CN111019339A - Spraying-free metallic polyamide material and preparation method and application thereof - Google Patents
Spraying-free metallic polyamide material and preparation method and application thereof Download PDFInfo
- Publication number
- CN111019339A CN111019339A CN201911345777.0A CN201911345777A CN111019339A CN 111019339 A CN111019339 A CN 111019339A CN 201911345777 A CN201911345777 A CN 201911345777A CN 111019339 A CN111019339 A CN 111019339A
- Authority
- CN
- China
- Prior art keywords
- mineral
- bis
- modified
- ion
- metal powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- 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
- C08L77/06—Polyamides derived from polyamines and polycarboxylic acids
-
- 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
- C08K3/08—Metals
- C08K2003/0806—Silver
-
- 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
- C08K3/08—Metals
- C08K2003/0812—Aluminium
-
- 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
- C08K3/08—Metals
- C08K2003/085—Copper
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Landscapes
- 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 provides a spraying-free metallic polyamide material and a preparation method and application thereof. The polyamide material comprises, by weight, 70-99 parts of polyamide, 1-20 parts of modified metal powder, 2-10 parts of modified mineral and 3-10 parts of a compatilizer. The modified metal powder and the modified mineral have good dispersibility in the polyamide matrix and strong interaction with the polyamide matrix, the obtained polyamide material is not easy to generate appearance defects such as blackening, flow marks and the like, the impact toughness, the tensile strength and the heat distortion temperature of the material are obviously improved, and the heat distortion temperature can reach 95.3-117.3 ℃. Therefore, the material has high apparent qualification rate when used for product molding, is not easy to break when assembled and used, and has high industrial value.
Description
Technical Field
The invention belongs to the field of high polymer materials, and particularly relates to a polyamide material, a preparation method and application thereof, in particular to a spraying-free metallic high-heat-resistance polyamide material, and a preparation method and application thereof.
Background
Polyamide (PA), commonly known as nylon, is a linear polymer having an amide bond (-CONH-) as a repeating unit in the molecule, and can be prepared by polycondensation of dibasic acid and diamine, or by ring-opening polymerization of amino acid caprolactam. PA is an engineering plastic with excellent performance, has the characteristics of good mechanical strength, self-lubricating performance, easy processability, good wear resistance, shock absorption, noise reduction and the like, and is widely applied to the industries of machinery, automobiles, electric appliances and the like. However, polar amide bonds exist in PA molecules, so that the PA molecules are easy to absorb water, the dimensional stability and the mechanical strength of the PA molecules are poor, the notch impact toughness of the PA molecules is poor, and the aliphatic polyamides (such as PA6, PA66, PA46 and the like) have high Vicat Softening Temperature (VST) but low thermal deformation temperature, so that the application range of the PA molecules is limited.
At present, when the modified polyamide material is applied to the fields of household appliances (such as liquid crystal display television shells and sound shells), automobile interior and exterior trimming parts (such as decorative strips, decorative plates, handles and buckles) and the like, secondary processing (such as electroplating, paint spraying and the like) is often required to meet the requirements of people on the aspects of product attractiveness, wear resistance and the like, but the problems of production cost increase, environmental pollution and the like are caused by the secondary processing. The aliphatic polyamide has the characteristics of excellent mechanical property, good processing property, good metal texture, good surface scratch resistance and the like, so the aliphatic polyamide can be used as a spraying-free high-gloss strong-metal texture material and has wide market prospect.
CN108456419A discloses a low-viscosity spraying-free metallic silver polyamide composition and a preparation method thereof, wherein the raw materials are PA6 resin, metallic silver powder, a coupling agent, a low-viscosity high polymer substance, a lubricating agent, an antioxidant, an ultraviolet absorbent, montmorillonite, a flame retardant, MDI, nano aluminum oxide, molybdenum disulfide, nano silicon dioxide, polytetrafluoroethylene, glass beads, polyethylene oxide, glass fibers, a chain extender and polyarylate, the low-viscosity polyamide composition has the characteristics of low viscosity, solves the problem of gas lines of products and has high barrier property; the glass fiber has the characteristic of no spraying, replaces a plating or vacuum plating mode, has small residual internal stress, but has the problem of poor luster and appearance of a formed product due to the addition of the glass fiber.
CN102372921A discloses a heat-resistant polyamide composition and an application thereof, wherein the composition comprises the following components in percentage by weight: 40-90% of heat-resistant polyamide resin, 5-35% of mineral fiber A, 0-35% of mineral filler B, 0.1-1% of light stabilizer, 0.1-1% of flow modifier and 0.1-1% of antioxidant. The invention selects the heat-resistant polyamide resin with the concentration ratio of the terminal amino group to the terminal carboxyl group between 0.1 and 0.8, and combines the profiled glass fiber with the flatness ratio between 2 and 6, the mineral filler B and the flow modifier to obtain the polyamide composition, although the heat resistance is better, the obtained polyamide composition has no metal texture and has the problem of poor appearance of a formed product.
CN107353635A discloses a nano polyamide composition with metallic luster and a preparation method thereof, wherein the nano polyamide composition comprises the following raw material components in parts by weight: 100 parts of polyamide resin, 5-40 parts of nano polyamide master batch, 0.3-2 parts of metal pigment, 0.051 parts of dispersing aid and 0.5-2 parts of processing aid. The invention selects the self-made nanometer polyamide master batch as a reinforcing material, interacts with the core-shell type dispersing agent, is compounded with the polyamide resin, and is assisted by the corresponding processing aid, so that the nanometer polyamide composition with metallic luster is obtained, and has good mechanical property and surface property. But the obtained material has low thermal deformation temperature and is easy to deform, so that the application range and the qualification rate of finished products are greatly limited.
In the actual use process, the metallic aliphatic polyamide material is easy to blacken, appearance defects such as 'flow marks' and the like are easy to form when the material is prepared into a product, the heat distortion temperature of the obtained material is low, and the application range and the finished product qualification rate are limited by the problems; on the other hand, the metallic polyamide material has low notched impact strength and, when used as a long trim strip for automotive interior trim and a decorative panel, there is a risk of breakage during actual assembly and use.
Therefore, there is a need in the art for a polyamide material having high gloss, high metallic quality, high quality of molded articles, high impact toughness at normal and low temperatures, and high thermal properties.
Disclosure of Invention
In order to solve the technical problems, the invention provides a spraying-free metallic high-heat-resistance polyamide material and a preparation method and application thereof. The spraying-free metallic high-heat-resistance polyamide material provided by the invention has the advantages of strong metal texture, good heat resistance and good normal and low temperature impact toughness, and is not easy to break in the using process; at the same time, the product made with this material has less risk of "blackening" or "flow marks" on the surface. In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a polyamide material, comprising the following components in parts by weight:
the components are proportioned, the polyamide material is used as a matrix, and the modified metal powder and the modified mineral are added, so that the obtained spraying-free metallic high-heat-resistance polyamide material has strong metal texture, is not easy to break, and has good toughness and heat resistance at normal and low temperatures.
