample plate to obtain materials with surface resistivity of 3.3X10 s in example 1, example 2, example 3, example 4, comparative example 1, comparative example 2 9 Ω、6.5×10 8 Ω、7.7×10 7 Ω、2.1×10 7 Ω、2.4×10 7 Ω、4.4×10 8 Ω。
Test bars of 160mm by 10mm by 4mm were injection molded according to the above method, and the tensile properties of the bars were measured according to GB/T1040-2006 standard, the tensile speed was 50mm/min, and the average value of 5 bars per group was obtained to obtain materials of example 1, example 2, example 3, example 4, comparative example 1, comparative example 2, and tensile strengths of 77.3MPa, 81.4MPa, 85.7MPa, 88.8MPa, 81.7MPa, and 79.5MPa, respectively.
Test bars of 130mm by 10mm by 4mm were injection molded according to the above method, the bending properties of the test bars were measured according to GB/T9341-2008 standard, the bending speed was 5mm/min, and the average value was taken for 5 bars of each group, to obtain materials of example 1, example 2, example 3, example 4, comparative example 1, comparative example 2, and bending strengths of 107.1MPa, 110.9MPa, 115.3MPa, 118.6MPa, 111.5MPa, and 109.2MPa, respectively.
Claims (8)
1. The components of the polyamide engineering plastic comprise PA6, a stabilizer, stearic acid and white oil, and the polyamide engineering plastic is characterized by further comprising core-shell antistatic particles; the core layer of the core-shell antistatic particle is Ti (2-m-n) Y m Yb n AlN layered ceramic powder, wherein a shell layer is copper doped polydopamine;
the preparation process of the core-shell antistatic particle comprises the following steps:
step1, uniformly mixing TiN powder, YN powder, ybN powder, ti powder and Al powder by adopting a mixer under the protection of argon, putting into a die, sintering to obtain a block material, crushing and grinding, and sieving with a 400-800-mesh sieve to obtain Y/Yb co-doped Ti 2 AlN layered ceramic powder, i.e. Ti (2-m-n) Y m Yb n AlN layered ceramic powder; tiN, YN, ybN, ti, al is 2-m-n: m: n:1:1, wherein m=0.02-0.1, n=0.02-0.1;
step2, heating a sodium hydroxide solution to 60-80 ℃, atomizing and spraying the sodium hydroxide solution onto the surface of the layered ceramic powder, and washing the layered ceramic powder with deionized water after 10-20min to obtain surface hydroxylation ceramic powder;
step3, adding dopamine hydrochloride into deionized water, uniformly stirring, and spraying and depositing on the surface of the surface hydroxylation ceramic powder to obtain dopamine-loaded ceramic powder;
step4, preparing Tris-HCl buffer solution with pH of 8.5, adding copper sulfate pentahydrate, mixing, adding hydrogen peroxide, mixing to obtain mixed solution, spraying the mixed solution on the surface of the dopamine-loaded ceramic powder in an atomized manner, washing with deionized water after 4-6 hours, and drying to obtain the core-shell antistatic particles.
2. The durable antistatic high-strength polyamide engineering plastic according to claim 1, wherein: the stabilizer is an organic copper salt heat stabilizer.
3. The durable antistatic high-strength polyamide engineering plastic according to claim 1, wherein: the mass ratio of the PA6 to the core-shell antistatic particles to the stabilizer to the stearic acid to the white oil is 100:4-10:0.2-0.5:0.3-1:0.2-0.5.
4. The durable antistatic high-strength polyamide engineering plastic according to claim 1, wherein: in Step1, m=0.04-0.08, and n=0.04-0.08.
5. The durable antistatic high-strength polyamide engineering plastic according to claim 1, wherein: in Step1, spark plasma sintering is adopted for sintering, and the specific process is that mixed powder is placed into a spark plasma sintering furnace, vacuumizing is firstly carried out, heating is started when the vacuum degree reaches 10Pa, the temperature is increased to 900 ℃ at 90 ℃/min, the temperature is kept for 1min, then the pressure is increased to 30Pa, the temperature is increased to 1200 ℃ at 60 ℃/min, the temperature is kept for 5min, the pressure is removed, and the furnace is cooled.
6. The durable antistatic high-strength polyamide engineering plastic according to claim 1, wherein:
in Step1, m=0.06, n=0.06;
in Step2, the concentration of the sodium hydroxide solution is 2mol/L; the mass ratio of the sodium hydroxide solution to the layered ceramic powder is 0.5:1, a step of;
in Step3, the mass ratio of dopamine hydrochloride to the surface hydroxylation ceramic powder is 0.1:1, a step of;
in Step4, the mass ratio of Tris-HCl buffer solution, hydrogen peroxide and copper sulfate pentahydrate is 1:0.18:0.12; the mass ratio of the mixed solution to the dopamine-loaded ceramic powder is 0.2:1.
7. a process for the preparation of a polyamide engineering plastic as claimed in any one of claims 1 to 6, characterized in that: uniformly mixing PA6, core-shell antistatic particles, a stabilizer, stearic acid and white oil, extruding and granulating by using an extruder, cooling and drying to obtain the durable antistatic high-strength polyamide engineering plastic.
8. The method for producing a polyamide engineering plastic according to claim 7, wherein: the extruder is a double-screw extruder, the temperature of each section of the machine barrel is 200 ℃, 210 ℃, 220 ℃, 230 ℃, 235 ℃ and the temperature of the machine head is 240 ℃.
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