In the present invention, the polyamide is 70 to 99 parts by weight, and may be, for example, 70 parts, 75 parts, 80 parts, 85 parts, 90 parts, 92 parts, 95 parts, 98 parts, 99 parts, or the like.
The modified metal powder is 1-20 parts by weight, and may be, for example, 1 part, 3 parts, 5 parts, 7 parts, 9 parts, 10 parts, 12 parts, 15 parts, 16 parts, 18 parts, 20 parts, or the like.
The modified mineral is 2-10 parts by weight, for example, 2 parts, 3 parts, 4 parts, 5 parts, 6 parts, 8 parts, 9 parts or 10 parts.
The weight portion of the compatilizer is 3-10 portions, and can be 3 portions, 4 portions, 5 portions, 6 portions, 8 portions or 10 portions, etc.
As a preferable technical scheme of the invention, the modified metal powder is metal powder modified by a modifier.
Preferably, the polyamide is selected from any one or combination of more than two of PA6, PA46, PA56, PA66, PA610, PA612, PA613, PA11, PA12, PA1010, PA1012, PA1111 and PA 1313.
Preferably, the metal powder is selected from one or a combination of more than two of magnesium powder, silver powder, aluminum powder, copper powder, zinc powder, lead powder, titanium powder, stainless steel powder or gold powder.
Preferably, the mineral is selected from any one or a combination of more than two of mineral minerals, carbonate minerals, borate or metal oxides.
Preferably, the mineral is selected from any one or a combination of two or more of wollastonite, pyroxene, dickite, vermiculite, halloysite, sepiolite, montmorillonite, bentonite, kaolin, talc, nacrite, phlogopite, sericite, biotite, muscovite, limestone, nahcolite, barite, calcite, dolomite, huntite, nesotaite, brucite, trona, monetite, ludwigite, paigeite, gavite, alumina, iron oxide, magnesium oxide, zinc oxide, copper oxide or calcium oxide.
Preferably, the modified metal powder is the same as or different from the modifying agent used to modify the mineral, and the modifying agent includes a coupling agent, a compatibilizing agent, and rare earth ions.
Preferably, the coupling agent is selected from any one or a combination of more than two of silane coupling agent, phthalate coupling agent, aluminate coupling agent or zirconate coupling agent.
Preferably, the coupling agent is selected from one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-ureidopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilanes, anilinomethyltrimethoxysilane, isopropyl tri (dioctylphosphoryloxy) titanate, isopropyl triisostearate, isopropyldioleate acyloxy (dioctylphosphoryloxy) titanate, isopropyl tri (dioctylphosphoryloxy) titanate, isopropyltrioleate acyloxy titanate, isopropyl tri (dioctylphosphoryloxy) titanate, bis (dioctyloxypyrophosphate) ethoxyphosphate, bis (dioctyloxypyrophosphate) ethylenetitanate, bis (trioctyloxyphosphate) ethylenephosphate and triethanolamine titanate, bis (dioctyloxypropylphosphate) titanate, bis (triethoxyzirconate chelate, bis (octyloxy) titanate, bis (triethoxy) zirconate chelate, bis (triethoxy) aluminate chelate, bis (triethoxy) titanate, bis (triethoxy) acrylate, bis (triethoxy) titanate, bis (triethoxy) acrylate, bis (triethoxy aluminate chelate, bis (triethoxy) titanate, bis (triethoxy aluminate, bis (triethoxy) titanate, tris (triethoxy aluminate, tris (triethoxy) titanate, tris (triethoxy aluminate, tris (triethoxy) titanate, tris (triethoxy aluminate, tris (triethoxy.
Preferably, the rare earth ion is selected from any one or a combination of more than two of zirconium ion, cobalt ion, lanthanum ion, praseodymium ion, samarium ion, europium ion, gadolinium ion, holmium ion, erbium ion, ytterbium ion, lutetium ion, scandium ion, indium ion, neodymium ion, cerium ion, yttrium ion, thulium ion, dysprosium ion or terbium ion.
Compared with unmodified metal powder and mineral, the modified metal powder and mineral have the advantages that the dispersibility of the modified metal powder and the modified mineral in the polyamide matrix is improved, the interaction between the modified metal powder and the polyamide matrix is enhanced, the modified metal powder avoids appearance defects such as 'flow marks' formed in the material during product forming, the 'blackening' phenomenon caused by excessive shearing in the production process of the material is avoided, the impact toughness and the tensile strength of the material are improved, and the thermal deformation temperature and the rigidity of the material are obviously improved by the modified mineral.
As a preferable technical scheme of the invention, the compatilizer used in the modifier is the same as or different from a compatilizer added in the polyamide material, and the compatilizer is selected from POE-g-MAH (maleic anhydride grafted ethylene-octene copolymer elastomer), SBS-g-MAH (styrene butadiene styrene copolymer grafted maleic anhydride), SEBS-g-MAH (styrene-butadiene-styrene block copolymer grafted maleic anhydride), EPDM-g-MAH (ethylene propylene diene monomer grafted maleic anhydride), ABS-g-MAH (maleic anhydride grafted acrylonitrile-butadiene-styrene copolymer), ASA-g-MAH (maleic anhydride grafted acrylonitrile-styrene-acrylate copolymer), LDPE-g-MAH (low-density polyethylene grafted maleic anhydride), Any one or the combination of more than two of LLDPE-g-MAH (linear low density polyethylene grafted maleic anhydride), UHMWPE-g-MAH (ultrahigh molecular weight polyethylene grafted maleic anhydride), SMA (styrene-maleic anhydride copolymer), SAN-g-MAH (acrylonitrile-styrene grafted maleic anhydride), POE-g-GMA (ethylene-octene copolymer grafted glycidyl methacrylate), EPDM-g-GMA (ethylene propylene diene monomer grafted glycidyl methacrylate), PE-g-GMA (polyethylene grafted glycidyl methacrylate), MB-g-GMA (polybutadiene grafted glycidyl methacrylate), MGE (methyl methacrylate-glycidyl methacrylate-ethyl acrylate terpolymer) or IA (phthalimidized acrylic acid), preferably UHMWPE-g-MAH.
Among them, Ultra-High Molecular Weight Polyethylene (UHMWPE) is unbranched linear Polyethylene having a Molecular Weight of 150 ten thousand or more. The UHMWPE-g-MAH leads the material to have high polarity and reactivity by introducing strong polar reactive groups, and can greatly improve the compatibility of the composite material and the dispersibility of the filler, thereby improving the mechanical strength of the composite material.
Preferably, the modifying agent comprises a coupling agent, UHMWPE-g-MAH and rare earth ions.
As a preferred embodiment of the present invention, the polyamide material further comprises 0.1 to 1.0 part by weight, for example, 0.1 part, 0.2 part, 0.3 part, 0.5 part, 0.6 part, 0.7 part, 0.8 part, 0.9 part, or 1.0 part, etc.) of an antioxidant.
Preferably, the polyamide material further comprises 0.1-1.0 parts (e.g., may be 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1.0 parts, etc.) by weight of an ultraviolet absorber.
Preferably, the polyamide material further comprises 0.1-1.0 parts (e.g., may be 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1.0 parts, etc.) by weight of a light stabilizer.
Preferably, the polyamide material further comprises 0.1-1.0 parts (e.g., may be 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1.0 parts, etc.) of a heat stabilizer, by weight.
Preferably, the polyamide material further comprises 0.1 to 1.0 parts (e.g., may be 0.1 parts, 0.2 parts, 0.3 parts, 0.5 parts, 0.6 parts, 0.7 parts, 0.8 parts, 0.9 parts, or 1.0 parts, etc.) by weight of a lubricant.
In a preferred embodiment of the present invention, the antioxidant is one or more selected from tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythrityl tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butyl) phosphite, octadecyl hindered phenol (3, 5-dibutyl-4-hydroxy-phenylpropionate), octadecyl 1,3, 5-tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine, 2,4,6- (1H,3H,5H) trione, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, diethylene glycol bis [ β - (3-tert-butyl-4-hydroxyphenyl) propionate ] dipentaerythritol or a combination of any two or more.
Preferably, the ultraviolet absorbent is selected from any one or the combination of more than two of benzoate, salicylate, benzophenone, benzotriazole or triazine ultraviolet absorbent.
The ultraviolet absorbers of benzoate, salicylate, benzophenone, benzotriazole and triazine can strongly absorb ultraviolet light, convert light energy into heat energy and release the heat energy, and improve the ultraviolet resistance of the material. The benzoate, salicylate, benzophenone, benzotriazole and triazine are all organic compounds, have good compatibility with matrix materials, and cannot influence the mechanical properties of the alloy materials.
Preferably, the ultraviolet absorber is selected from one or more of 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -bis (α -dimethylbenzyl) phenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-ditert-pentyl) benzotriazole, 2- (2' -hydroxy-4 ' -benzoyloxyphenyl) -5-chloro-2H-benzotriazole, resorcinol monobenzoate, 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-octyloxyphenol, 2,4, 6-tris (2' n-butoxyphenyl) -1,3, 5-triazine, 2- (4-n-hexyloxyphenyl) -1,3, 5-triazine, 5-hexyloxyphenol, 2, 5-diphenylsalicylic acid, 2-hexylsalicylic acid, or hexamethylphosphoric triamide.
Preferably, the light stabilizer is 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine, bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, 2,2,6, 6-tetramethylpiperidine benzoate, a polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate or poly { [6- [ (1,1,3, 3-tetramethylbutyl) imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidinyl) -nitrilo ] -hexamethylene- [4- (2,2,6, 6-tetramethylpiperidyl) -nitrilo ] }.
The light stabilizer can effectively capture active free radicals generated by the high polymer material under the action of ultraviolet rays, thereby exerting the light stabilizing effect; the ultraviolet light-absorbing agent is compounded with an ultraviolet light-absorbing agent, so that the photodegradation of high polymer materials can be effectively avoided.
Preferably, the heat stabilizer is selected from any one or a combination of two or more of cuprous halides, copper salts phosphates, and phosphates.
The heat stabilizer can provide long-term stability for the polyamide material, can prevent the material from becoming brittle at the highest working temperature and pressure, can prevent the polyamide material from generating premature mechanical fatigue under the conditions of high temperature, chemical corrosion and severe environment, and comprises BRUGGOLEN H320, PolyAd HS-01, PolyAd HS-03 and the like.
Preferably, the lubricant is any one or a combination of two or more of silane polymer, solid paraffin, liquid paraffin, fatty acid salt, calcium stearate, zinc stearate, fatty amide, methylene bis stearamide, oleamide, stearamide, ethylene bis stearamide or N, N-ethylene bis stearamide. The lubricant has the function of improving the processing fluidity of the alloy material and also has certain help for improving the wear resistance.
As a preferable technical scheme of the invention, the polyamide material comprises the following components in parts by weight:
in a second aspect, the present invention provides a method for preparing the polyamide material according to the first aspect, the method comprising: preparing modified metal powder and modified mineral, mixing the polyamide, the modified metal powder, the modified mineral and the compatilizer according to the formula ratio, adding the mixture into an extruder for melt blending, cooling, drying and granulating the mixture after extrusion to obtain the polyamide material.
As a preferable technical scheme of the invention, the preparation method of the modified metal powder or the modified mineral comprises the following steps:
(1) drying metal powder or mineral in vacuum, dispersing the metal powder or mineral in a solvent, and mixing a coupling agent with the metal powder or mineral for reaction to obtain the metal powder or mineral modified by the coupling agent;
(2) dispersing the metal powder or mineral modified by the coupling agent in a solvent, and then reacting with a compatilizer for modification;
(3) modifying the metal powder or mineral obtained in the step (2) by using a solution containing rare earth ions to obtain the modified metal powder or modified mineral.
Preferably, the solvent in step (1) is toluene.
Preferably, the reaction temperature in step (1) is 80-100 ℃, for example 80 ℃, 85 ℃, 88 ℃, 90 ℃, 95 ℃ or 100 ℃; the time is 6-8h, for example 6h, 6.2h, 6.5h, 7h, 7.5h or 8 h.
Preferably, the solvent in step (2) is decalin.
Preferably, the solution containing rare earth ions in the step (3) is a rare earth acetate solution.
In a preferred embodiment of the present invention, the time for mixing the polyamide, the modified metal powder, the modified mineral and the compatibilizer is 5 to 10min, for example, 5min, 6min, 7min, 8min, 9min or 10 min.
Preferably, the extruder is a twin screw extruder.
Preferably, the working temperature of the twin-screw extruder is 210 ℃ or 300 ℃, and can be, for example, 210 ℃, 220 ℃, 230 ℃, 240 ℃, 250 ℃, 255 ℃, 260 ℃, 270 ℃, 280 ℃, 290 ℃ or 300 ℃, etc.
Preferably, the screw speed of the extruder is 300-1000 rpm, and may be, for example, 300 rpm, 400 rpm, 450 rpm, 500 rpm, 550 rpm, 600 rpm, 650 rpm, 700 rpm, 750 rpm, 800 rpm, 850 rpm or 1000 rpm.
Preferably, the residence time of the mass in the extruder is 1-3min, for example 1min, 1.5min, 2min, 2.5min or 3min, etc.
In a third aspect, the invention also provides the use of the polyamide material according to the first aspect in the preparation of interior and exterior parts of automobiles or interior and exterior parts of electronic appliances.
The material provided by the invention can be used for preparing automobile interior and exterior trimming parts, household appliance shells, electronic appliance framework structures or electronic communication equipment shells and the like, but is not limited to the application range listed above.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the modified metal powder obtained by modifying the metal powder with the coupling agent, the compatilizer and the rare earth ions not only improves the dispersibility of the original metal powder in the polyamide matrix, but also enhances the interaction between the metal powder and the polyamide matrix, avoids the phenomenon of blackening caused by excessive shearing in the production process of the material, avoids the appearance defects of 'flow marks' and the like formed when the material is molded, and also improves the impact toughness and the tensile strength of the material to a certain extent;
(2) the modified mineral obtained by modifying the mineral through the coupling agent, the compatilizer and the rare earth ions not only improves the dispersibility of the mineral in the polyamide matrix, but also enhances the interaction between the mineral and the polyamide matrix, and obviously improves the thermal deformation temperature and the rigidity of the material;
(3) the polyamide material provided by the invention has the advantages that the thermal deformation temperature (1.80MPa) is 95.3-117.3 ℃, the apparent mass percent of pass is 85-95%, and the notch impact strength at normal temperature (23 ℃) under the ISO standard is 5.3-11.8 kJ/m2The low-temperature (-30 ℃) notch impact strength is 3.9-10.6 kJ/m2The tensile strength is 81.2 to 95.7MPa, and the flexural modulus is 3868 to 5379 MPa.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
The experimental materials used in the following examples were purchased from conventional reagent materials manufacturers unless otherwise specified. In the following examples, the compatibilizer can be prepared by the prior art, taking the preparation of UHMWPE-g-MAH as an example, and the UHMWPE-g-MAH is prepared by the following method:
placing a three-neck flask in an oil bath kettle at 120 ℃, adding 100ml of dimethylbenzene and 20 parts by mass of UHMWPE, heating to fully dissolve the UHMWPE, adding 0.5 part by mass of initiator BPO and 10 parts by mass of maleic anhydride, introducing nitrogen for protection, fully reacting for 4 hours, cooling to room temperature, and filtering to obtain UHMWPE-g-MAH; packing 5 parts by mass of UHMWPE-g-MAH with filter paper, putting the packed UHMWPE-g-MAH into a Soxhlet extractor, extracting the packed UHMWPE-g-MAH with acetone for 36 hours to fully remove unreacted initiator, grafting monomer and MAH homopolymer possibly generated, drying the extracted UHMWPE-g-MAH in an oven at 60 ℃ for 10 hours, and then drying the dried UHMWPE-g-MAH in a vacuum drying oven to constant weight.
Example 1
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material comprises the following steps:
the components in the formula are uniformly mixed for 5min by a high-speed mixer, and then the mixture is added into a double-screw extruder for melt blending, wherein the working parameters of the extruder are as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the eleventh zone is 235 ℃, the rotating speed of the screw is 350 revolutions per minute, the retention time is 3min, and the spraying-free metallic color high heat-resistant polyamide material is obtained by cooling, drying and grain cutting after extrusion.
The preparation method of the modified metal powder comprises the following steps:
(1) firstly, 100 parts by mass of metal aluminum powder is vacuumized and dried for 4 hours at the temperature of 100 ℃, and then cooled to 25 ℃ under the vacuum condition.
(2) Adding 0.8 part by mass of silver powder into 20mL of methylbenzene, and performing ultrasonic dispersion at 25 ℃ for 30min to obtain a uniform suspension; then 0.364 mass part of coupling agent KH-550 is added into the suspension, and ultrasonic mixing is carried out for 5 min; reacting for 6 hours in a constant temperature tank at 90 ℃; and then carrying out centrifugal separation at 25 ℃ of 12000r/min to obtain metal powder modified by the coupling agent, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum drying for 8 hours for later use.
(3) Adding 1 part by mass of the metal powder obtained in the step (2) into 100 parts by mass of decahydronaphthalene, and performing ultrasonic dispersion at normal temperature for 30min to obtain a uniform suspension; then adding 5 parts by mass of compatilizer UHMWPE-g-MAH into the suspension, and ultrasonically mixing for 20 min; reacting for 8 hours in a constant temperature bath at 100 ℃ to obtain metal powder modified by a coupling agent and a compatilizer; centrifuging at 25 deg.C 12000r/min, washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr.
(4) And (3) adding 10 parts by mass of the metal powder modified by the coupling agent and the compatilizer obtained in the step (3) into absolute ethyl alcohol for cleaning, stirring, standing for 20 hours, filtering and drying, preparing a thulium acetate deionized water solution with the mass concentration of 1%, standing for 24 hours, then adding the cleaned metal powder, ultrasonically dispersing for 2 hours, standing for 36 hours, filtering, and drying in vacuum to constant weight to obtain the modified metal powder.
The preparation method of the modified mineral comprises the following steps:
(1) firstly, 100 parts by mass of montmorillonite is vacuumized and dried for 6 hours at the temperature of 120 ℃, and then cooled to 25 ℃ under the vacuum condition.
(2) Adding 0.8 part by mass of montmorillonite into 20mL of toluene, and ultrasonically dispersing for 60min at 25 ℃ to obtain a uniform suspension; then 0.364 mass part of coupling agent KH-550 is added into the suspension, and ultrasonic mixing is carried out for 10 min; reacting for 8 hours in a constant temperature tank at 90 ℃; then carrying out centrifugal separation at 25 ℃ of 12000r/min to obtain montmorillonite modified by the coupling agent; washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr.
(3) Adding 1 part by mass of the montmorillonite obtained in the step (2) into 100 parts by mass of decahydronaphthalene, and performing ultrasonic dispersion at normal temperature for 30min to obtain a uniform suspension; then adding 5 parts by mass of compatilizer UHMWPE-g-MAH into the suspension, and ultrasonically mixing for 10 min; reacting in a constant temperature tank at 130 ℃ for 8h to obtain montmorillonite modified by a coupling agent and a compatilizer; centrifuging at 25 deg.C 12000r/min, washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr.
(4) And (3) adding 10 parts by mass of the mineral obtained in the step (3) into absolute ethyl alcohol for cleaning, stirring, standing for 20 hours, filtering and drying, preparing 1% thulium acetate deionized water solution with mass concentration, standing for 24 hours, then adding the montmorillonite obtained in the step (3) after cleaning, ultrasonically dispersing for 2 hours, standing for 36 hours, filtering, and drying in vacuum to constant weight to obtain the modified mineral.
Example 2
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material comprises the following steps:
the components in the formula are uniformly mixed for 5min by a high-speed mixer, and then the mixture is added into a double-screw extruder for melt blending, wherein the working parameters of the extruder are as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the eleventh zone is 235 ℃, the rotating speed of the screw is 350 revolutions per minute, the retention time is 3min, and the spraying-free metallic color high heat-resistant polyamide material is obtained by cooling, drying and grain cutting after extrusion.
The preparation method of the modified metal powder comprises the following steps:
(1) firstly, 100 parts by mass of silver powder is vacuumized and dried for 5 hours at the temperature of 110 ℃, and then cooled to 25 ℃ under the vacuum condition.
(2) Adding 0.8 part by mass of silver powder into 20mL of methylbenzene, and performing ultrasonic dispersion at 25 ℃ for 40min to obtain a uniform suspension; then 0.364 mass part of coupling agent KH-550 is added into the suspension, and ultrasonic mixing is carried out for 8 min; reacting for 7 hours in a constant temperature tank at 90 ℃; and then carrying out centrifugal separation at 25 ℃ of 12000r/min to obtain metal powder modified by the coupling agent, washing for 3 times by using absolute ethyl alcohol, and carrying out vacuum drying for 8 hours for later use.
(3) Adding 1 part by mass of the metal powder obtained in the step (2) into 100 parts by mass of decahydronaphthalene, and performing ultrasonic dispersion at normal temperature for 50min to obtain a uniform suspension; then adding 5 parts by mass of compatilizer UHMWPE-g-MAH into the suspension, and ultrasonically mixing for 15 min; reacting in a thermostatic bath at 115 ℃ for 8 hours to obtain metal powder modified by a coupling agent and a compatilizer; centrifuging at 25 deg.C 12000r/min, washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr.
(4) And (3) adding 10 parts by mass of the metal powder modified by the coupling agent and the compatilizer obtained in the step (3) into absolute ethyl alcohol, cleaning, stirring, standing for 20 hours, filtering and drying, preparing a dysprosium acetate deionized water solution with the mass concentration of 1%, standing for 24 hours, then adding the cleaned metal powder, performing ultrasonic dispersion for 2 hours, standing for 36 hours, filtering, and performing vacuum drying to constant weight to obtain the modified metal powder.
The preparation method of the modified mineral comprises the following steps:
(1) firstly, 100 parts by mass of montmorillonite is vacuumized and dried for 5.5 hours at the temperature of 118 ℃, and then cooled to 25 ℃ under the vacuum condition.
(2) Adding 0.8 part by mass of montmorillonite into 20mL of toluene, and ultrasonically dispersing for 35min at 25 ℃ to obtain a uniform suspension; then 0.364 mass part of coupling agent KH-550 is added into the suspension, and ultrasonic mixing is carried out for 7.5 min; reacting for 7.5 hours in a constant temperature tank at 90 ℃; centrifugally separating the reaction solution at 25 ℃ and 12000r/min to obtain montmorillonite modified by the coupling agent; washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr.
(3) Adding 1 part by mass of the montmorillonite obtained in the step (2) into 100 parts by mass of decahydronaphthalene, and ultrasonically dispersing at normal temperature for 55min to obtain a uniform suspension; then adding 5 parts by mass of compatilizer UHMWPE-g-MAH into the suspension, and ultrasonically mixing for 18 min; reacting in a constant temperature bath at 120 ℃ for 8 hours to obtain montmorillonite modified by a coupling agent and a compatilizer; centrifuging at 25 deg.C 12000r/min, washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr.
(4) And (3) adding 10 parts by mass of the mineral obtained in the step (3) into absolute ethyl alcohol for cleaning, stirring, standing for 20 hours, filtering and drying, preparing 1% thulium acetate deionized water solution with mass concentration, standing for 24 hours, then adding the montmorillonite obtained in the step (3) after cleaning, ultrasonically dispersing for 2 hours, standing for 36 hours, filtering, and drying in vacuum to constant weight to obtain the modified mineral.
Example 3
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material comprises the following steps:
the components in the formula are uniformly mixed for 5min by a high-speed mixer, and then the mixture is added into a double-screw extruder for melt blending, wherein the working parameters of the extruder are as follows: the temperature of the first zone is 210 ℃, the temperature of the second zone is 220 ℃, the temperature of the third zone is 230 ℃, the temperature of the fourth zone is 240 ℃, the temperature of the fifth zone is 240 ℃, the temperature of the sixth zone is 240 ℃, the temperature of the seventh zone is 240 ℃, the temperature of the eighth zone is 240 ℃, the temperature of the ninth zone is 240 ℃, the temperature of the tenth zone is 240 ℃, the temperature of the eleventh zone is 235 ℃, the rotating speed of the screw is 350 revolutions per minute, the retention time is 3min, and the spraying-free metallic color high heat-resistant polyamide material is obtained by cooling, drying and grain cutting after extrusion.
The preparation method of the modified metal powder is different from that of the embodiment 2 in that the silver powder is replaced by copper powder, and the other conditions are the same; the modified mineral was prepared as in example 2 except that the montmorillonite was replaced with bentonite and the remaining conditions were the same.
Example 4
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material is the same as that of the embodiment 2; wherein, the preparation method of the modified metal powder is the same as that of the embodiment 2; the modified mineral was prepared in the same manner as in example 2 except that the montmorillonite was replaced with talc.
Example 5
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material is the same as that of the embodiment 2; the preparation method of the modified metal powder and the preparation method of the modified mineral are the same as those in the example 2.
Example 6
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material is the same as that of the embodiment 2; the preparation method of the modified metal powder and the preparation method of the modified mineral are the same as those in the example 2.
Example 7
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material is the same as that of the embodiment 2; the preparation method of the modified metal powder and the preparation method of the modified mineral are the same as those in the example 2.
Example 8
The embodiment provides a spraying-free metallic high-heat-resistance polyamide material which comprises the following components in parts by weight:
the preparation method of the polyamide material is the same as that of the embodiment 2; the preparation method of the modified metal powder and the preparation method of the modified mineral are the same as those in the example 2.
Comparative examples 1 to 12
Polyamide materials of different compositions are provided, the contents of the components are shown in Table 1 in parts by weight, and the preparation method is the same as that of example 2. In the comparative example, the metal powder is silver powder, and the mineral is montmorillonite.
TABLE 1
The preparation method of the mineral treated by the coupling agent and the rare earth ions comprises the following steps:
(1) firstly, 100 parts by mass of montmorillonite is vacuumized and dried for 4 hours at the temperature of 100 ℃, and then is cooled to 25 ℃ under the vacuum condition;
(2) adding 0.8 part by mass of montmorillonite into 20mL of toluene, and ultrasonically dispersing for 30min at 25 ℃ to obtain a uniform suspension; then 0.364 mass part of coupling agent KH-550 is added into the suspension, and ultrasonic mixing is carried out for 5 min; reacting for 6 hours in a constant temperature tank at 90 ℃; centrifugally separating the reaction solution at 25 ℃ and 12000r/min to obtain montmorillonite modified by the coupling agent; washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr;
(3) adding 10 parts by mass of coupling agent modified montmorillonite into absolute ethyl alcohol for cleaning, stirring, standing for 20 hours, filtering and drying, preparing 1% thulium acetate deionized water solution, standing for 24 hours, then adding the cleaned montmorillonite, ultrasonically dispersing for 2 hours, standing for 36 hours, filtering, and drying in vacuum to constant weight to obtain the mineral treated by the coupling agent and rare earth ions.
The preparation method of the metal powder treated by the rare earth ions comprises the following steps:
(1) firstly, 100 parts by mass of metal silver powder is vacuumized and dried for 6 hours at the temperature of 100 ℃, and then is cooled to 25 ℃ under the vacuum condition;
(2) adding 10 parts by mass of metal silver powder into absolute ethyl alcohol, cleaning, stirring, standing for 20 hours, filtering and drying, preparing 1% thulium acetate deionized water solution, standing for 24 hours, adding the cleaned metal silver powder, dispersing for 2 hours by ultrasonic waves, standing for 36 hours, filtering, and drying in vacuum to constant weight to obtain the metal powder treated by rare earth ions.
The preparation method of the metal powder treated by the compatilizer and the rare earth ions comprises the following steps:
(1) adding 1 part by mass of metal silver powder into 100 parts by mass of decalin, and ultrasonically dispersing for 60min at normal temperature to obtain a uniform suspension; then adding 5 parts by mass of compatilizer UHMWPE-g-MAH into the suspension, and ultrasonically mixing for 20 min; reacting for 8 hours in a constant temperature bath at 130 ℃ to obtain metal silver powder modified by a compatilizer; centrifuging at 25 deg.C 12000r/min, washing with anhydrous ethanol for 3 times, and vacuum drying for 8 hr;
(2) adding 10 parts by mass of metal silver powder modified by a compatilizer into absolute ethyl alcohol for cleaning, stirring, standing for 20 hours, filtering and drying, preparing 1% thulium acetate deionized water solution with mass concentration, standing for 24 hours, then adding the cleaned metal powder, dispersing for 2 hours by ultrasonic waves, standing for 36 hours, filtering, and drying in vacuum to constant weight to obtain the metal powder treated by the compatilizer and rare earth ions.
Performance testing
The polyamide materials prepared in examples 1-8 and comparative examples 1-12 were subjected to performance tests, wherein the performance indexes include apparent mass percent of pass, heat distortion temperature, flexural modulus, tensile strength, notched impact strength of a simple beam at 23 ℃ and-30 ℃, and the specific data of the tests are shown in the following table 2: (wherein the measurement of the apparent yield and the surface gloss requires pretreatment of the above materials by injection molding the polyamides prepared in examples 1 to 8 and comparative examples 1 to 12 into a 100mm X120 mm large plate).
TABLE 2
The experimental results show that after the modified metal powder, the modified mineral and the compatilizer are added into the polyamide matrix, the apparent qualification rate of the obtained material can reach 95 percent, the maximum thermal deformation temperature can reach 117.3 ℃, and the toughness and the strength of the obtained material are excellent.
Among them, as can be seen from example 2, comparative example 3 and comparative example 8, the addition of the compatibilizer can improve the impact toughness at normal and low temperatures of the material; as can be seen from the example 2, the comparative example 2 and the comparative examples 10 to 12, the metal powder has better property improvement effect on the polyamide material than that of the polyamide material modified by a single modifier or modified by any two modifiers after being modified by the coupling agent, the compatilizer and the rare earth ions; similarly, it can be seen from example 2 and comparative examples 4 to 7 and 9 that the mineral, after being modified by the coupling agent, the compatibilizer and the rare earth ion, has a property improvement effect on the polyamide material better than that of the polyamide material modified by a single modifier or modified by any two modifiers.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The polyamide material is characterized by comprising the following components in parts by weight:
2. the polyamide material as claimed in claim 1, wherein the modified metal powder is a metal powder modified with a modifier;
preferably, the polyamide is selected from any one or combination of more than two of PA6, PA56, PA66, PA610, PA612, PA613, PA11, PA12, PA1010, PA1012, PA1111 and PA 1313;
preferably, the metal powder is selected from one or a combination of more than two of magnesium powder, silver powder, aluminum powder, copper powder, zinc powder, lead powder, titanium powder, stainless steel powder or gold powder;
preferably, the modified mineral is a mineral modified by a modifier;
preferably, the mineral is selected from any one or a combination of more than two of silicate mineral, carbonate mineral, borate or metal oxide;
preferably, the mineral is selected from any one or a combination of two or more of wollastonite, pyroxene, dickite, vermiculite, halloysite, sepiolite, montmorillonite, bentonite, kaolin, talc, nacrite, phlogopite, sericite, biotite, muscovite, limestone, nahcolite, barite, calcite, dolomite, huntite, nesotaite, brucite, trona, monetite, ludwigite, paigeite, gavite, alumina, iron oxide, magnesium oxide, zinc oxide, copper oxide or calcium oxide;
preferably, the modified metal powder is the same as or different from a modifying agent used for modifying the mineral, and the modifying agent comprises a coupling agent, a compatilizer and rare earth ions;
preferably, the coupling agent is selected from any one or the combination of more than two of silane coupling agent, phthalate coupling agent, aluminate coupling agent or zirconate coupling agent;
preferably, the coupling agent is selected from one or more of gamma-aminopropyltrimethoxysilane, gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma-glycidoxypropyltriethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltrimethoxysilane, N- (β -aminoethyl) -gamma-aminopropylmethyldimethoxysilane, gamma-ureidopropyltriethoxysilane, N-aminoethyl-gamma-aminopropyltriethoxysilane, gamma-aminopropylmethyldiethoxysilane, N- (β -aminoethyl) -gamma-aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilanes, anilinomethyltrimethoxysilane, isopropyl tri (dioctylphosphoryloxy) titanate, isopropyl triisostearate, isopropyldioleate acyloxy (dioctylphosphoryloxy) titanate, isopropyl tri (dioctylphosphoryloxy) titanate, isopropyltrioleate acyloxy titanate, isopropyl tri (dioctylphosphoryloxy) titanate, bis (dioctyloxypyrophosphate) ethoxyphosphate, bis (dioctyloxypyrophosphate) ethylenetitanate, bis (trioctyloxyphosphate) ethoxyphosphate and triethanolamine titanate, bis (dioctyloxypropylphosphate) titanate, bis (triethoxyzirconate chelate, bis (triethoxyaluminate) titanate, bis (triethoxyaluminate chelate, tris (triethoxyaluminate) titanate, tris (triethoxyaluminate) zirconate, tris (triethoxyaluminate chelate, tris (triethoxyaluminate) titanate, tris (triethoxyaluminate, tris;
preferably, the rare earth ion is selected from any one or a combination of more than two of zirconium ion, cobalt ion, lanthanum ion, praseodymium ion, samarium ion, europium ion, gadolinium ion, holmium ion, erbium ion, ytterbium ion, lutetium ion, scandium ion, indium ion, neodymium ion, cerium ion, yttrium ion, thulium ion, dysprosium ion or terbium ion.
3. Polyamide material according to claim 1 or 2, characterized in that the compatibilizer used in the modifier is the same or different from the compatibilizer added in the polyamide material, and comprises any one or a combination of two or more of POE-g-MAH, SBS-g-MAH, SEBS-g-MAH, EPDM-g-MAH, ABS-g-MAH, ASA-g-MAH, LDPE-g-MAH, LLDPE-g-MAH, UHMWPE-g-MAH, SMA, SAN-g-MAH, POE-g-GMA, EPDM-g-GMA, PE-g-GMA, MB-g-GMA, MGE or IA, preferably UHMWPE-g-MAH;
preferably, the modifying agent comprises a coupling agent, UHMWPE-g-MAH and rare earth ions.
4. Polyamide material according to any one of claims 1 to 3, characterized in that the polyamide material further comprises, in parts by weight, 0.1 to 1.0 part of an antioxidant;
preferably, the polyamide material further comprises 0.1-1.0 part by weight of an ultraviolet absorber;
preferably, the polyamide material further comprises 0.1-1.0 part by weight of a light stabilizer;
preferably, the polyamide material further comprises 0.1-1.0 part of heat stabilizer by weight;
preferably, the polyamide material further comprises 0.1-1.0 part by weight of a lubricant.
5. The polyamide material according to any one of claims 1-4, characterized in that the antioxidant is selected from one or more of tris (2, 4-di-tert-butylphenyl) phosphite, pentaerythritol tetrakis [ β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ], N '-bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, bis (2, 4-di-tert-butylphenyl) pentaerythritol diphosphite, N-octadecyl β - (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate, tris (2, 4-di-tert-butyl) phosphite, octadecyl hindered phenol (3, 5-dibutyl-4-hydroxy-phenylpropionate), 1,3, 5-tris (3, 5-di-tert-butyl, 4-hydroxybenzyl) s-triazine, 2,4,6- (1H,3H,5H) trione, N' -bis- (3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionyl) hexanediamine, bis [ 3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ] bis (3-di-tert-butyl-4-hydroxyphenyl) propionate), or a combination of any two or more of these pentaerythritol bis- (3, 4-di-tert-butyl-4-hydroxyphenyl) propionate;
preferably, the ultraviolet absorbent is selected from any one or the combination of more than two of benzoate, salicylate, benzophenone, benzotriazole or triazine ultraviolet absorbent;
preferably, the ultraviolet absorber is selected from one or more of 2, 4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 2- (2' -hydroxy-3 ',5' -bis (α -dimethylbenzyl) phenyl) benzotriazole, 2- (2-hydroxy-3-tert-butyl-5-methylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-tert-phenyl) -5-chlorobenzotriazole, 2- (2-hydroxy-3, 5-ditert-pentyl) benzotriazole, 2- (2' -hydroxy-4 ' -benzoyloxyphenyl) -5-chloro-2H-benzotriazole, resorcinol monobenzoate, 2- (4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazin-2-yl) -5-octyloxyphenol, 2,4, 6-tris (2' n-butoxyphenyl) -1,3, 5-triazine, 2- (4-hexyloxy-phenyl) salicylate, 5-diphenylhexanoate, 2-hydroxy-4-n-octyloxyphenyl-phenyl salicylate, 5-phenyl salicylate, 2-methyl-phenyl ester, and a combination of n-butyl-5-phenyl salicylate;
preferably, the light stabilizer is 4-benzoyloxy-2, 2,6, 6-tetramethylpiperidine, bis (1,2,2,6, 6-pentamethylpiperidinol) sebacate, 2,2,6, 6-tetramethylpiperidine benzoate, a polymer of succinic acid with 4-hydroxy-2, 2,6, 6-tetramethyl-1-piperidineethanol, bis (2,2,6, 6-tetramethyl-4-piperidinyl) sebacate or poly { [6- [ (1,1,3, 3-tetramethylbutyl) imino ] -1,3, 5-triazine-2, 4-diyl ] [2- (2,2,6, 6-tetramethylpiperidinyl) -nitrilo ] -hexamethylene- [4- (2,2,6, 6-tetramethylpiperidyl) -nitrilo ] };
preferably, the heat stabilizer is any one or a combination of more than two of halogenated cuprous compounds, copper salt phosphates or phosphates;
preferably, the lubricant is any one or a combination of two or more of silane polymer, solid paraffin, liquid paraffin, fatty acid salt, calcium stearate, zinc stearate, fatty amide, methylene bis stearamide, oleamide, stearamide, ethylene bis stearamide or N, N-ethylene bis stearamide.
6. Polyamide material according to any one of claims 1 to 5, characterized in that it comprises the following components in parts by weight:
7. a process for the preparation of a polyamide material according to any one of claims 1 to 6, characterized in that it comprises:
preparing modified metal powder and modified mineral, mixing the polyamide, the modified metal powder, the modified mineral and the compatilizer according to the formula ratio, adding the mixture into an extruder for melt blending, cooling, drying and granulating the mixture after extrusion to obtain the polyamide material.
8. The method according to claim 7, wherein the modified metal powder or the modified mineral is prepared by:
(1) drying metal powder or mineral in vacuum, dispersing the metal powder or mineral in a solvent, and mixing a coupling agent with the metal powder or mineral for reaction to obtain the metal powder or mineral modified by the coupling agent;
(2) dispersing the metal powder or mineral modified by the coupling agent in a solvent, and then reacting with a compatilizer for modification;
(3) modifying the metal powder or mineral obtained in the step (2) by using a solution containing rare earth ions to obtain modified metal powder or modified mineral;
preferably, the solvent in step (1) is toluene;
preferably, the reaction temperature in the step (1) is 80-100 ℃, and the reaction time is 6-8 h;
preferably, the solvent in step (2) is decalin;
preferably, the solution containing rare earth ions in the step (3) is any one of a rare earth acetate solution, a rare earth nitrate solution or a rare earth sulfate solution.
9. The method according to claim 7 or 8, wherein the time for mixing the polyamide, the modified metal powder, the modified mineral and the compatibilizer is 5 to 10 min;
preferably, the extruder is a twin screw extruder;
preferably, the working temperature of the double-screw extruder is 210-300 ℃;
preferably, the screw rotating speed of the extruder is 300-1000 revolutions per minute;
preferably, the residence time of the mass in the extruder is 1 to 3 min.
10. Use of the polyamide material as claimed in any one of claims 1 to 6 for the production of interior and exterior automotive parts or interior and exterior parts for electronic appliances.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911345777.0A CN111019339B (en) | 2019-12-24 | 2019-12-24 | Spraying-free metallic polyamide material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911345777.0A CN111019339B (en) | 2019-12-24 | 2019-12-24 | Spraying-free metallic polyamide material and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111019339A true CN111019339A (en) | 2020-04-17 |
| CN111019339B CN111019339B (en) | 2022-05-13 |
Family
ID=70212013
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911345777.0A Active CN111019339B (en) | 2019-12-24 | 2019-12-24 | Spraying-free metallic polyamide material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111019339B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410790A (en) * | 2020-04-29 | 2020-07-14 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111704796A (en) * | 2020-06-29 | 2020-09-25 | 上海中镭新材料科技有限公司 | Electroplating nylon material and preparation method thereof |
| CN113512265A (en) * | 2021-07-29 | 2021-10-19 | 深圳免喷材料科技有限公司 | Preparation method of anodic oxidation effect imitation spraying-free aesthetic ABS material |
| CN113999512A (en) * | 2021-11-23 | 2022-02-01 | 上海中镭新材料科技有限公司 | PC material and preparation method and application thereof |
| CN117534932A (en) * | 2023-10-08 | 2024-02-09 | 广东易聚源塑业科技有限公司 | Silencing self-lubricating high-wear-resistance POE master batch and preparation method thereof |
| WO2024066600A1 (en) * | 2022-09-29 | 2024-04-04 | 上海中镭新材料科技有限公司 | Polymeric alloy material, preparation method therefor, and use thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020198295A1 (en) * | 2000-05-29 | 2002-12-26 | Hiroshi Urabe | Flame retardant resin composition |
| CN107722620A (en) * | 2017-10-27 | 2018-02-23 | 上海金发科技发展有限公司 | A kind of low smell high glaze exempts to spray daiamid composition and preparation method thereof |
| CN110079019A (en) * | 2019-05-21 | 2019-08-02 | 合肥市丽红塑胶材料有限公司 | A kind of PA-PP hybrid resin material of toughening modifying and preparation method thereof |
-
2019
- 2019-12-24 CN CN201911345777.0A patent/CN111019339B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20020198295A1 (en) * | 2000-05-29 | 2002-12-26 | Hiroshi Urabe | Flame retardant resin composition |
| CN107722620A (en) * | 2017-10-27 | 2018-02-23 | 上海金发科技发展有限公司 | A kind of low smell high glaze exempts to spray daiamid composition and preparation method thereof |
| CN110079019A (en) * | 2019-05-21 | 2019-08-02 | 合肥市丽红塑胶材料有限公司 | A kind of PA-PP hybrid resin material of toughening modifying and preparation method thereof |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111410790A (en) * | 2020-04-29 | 2020-07-14 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111410790B (en) * | 2020-04-29 | 2022-10-25 | 广东圆融新材料有限公司 | Humidity-sensitive fluorescent modified polypropylene material and preparation method thereof |
| CN111704796A (en) * | 2020-06-29 | 2020-09-25 | 上海中镭新材料科技有限公司 | Electroplating nylon material and preparation method thereof |
| CN111704796B (en) * | 2020-06-29 | 2023-02-17 | 上海中镭新材料科技有限公司 | Electroplating nylon material and preparation method thereof |
| CN113512265A (en) * | 2021-07-29 | 2021-10-19 | 深圳免喷材料科技有限公司 | Preparation method of anodic oxidation effect imitation spraying-free aesthetic ABS material |
| CN113999512A (en) * | 2021-11-23 | 2022-02-01 | 上海中镭新材料科技有限公司 | PC material and preparation method and application thereof |
| WO2024066600A1 (en) * | 2022-09-29 | 2024-04-04 | 上海中镭新材料科技有限公司 | Polymeric alloy material, preparation method therefor, and use thereof |
| CN117534932A (en) * | 2023-10-08 | 2024-02-09 | 广东易聚源塑业科技有限公司 | Silencing self-lubricating high-wear-resistance POE master batch and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111019339B (en) | 2022-05-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111019339B (en) | Spraying-free metallic polyamide material and preparation method and application thereof | |
| CN111004497B (en) | Electroplating nylon material and preparation method thereof | |
| CN111019315B (en) | Glass fiber reinforced PC material and preparation method and application thereof | |
| CN111019334B (en) | Glass fiber reinforced polyamide material and preparation method and application thereof | |
| CN102766299B (en) | Anti-impacting anti-ageing modified polypropylene material and preparation method thereof | |
| CN111607213B (en) | Polycarbonate material and preparation method and application thereof | |
| CN102134366A (en) | Polycarbonate (PC)/acrylonitrile-butadiene-styrene (ABS) or polyvinyl chloride (PVC)/ABS alloy with low linear expansion coefficient and preparation method thereof | |
| CN102134367A (en) | Polymer alloy with added wood (bamboo) powder and flake material and preparation method thereof | |
| JP2017061675A (en) | Polyamide compositions | |
| CN107082949B (en) | High-performance polypropylene plastic packaging barrel and preparation method thereof | |
| CN101735577A (en) | High weld mark strength reinforced polybutylene terephthalate material and preparation method thereof | |
| JP2014141630A (en) | Polyamide resin composition | |
| CN102702612B (en) | High-flow precipitation-resistant halogen-free flame-retardant polypropylene composite material and preparation method thereof | |
| CN114656782A (en) | Low-precipitation environment-friendly flame-retardant bio-based nylon composite material and preparation method thereof | |
| CN104845026A (en) | Heat-resistant ABS (acrylonitrile-butadiene-styrene) resin composition high in scratch resistance and preparation method of heat-resistant ABS resin composition | |
| JP2015224286A (en) | Polyamide resin composition | |
| CN110982253B (en) | Polyamide material and preparation method and application thereof | |
| CN114736456B (en) | Polypropylene composition and preparation method and application thereof | |
| WO2022210019A1 (en) | Polyamide resin composition and polyamide molded body | |
| CN106479035B (en) | Flame-retardant impact-resistant polypropylene composite material and preparation method thereof | |
| CN102382347A (en) | Injection molding grade environment-friendly anti-flaming ultra-high molecular weight polyethylene and preparation method thereof | |
| CN108003610B (en) | Polyamide resin composition and molded article thereof | |
| CN104693756A (en) | Toughened, weather-resistant and modified fame-retardant PC/PBT alloy | |
| KR101447352B1 (en) | Polypropylene Resin Composition | |
| CN114940818B (en) | Polyurethane master batch, laser-weldable polyamide composition and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |