WO2021128964A1 - 一种电镀尼龙材料及其制备方法 - Google Patents

一种电镀尼龙材料及其制备方法 Download PDF

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WO2021128964A1
WO2021128964A1 PCT/CN2020/115200 CN2020115200W WO2021128964A1 WO 2021128964 A1 WO2021128964 A1 WO 2021128964A1 CN 2020115200 W CN2020115200 W CN 2020115200W WO 2021128964 A1 WO2021128964 A1 WO 2021128964A1
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electroplated
optionally
nylon material
parts
ion
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French (fr)
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刘春艳
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SHANGHAI ZHONGLEI NEW MATERIAL SCIENCE CO Ltd
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SHANGHAI ZHONGLEI NEW MATERIAL SCIENCE CO Ltd
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • 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
    • C08K9/00—Use of pretreated ingredients
    • C08K9/02—Ingredients treated with inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/04—Ingredients treated with organic substances
    • C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/54—Electroplating of non-metallic surfaces
    • C25D5/56—Electroplating of non-metallic surfaces of plastics
    • 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • 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
    • C08K3/34—Silicon-containing compounds
    • C08K3/346—Clay
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone

Definitions

  • This application belongs to the field of polymer materials, for example, it relates to an electroplated nylon material and a preparation method thereof.
  • Polyamide is commonly known as nylon (Nylon). It is a linear polymer with repeating unit amide bonds (-CONH-) in the molecule. It is formed by polycondensation of dibasic acid and diamine. It can also be opened by amino acid caprolactam. Ring polymerization. It is an engineering plastic with excellent performance. It has good mechanical strength, self-lubricating performance, good wear resistance, shock absorption and noise reduction. It is widely used in machinery, automobiles, electrical appliances and other industries. However, there are polar amide bonds in the polyamide molecules, which are easy to absorb water, resulting in poor dimensional stability and reduced mechanical strength. On the other hand, the notched impact toughness of polyamide is poor. These problems limit the scope of its application.
  • Plastic electroplating is to coat the plastic surface with metal, which can not only achieve a good metal texture, but also reduce the weight of the product. While effectively improving the appearance and decoration of the plastic, it also improves its electrical, thermal and corrosion resistance. Performance, so today there are a large number of plastic electroplating products used in electronics, automobiles, home appliances and other industries. At present, the usual method to realize polyamide electroplating is to add inorganic minerals, metal oxides and glass fibers to the polyamide.
  • CN101787204A provides a low water absorption polyamide composition and a preparation method thereof.
  • the polyamide composition is composed of 10 to 90 parts by weight of polyamide, 10 to 60 parts of styrene resin, and 3 parts by weight of layered silicate clay. -10 parts, less than 2 parts of additives, 2-10 parts of compatibilizer and 5-20 parts of chopped glass fiber.
  • This invention combines the characteristics of polyamide solvent resistance, high toughness, easy processing and low water absorption of ABS resin.
  • the layered silicate clay accelerates the crystallization speed of polyamide, improves the crystallinity and mechanical strength, and obtains
  • the extremely low water absorption greatly improves the dimensional stability of the material while maintaining impact toughness, but the polyamide polymer prepared by this method cannot be used for electroplating.
  • CN106046781A provides an aromatic polyamide compound for electroplating treatment, which, in terms of mass percentage, includes the following components: aromatic polyamide resin 40%-70%, aliphatic polyamide powder 5%-10%, caprolactam 0.2%-1%, sodium caprolactam 0.1%-0.5% and inorganic oxide mineral powder 20%-50%.
  • aromatic polyamide resin 40%-70% aliphatic polyamide powder 5%-10%
  • caprolactam 0.2%-1% sodium caprolactam 0.1%-0.5%
  • inorganic oxide mineral powder 20%-50% The obtained aromatic polyamide composite has been greatly improved in terms of electroplating layer adhesion, water resistance, tensile strength, bending strength and impact resistance, and is more suitable for the needs of consumers and industry development.
  • the moldability of aromatic polyamide and semi-aromatic polyamide is worse than that of aliphatic polyamide, and the injection molded parts are prone to residual internal stress, which eventually leads to poor electroplating, and at the same time, its cost is higher.
  • CN108164995A provides a high-strength, easily electroplated polyamide composite material and a preparation method thereof, which comprises the following components in a certain proportion by weight: polyamide resin, organically modified nano-montmorillonite, inorganic filler, Silane coupling agent, caprolactam, initiator, antioxidant and lubricant.
  • the high-strength, easily electroplated polyamide composite material of this invention realizes the uniform dispersion of montmorillonite and inorganic fillers in the polyamide substrate at the nanometer scale, and can be used as a riveting point to increase the resin substrate and the metal coating during the electroplating roughening process
  • the purpose of this application is to provide an electroplated nylon material and a preparation method thereof.
  • the electroplated nylon material provided by the application has the characteristics of excellent rigidity, good impact toughness at normal and low temperature, and high electroplating qualification rate, and is an electroplated nylon material with good performance.
  • this application adopts the following technical solutions:
  • the present application provides an electroplated nylon material, based on the total weight of the electroplated nylon material being 100 parts, the electroplated nylon material includes the following components in parts by weight:
  • the electroplated nylon material provided in this application uses polyamide as the matrix material, adds modified minerals and compatibilizers, and adjusts the amount of each component to match each other, so that the composite material has a high and excellent electroplating pass rate, excellent rigidity and High impact toughness at normal and low temperature.
  • the weight parts of the polyamide is 50-80 parts, for example, it can be 50 parts, 55 parts, 60 parts, 65 parts, 70 parts, 75 parts or 80 parts.
  • the weight part of the modified mineral is 20-50 parts, for example, it can be 20 parts, 25 parts, 30 parts, 35 parts, 40 parts, 45 parts or 50 parts.
  • the weight part of the compatibilizer is 2-8 parts, for example, it can be 2 parts, 2.5 parts, 3 parts, 3.5 parts, 4 parts, 5 parts, 6 parts, 7 parts or 8 parts.
  • the dispersibility and compatibility of minerals in the PA matrix material can be further improved, and it has the function of providing physical crosslinking points for minerals, which significantly improves the impact toughness of composite materials at normal and low temperatures.
  • the polyamide is selected from PA6, PA46, PA56, PA66, PA610, PA612, PA613, PA11, PA12, PA1010, PA1012, PA1111, PA1313, PA6T, PA9T, PA10T, PA6I or PA6I /6T Any one or a combination of two or more;
  • the modified mineral is a mineral modified by a modifier.
  • the mineral is selected from any one or a combination of two or more of silicate minerals, carbonate minerals, borate minerals or metal oxides;
  • the mineral is selected from wollastonite, pyroxene, dickite, vermiculite, halloysite, sepiolite, montmorillonite, bentonite, kaolin, talc, pearl mica, phlogopite, sericite, Biotite, Muscovite, Limestone, Sodalite, Potashite, Calcite, Dolomite, Iron Dolomite, Walnutite, Potashite, Sodium Carbonate, Sodalite, Bicarbonate, Any of trona, plagioclase, hydromagnesite, magnesite, boronite, boronite, schnite, alumina, iron oxide, magnesium oxide, zinc oxide, copper oxide or calcium oxide One or a combination of two or more.
  • the modifier is a coupling agent and a rare earth ion.
  • the modified minerals described in this application are minerals that are treated with a coupling agent and then treated with rare earth ions.
  • the dispersibility of minerals in PA is improved from both chemical and physical aspects, which not only improves the rigidity of the mixture, makes the obtained electroplated nylon material excellent in rigidity, but also makes its impact toughness at normal and low temperature. Better, suitable for electroplating at the same time, with a higher electroplating qualification rate.
  • the coupling agent is any one or a combination of two or more of a silane coupling agent, a phthalate coupling agent, an aluminate coupling agent, or a zirconate coupling agent.
  • the coupling agent is selected from the group consisting of ⁇ -aminopropyltrimethoxysilane, ⁇ -aminopropyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -glycidyl ether Oxypropyltriethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxy Silane, ⁇ -ureapropyltriethoxysilane, N-aminoethyl- ⁇ -aminopropyltriethoxysilane, ⁇ -aminopropylmethyldiethoxysilane, N-( ⁇ -aminoethyl Group)- ⁇ -aminopropyltriethoxysilane, polyaminoalkyltrialkoxysilane, poly
  • the rare earth ion is selected from 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 Any one or a combination of two or more of ions, cerium ions, yttrium ions, thulium ions, dysprosium ions, or terbium ions.
  • the preparation method of the modified mineral includes the following steps:
  • the temperature of vacuum drying in step (1) is 100-120°C, for example, it can be 100°C, 105°C, 110°C, 112°C, 115°C, or 120°C; the time is 4-6h, for example, 4h, 4.2h, 4.5h, 5h, 5.5h or 6h.
  • the solvent in step (1) is toluene.
  • the reaction temperature in step (2) is 80-100°C, for example, it can be 80°C, 85°C, 88°C, 90°C, 95°C or 100°C, etc.; the time is 6-8h, for example, it can be 6h, 6.2h, 6.5h, 7h, 7.5h or 8h etc.
  • the solution containing rare earth ions in step (3) is selected from any one of a rare earth acetate solution, a rare earth nitrate solution or a rare earth sulfate solution.
  • the mass concentration of rare earth ions in the solution containing rare earth ions in step (3) is 0.5-1.5%, for example, it can be 0.5%, 0.8%, 1%, 1.2%, 1.3%, or 1.5%.
  • the dispersion method in step (3) is ultrasonic dispersion, and the dispersion time is 1.5-2.5h, for example, it can be 1.5h, 1.8h, 2h, 2.1h, 2.3h or 2.5h.
  • the compatibilizer 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 with maleic anhydride), EPDM-g-MAH (ethylene propylene rubber grafted with 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), LLDPE-g-MAH (linear low density
  • the electroplated nylon material further includes 0.1-1.0 parts by weight (for example, it can 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). Parts or 1.0 parts etc.) of antioxidants.
  • the electroplated nylon material further comprises 0.1-1.0 parts by weight (for example, it can 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. ) UV absorber.
  • the electroplated nylon material further comprises 0.1-1.0 parts by weight (for example, it can be 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. )'S light stabilizer.
  • the electroplated nylon material further comprises 0.1-1.0 parts by weight (for example, it can be 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. )'S heat stabilizer.
  • the electroplated nylon material further comprises 0.1-1.0 parts by weight (for example, it can be 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 lubricants.
  • Lubricant has the function of improving the processing fluidity of alloy materials, and it also helps to improve the wear resistance.
  • the antioxidant is selected from tris(2,4-di-tert-butylphenyl) phosphite, tetrakis[ ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid] Pentaerythritol ester, N,N'-bis-(3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionyl)hexamethylene diamine, bis(2,4-di-tert-butylphenyl) pentaerythritol Diphosphite, ⁇ -(3,5-di-tert-butyl-4-hydroxyphenyl) n-octadecyl propionate, tris(2,4-di-tert-butyl) phosphite, hindered phenol ( 3,5-dibutyl-4-hydroxy-phenylpropionic acid octadecyl) ester, 1,3,
  • the ultraviolet absorber is selected from any one or two or more of benzoate, salicylate, benzophenone, benzotriazole or triazine ultraviolet absorbers combination.
  • UV absorbers of benzoate, salicylate, benzophenone, benzotriazole and triazine can strongly absorb ultraviolet light and convert light energy into heat energy to release, improving the material’s performance UV resistance.
  • Benzoates, salicylates, benzophenones, benzotriazoles and triazines are all organic compounds, which have good compatibility with the matrix material and will not affect the mechanical properties of the alloy material performance.
  • the ultraviolet absorber is selected from 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone , 2-(2-hydroxy-5-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'bis( ⁇ , ⁇ -dimethylbenzyl)phenyl)benzene O-triazole, 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-3',5'-di-tert-benzene Yl)-5-chlorobenzotriazole, 2-(2-hydroxy-3,5-di-tertpentylphenyl)benzotriazole, 2-(2'-hydroxy-4'-benzoic acid phenyl Yl)-5chloro-2H-benzotriazole, resorcinol monobenzoate, 2-(4,6-bis(2,4-di
  • the light stabilizer is selected from 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, sebacic acid bis(1,2,2,6,6-pentamethyl Piperidinol) ester, 2,2,6,6-tetramethylpiperidine benzoate, succinic acid and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidine ethanol Polymer, bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate or poly ⁇ [6-[(1,1,3,3-tetramethylbutyl) Amino]-1,3,5-triazine-2,4-diyl][2-(2,2,6,6-tetramethylpiperidinyl)-nimino]-hexamethylene-[4 -(2,2,6,6-tetramethylpiperidinyl)-nimino] ⁇ any one or a combination of two or more.
  • the light stabilizer can effectively capture the active free radicals generated by the polymer material under the action of ultraviolet light, thereby exerting the light stabilizing effect; it can be used in combination with the ultraviolet absorber to more effectively avoid the photodegradation of the polymer material.
  • the heat stabilizer is selected from any one or a combination of two or more of cuprous halides, copper salt phosphates, or phosphates.
  • Thermal stabilizers can provide polyamide materials with long-term stability and prevent materials from becoming brittle under the highest working temperature and pressure. Thermal stabilizers can prevent polyamide materials from premature mechanical fatigue under high temperature, chemical corrosion and harsh environmental conditions. , Commonly used heat stabilizers include BRUGGOLEN H320, PolyAd HS-01 and PolyAd HS-03, etc.
  • the lubricant is silane polymer, solid paraffin, liquid paraffin, fatty acid salt, calcium stearate, zinc stearate, fatty amide, methylene bis-stearic acid amide, oleic acid amide, stearin Any one or a combination of two or more of amide, ethylenebisstearic acid amide or N,N-ethylenebisstearic acid amide.
  • the electroplated nylon material includes the following components in parts by weight:
  • the present application provides a method for preparing electroplated nylon material as described in the first aspect.
  • the preparation method is: mixing the formulated amount of polyamide, modified mineral and compatibilizer and adding to the extruder
  • the electroplated nylon material is obtained by melt blending, cooling, drying and pelletizing after extrusion.
  • the time for mixing each component material of the formula amount is 5-10 min, for example, it may be 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min.
  • the extruder is a twin screw extruder.
  • the working temperature of the extruder is 210-330°C, for example 210°C, 220°C, 230°C, 240°C, 250°C, 255°C, 260°C, 270°C, 280°C, 290°C , 300°C, 310°C, 320°C or 330°C etc.
  • the screw speed of the extruder is 300-1000 revolutions per minute, for example, 300 revolutions per minute, 400 revolutions per minute, 450 revolutions per minute, 500 revolutions per minute, 550 revolutions per minute, and 600 revolutions per minute. Minutes, 650 rpm, 700 rpm, 750 rpm, 800 rpm, 850 rpm or 1000 rpm, etc.
  • the residence time of the material in the extruder is 1-3 min, for example, it can be 1 min, 1.5 min, 2 min, 2.5 min, or 3 min.
  • the electroplated nylon material provided by this application is added with modified minerals and compatibilizers treated with coupling agent and rare earth ion. Through the synergistic effect of coupling agent and rare earth ionization, the dispersibility of minerals is improved, and the nylon is improved at the same time.
  • the obtained electroplated nylon material has a normal temperature notched impact strength of 8.1-15.1 kJ/m 2 , a low temperature notched impact strength of 4.9-10.3 kJ/m 2 , a tensile strength of up to 93.6 MPa, and a flexural modulus of It can reach 6500MPa; and the material is suitable for electroplating, and its electroplating qualification rate is 78%-90%.
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is:
  • the components in the above formula are uniformly mixed with a high-speed mixer for 5 minutes, and then the mixture is added to the twin-screw extruder for melt blending.
  • the working parameters of the extruder are as follows: the temperature in the first zone is 210°C, and the temperature in the second zone is 220°C, the temperature in zone three is 230°C, zone four is 240°C, zone five is 240°C, zone six is 240°C, zone seven is 240°C, zone eight is 240°C, zone nine is 240 The temperature in the ten zone is 240°C, the temperature in the eleven zone is 235°C, the screw speed is 350 revolutions/minute, and the residence time is 3 minutes. After extrusion, it is cooled, dried, and pelletized to obtain the electroplated nylon material.
  • the preparation method of the modified mineral includes the following steps:
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is:
  • the components in the above formula are uniformly mixed with a high-speed mixer for 8 minutes, and then the mixture is added to the twin-screw extruder for melt blending.
  • the working parameters of the extruder are as follows: the temperature in the first zone is 240°C, and the temperature in the second zone is 250°C, the temperature in zone three is 260°C, the temperature in zone four is 260°C, the temperature in zone five is 260°C, the temperature in zone six is 260°C, the temperature in zone seven is 260°C, the temperature in zone eight is 260°C, and the temperature in zone nine is 260
  • the temperature in the ten zone is 260°C, the temperature in the eleven zone is 255°C, the screw speed is 500 revolutions per minute, and the residence time is 1.5 min. After extrusion, it is cooled, dried, and pelletized to obtain the electroplated nylon material.
  • the preparation method of the modified mineral includes the following steps:
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is:
  • the components in the above formula are uniformly mixed with a high-speed mixer for 10 minutes, and then the mixture is added to the twin-screw extruder for melt blending.
  • the working parameters of the extruder are as follows: the temperature in the first zone is 240°C, and the temperature in the second zone is 250°C, the temperature in zone three is 260°C, the temperature in zone four is 260°C, the temperature in zone five is 260°C, the temperature in zone six is 260°C, the temperature in zone seven is 260°C, the temperature in zone eight is 260°C, and the temperature in zone nine is 260
  • the temperature in the ten zone is 260°C, the temperature in the eleven zone is 255°C, the screw speed is 850 revolutions per minute, and the residence time is 3 minutes. After extrusion, it is cooled, dried, and pelletized to obtain the electroplated nylon material.
  • the preparation method of the modified mineral includes the following steps:
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is the same as that of Example 2.
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is the same as that of Example 2.
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is the same as that of Example 2.
  • This embodiment provides an electroplated nylon material, which contains the following components in parts by weight:
  • the preparation method of the above-mentioned electroplated nylon material is the same as that of Example 2.
  • Example 3 Compared with Example 3, the weight of polyamide in this comparative example is 100 parts, without modified minerals and compatibilizer POE-g-MAH, and the remaining components and preparation methods are the same as in Example 3.
  • Example 3 Compared with Example 3, the weight parts of the polyamide in this comparative example is 70 parts, and the modified mineral is replaced with untreated minerals. The weight parts of the mineral is 30 parts and does not contain the compatibilizer POE. -g-MAH, other components and preparation methods are the same as in Example 3.
  • the weight parts of the polyamide in this comparative example is 70 parts, and the modified mineral is replaced with the mineral treated with the coupling agent, and the weight part of the mineral treated with the coupling agent is 30 parts, without compatibilizer POE-g-MAH, the other components and preparation method are the same as in Example 3;
  • Example 3 Compared with Example 3, the weight parts of the polyamide in this comparative example is 100 parts, without the compatibilizer POE-g-MAH, and the remaining components and preparation methods are the same as in Example 3.
  • Example 3 Compared with Example 3, the weight parts of the polyamide in this comparative example is 100 parts, without modified minerals, and the remaining components and preparation methods are the same as in Example 3.
  • the weight parts of polyamide in this comparative example is 70 parts.
  • the modified minerals are replaced with minerals treated with rare earth ions.
  • the weight parts of the minerals treated with rare earth ions is 30 parts.
  • the components and preparation method are the same as in Example 3;
  • the preparation method of the rare earth ion-treated mineral is as follows: first, 100 parts by weight of the mineral is vacuum dried at 100°C for 4 hours, the mineral is talc, and then cooled to normal temperature under vacuum; configuration 1 The rare earth acetate deionized water solution with a mass concentration of% mass concentration is allowed to stand for 24 hours, and then the mineral is added, ultrasonically dispersed for 2 hours, left to stand for 36 hours, filtered and dried in vacuum to a constant weight to prepare a mineral that has only been treated with rare earth ions.
  • Example 3 Compared with Example 3, the weight parts of polyamide in this comparative example is 70 parts, and the modified mineral is replaced with untreated minerals. The weight parts of the mineral is 30 parts, the remaining components and the preparation method The same as in Example 3.
  • Example 3 Compared with Example 3, the weight parts of the polyamide in this comparative example is 70 parts, and the modified mineral is replaced with the mineral treated with the coupling agent, and the weight part of the mineral treated with the coupling agent is 30 parts. , The remaining components and preparation methods are the same as in Example 3.
  • Example 3 and Comparative Example 5 it can be seen from Example 3 and Comparative Example 5 that without adding modified minerals, the tensile strength and flexural modulus of the obtained material are lower; from Example 3 and Comparative Examples 1-4, it can be seen that no matter if the compatibilizer is not included Whether the mineral is modified or not, the normal and low temperature impact toughness of the obtained material is relatively low; from Example 3 and Comparative Examples 6-8, it can be seen that after the mineral is treated with a coupling agent and rare earth ions, the normal and low temperature toughness of the obtained material is significantly better For unmodified minerals and minerals modified by coupling agent and rare earth ion alone.
  • Comparative example 2 40 Comparative example 3 66 Comparative example 4 84 Comparative example 5 0 Comparative example 6 73 Comparative example 7 70 Comparative example 8 75

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Abstract

本文公开了一种电镀尼龙材料及其制备方法。所述电镀尼龙材料按重量份计包括50-80份聚酰胺、20-50份改性矿物和2-8份相容剂。所述改性矿物由矿物经过偶联剂处理和稀土离子处理之后得到。

Description

一种电镀尼龙材料及其制备方法 技术领域
本申请属于高分子材料领域，例如涉及一种电镀尼龙材料及其制备方法。
背景技术
聚酰胺(Polyamide,PA)俗称尼龙(Nylon)，它是分子内具有重复单元酰胺键(-CONH-)的线性高分子，其由二元酸和二元胺缩聚而成，也可由氨基酸己内酰胺开环聚合。它是性能优异的工程塑料，具有良好的机械强度、自润滑性能、良好的耐磨性能及减震消音等特点，被广泛应用于机械、汽车、电器等行业。但聚酰胺分子内存在极性的酰胺键，容易吸水，导致其尺寸稳定性差且机械强度下降，另一方面聚酰胺的缺口冲击韧性较差，这些问题限制了其应用范围。
塑料电镀是将塑料表面披覆上金属，不仅可以实现良好的金属质感，而且能减轻制品重量，在有效改善塑料外观及装饰性的同时，也改善了其在电、热及耐蚀等方面的性能，因此今日已有大量塑料电镀产品应用在电子、汽车、家电用品等工业上，目前实现聚酰胺电镀的通常方法是在聚酰胺中添加无机矿物、金属氧化物和玻璃纤维等。
CN101787204A提供一种低吸水率聚酰胺组合物及其制备方法，所述聚酰胺组合物由按重量份计的聚酰胺10-90份、苯乙烯树脂10-60份、层状硅酸盐黏土3-10份、添加剂小于2份、相容剂2-10份及短切玻璃纤维5-20份组成。此发明兼备了聚酰胺耐溶剂性、高韧性、易加工性和ABS树脂的低吸水性的特点，同时层状硅酸盐黏土加快了聚酰胺的结晶速度，提高了结晶度和机械强度，获得极低的吸水率，极大的改善了材料的尺寸稳定性而又保持冲击韧性，但此方法 制备的聚酰胺聚合物不能用来电镀。
CN106046781A提供了一种用于电镀处理的芳香族聚酰胺复合物，按质量百分比计，包括如下组分：芳香族聚酰胺树脂40％-70％、脂肪族聚酰胺粉末5％-10％、己内酰胺0.2％-1％、己内酰胺钠0.1％-0.5％和无机氧化物矿粉20％-50％。所得到的芳香族聚酰胺复合物在电镀层结合力、耐水性、拉伸强度、弯曲强度和抗冲击性能上均获得了较大幅度的提升，更加适应消费者和行业发展的需求。但芳香族聚酰胺、半芳香族聚酰胺成型性较脂肪族聚酰胺差，注塑件容易残留内应力，最终导致电镀不良，同时其成本较高。
CN108164995A提供了一种高强度、易电镀的聚酰胺复合材料及其制备方法，其包括按一定重量份数配比的如下组分：聚酰胺树脂、有机改性纳米蒙脱土、无机填充物、硅烷偶联剂、己内酰胺、引发剂、抗氧剂和润滑剂。此发明的高强度、易电镀聚酰胺复合材料实现了蒙脱土和无机填充物在聚酰胺基材中纳米尺度上的均匀分散，电镀粗化过程中可以作为铆合点增加树脂基材与金属镀层之间的结合力，获得高电镀结合力的制件，然而此发明提供的尼龙材料在刚性和冲击韧性方面还有待提升，
因此，如何获得一种具有优异的刚性和较高的常低温冲击韧性，同时易于电镀的尼龙材料成为目前急需解决的问题。
发明内容
本申请的目的在于提供一种电镀尼龙材料及其制备方法。本申请提供的电镀尼龙材料，具有刚性优异、常低温冲击韧性良好且电镀合格率高的特点，是一种性能良好的电镀尼龙材料。为达此目的，本申请采用以下技术方案：
第一方面，本申请提供一种电镀尼龙材料，基于所述电镀尼龙材料的总重 量为100份，所述电镀尼龙材料按重量份计包括以下组分：
聚酰胺                  50-80份
改性矿物                20-50份
相容剂                  2-8份。
本申请提供的电镀尼龙材料，以聚酰胺为基体材料，添加了改性矿物和相容剂，调节各组分的用量，使其相互配合，使得复合材料具有高优良电镀合格率、优异刚性和较高的常低温冲击韧性。
在本申请中，所述聚酰胺的重量份为50-80份，例如可以是50份、55份、60份、65份、70份、75份或80份等。
所述改性矿物的重量份为20-50份，例如可以是20份、25份、30份、35份、40份、45份或50份等。
所述相容剂的重量份为2-8份，例如可以是2份、2.5份、3份、3.5份、4份、5份、6份、7份或8份等。
通过添加相容剂，可以进一步提高矿物在PA基体材料中分散性和相容性，而且具有为矿物提供物理交联点的作用，明显提高了复合材料的常低温冲击韧性。
作为本申请可选的技术方案，所述聚酰胺选自PA6、PA46、PA56、PA66、PA610、PA612、PA613、PA11、PA12、PA1010、PA1012、PA1111、PA1313、PA6T、PA9T、PA10T、PA6I或PA6I/6T任意一种或两种以上组合；
可选地，所述改性矿物为改性剂改性的矿物。
可选地，所述矿物选自硅酸盐矿物、碳酸盐矿物、硼酸盐矿物或金属氧化物中的任意一种或两种以上组合；
可选地，所述矿物选自硅灰石、辉石、地开石、蛭石、埃洛石、海泡石、蒙脱土、膨润土、高岭土、滑石、珍珠云母、金云母、绢云母、黑云母、白云母、石灰石、苏打石、重碳酸钾石、方解石、白云石、铁白云石、碳酸钙镁石、碳酸钾钙石、碳酸钠钙石、碳酸铈钠石、水碳镁石、天然碱、斜钠钙石、水菱镁矿、硼镁石、硼镁铁矿、硼铁矿、白硼钙石、氧化铝、氧化铁、氧化镁、氧化锌、氧化铜或氧化钙中任意一种或两种以上的组合。
可选地，所述改性剂为偶联剂和稀土离子。
本申请中所述的改性矿物是经过偶联剂处理之后再使用稀土离子进行处理得到的矿物。通过偶联剂和稀土离子处理，从化学和物理两个方面改善了矿物在PA中的分散性，不仅提高了混合物的刚性，使所得到的电镀尼龙材料刚性优异，而且使其常低温冲击韧性较好，同时适合电镀，电镀合格率较高。
可选地，所述偶联剂为硅烷偶联剂、酞酸酯偶联剂、铝酸酯偶联剂或锆酸酯偶联剂中任意一种或两种以上的组合。
可选地，所述偶联剂选自γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-脲丙基三乙氧基硅烷、N-氨乙基-γ-氨丙基三乙氧基硅烷、γ-氨丙基甲基二乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、多氨基烷基三烷氧基硅烷、苯胺甲基三甲氧基硅烷、三(二辛基磷酰氧基)钛酸异丙酯、三异硬脂酸钛酸异丙酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯和三乙 醇胺的螯合物、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、二硬脂酰氧异丙基铝酸酯、异丙氧基二硬脂酸酰氧基铝酸酯、铝酸三甲酯、铝酸三异丙酯、铝酸三苄酯、烷氧基三(乙烯基-乙氧基)锆酸酯、烷氧基三(对氨基苯氧基)锆酸酯、双(柠檬酸二乙酯)二丙氧基锆螯合物或四(三乙醇胺)锆酸酯中的任意一种或两种以上的组合。
可选地，所述稀土离子选自锆离子、钴离子、镧离子、镨离子、钐离子、铕离子、钆离子、钬离子、铒离子、镱离子、镥离子、钪离子、铟离子、钕离子、铈离子、钇离子、铥离子、镝离子或铽离子中任意一种或两种以上的组合。
作为本申请可选的技术方案，所述改性矿物的制备方法包括如下步骤：
(1)将矿物真空干燥后分散于溶剂中；
(2)将所述矿物与偶联剂混合反应，分离得到经偶联剂改性的矿物；
(3)将所述经偶联剂改性的矿物分散于含有稀土离子的溶液中得到所述改性矿物。
作为本申请可选的技术方案，步骤(1)中所述真空干燥的温度为100-120℃，例如可以是100℃、105℃、110℃、112℃、115℃或120℃等；时间为4-6h，例如可以是4h、4.2h、4.5h、5h、5.5h或6h等。
可选地，步骤(1)中所述溶剂为甲苯。
可选地，步骤(2)中所述反应温度为80-100℃，例如可以是80℃、85℃、88℃、90℃、95℃或100℃等；时间为6-8h，例如可以是6h、6.2h、6.5h、7h、7.5h或8h等。
可选地，步骤(3)中含有稀土离子的溶液选自稀土醋酸盐溶液、稀土硝酸盐溶液或稀土硫酸盐溶液中任意一种。
可选地，步骤(3)中所述含有稀土离子的溶液中稀土离子的质量浓度为0.5-1.5％，例如可以是0.5％、0.8％、1％、1.2％、1.3％或1.5％等。
可选地，步骤(3)中所述分散的方法为超声波分散，分散时间为1.5-2.5h，例如可以是1.5h、1.8h、2h、2.1h、2.3h或2.5h等。
作为本申请可选的技术方案，所述相容剂选自POE-g-MAH(马来酸酐接枝乙烯辛烯共聚弹性体)、SBS-g-MAH(苯乙烯丁二烯苯乙烯共聚物接枝马来酸酐)、SEBS-g-MAH(苯乙烯-丁二烯-苯乙烯嵌段共聚物接枝马来酸酐)、EPDM-g-MAH(三元乙丙橡胶接枝马来酸酐)、ABS-g-MAH(马来酸酐接枝丙烯腈-丁二烯-苯乙烯共聚物)、ASA-g-MAH(马来酸酐接枝丙烯腈-苯乙烯-丙烯酸酯共聚物)、LDPE-g-MAH(低密度聚乙烯接枝马来酸酐)、LLDPE-g-MAH(线型低密度聚乙烯接枝马来酸酐)、UHMWPE-g-MAH(超高分子量聚乙烯接枝马来酸酐)、SMA(苯乙烯-马来酸酐共聚物)、SAN-g-MAH(丙烯腈-苯乙烯接枝马来酸酐)、POE-g-GMA(乙烯-辛烯共聚物接枝甲基丙烯酸缩水甘油酯)、EPDM-g-GMA(三元乙丙橡胶接枝甲基丙烯酸缩水甘油酯)、PE-g-GMA(聚乙烯接枝甲基丙烯酸缩水甘油酯)、MB-g-GMA(聚丁二烯接枝甲基丙烯酸缩水甘油酯)、MGE(甲基丙烯酸甲酯-甲基丙烯酸缩水甘油酯-丙烯酸乙酯三元聚合物)或IA(酞亚胺化丙烯酸)中的任意一种或两种以上的组合，可选为POE-g-MAH。
作为本申请可选的技术方案，所述电镀尼龙材料按重量份计还包括0.1-1.0份(例如可以是0.1份、0.2份、0.3份、0.5份、0.6份、0.7份、0.8份、0.9份或1.0份等)的抗氧化剂。
可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份(例如可以是0.1 份、0.2份、0.3份、0.5份、0.6份、0.7份、0.8份、0.9份或1.0份等)的紫外吸收剂。
可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份(例如可以是0.1份、0.2份、0.3份、0.5份、0.6份、0.7份、0.8份、0.9份或1.0份等)的光稳定剂。
可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份(例如可以是0.1份、0.2份、0.3份、0.5份、0.6份、0.7份、0.8份、0.9份或1.0份等)的热稳定剂。
可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份(例如可以是0.1份、0.2份、0.3份、0.5份、0.6份、0.7份、0.8份、0.9份或1.0份等)的润滑剂。润滑剂具有提高合金材料加工流动性的作用，同时也对提高耐磨性有一定帮助。
可选地，所述抗氧化剂选自三(2,4-二叔丁基苯基)亚磷酸酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺、双(2,4-二叔丁基苯基)季戊四醇二亚磷酸酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、亚磷酸三(2,4-二叔丁基)酯、受阻酚(3,5-二丁基-4-羟基-苯基丙酸十八烷基)酯、1,3,5-三(3,5-二叔丁基,4-羟基苄基)均三嗪、2,4,6-(1H,3H,5H)三酮、N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]或季戊四醇二亚磷酸二硬脂基酯中的任意一种或两种以上的组合。
可选地，所述紫外吸收剂选自苯甲酸酯类、水杨酸酯类、二苯甲酮类、苯并三唑类或三嗪类紫外吸收剂中的任意一种或两种以上的组合。
苯甲酸酯类、水杨酸酯类、二苯甲酮类、苯并三唑类和三嗪类的紫外吸收剂，能强烈地吸收紫外光，并将光能转变为热能放出，提高材料的抗紫外性能。苯甲酸酯类、水杨酸酯类、二苯甲酮类、苯并三唑类和三嗪类均是有机化合物，与基体材料之间具有良好的相容性，不会影响合金材料的机械性能。
可选地，所述紫外吸收剂选自2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-(2-羟基-5-甲基苯基)苯并三氮唑、2-(2'-羟基-3',5'双(α,α-二甲基苄基)苯基)苯并三唑、2-(2-羟基-3-特丁基-5-甲基苯基)-5-氯苯并三唑、2-(2'-羟基-3',5'-二叔苯基)-5-氯化苯并三唑、2-(2-羟基-3,5-二特戊基苯基)苯并三唑、2-(2'-羟基-4'-苯甲酸基苯基)-5氯-2H-苯并三唑、单苯甲酸间苯二酚酯、2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-辛氧基酚、2,4,6-三(2'-羟基-4'-正丁氧基苯基)-1,3,5-三嗪、2-(4,6-二苯基-1,3,5-三嗪-2)-5-正己烷氧基苯酚、水杨酸苯酯、水杨酸-4异丙基苄酯、水杨酸-2-乙基己基酯或六甲基磷酰三胺中的任意一种或两种以上的组合。
可选地，所述光稳定剂选自4-苯甲酰氧基-2,2,6,6-四甲基哌啶、癸二酸双(1,2,2,6,6-五甲基哌啶醇)酯、苯甲酸2,2,6,6-四甲基哌啶脂、丁二酸与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯或聚{[6-[(1,1,3,3-四甲基丁基)亚氨基]-1,3,5-三嗪-2,4-二基][2-(2,2,6,6-四甲基哌啶基)-次氨基]-六亚甲基-[4-(2,2,6,6-四甲基哌啶基)-次氨基]}中的任意一种或两种以上的组合。
光稳定剂可有效地捕获高分子材料在紫外线作用下产生的活性自由基，从而发挥光稳定效用；其同紫外吸收剂复配使用，更能有效避免高分子材料的光降解。
可选地，所述热稳定剂选自卤化亚铜类、铜盐磷酸盐类或磷酸盐类中的任意一种或两种以上的组合。
热稳定剂能够为聚酰胺材料提供长期稳定性，而且可以防止材料在最高工作温度压力下变脆，热稳定剂能防止聚酰胺材料在高温、化学腐蚀以及恶劣环境条件下产生过早的机械疲劳，常用的热稳定剂包括BRUGGOLEN H320、PolyAd HS-01和PolyAd HS-03等。
可选地，所述润滑剂为硅烷聚合物、固体石蜡、液体石蜡、脂肪酸盐、硬脂酸钙、硬脂酸锌、脂肪酰胺、甲撑双硬脂酸酰胺、油酸酰胺、硬脂酰胺、乙撑双硬酯酰胺或N,N-乙撑双硬脂酸酰胺中的任意一种或两种以上的组合。
作为本申请可选的技术方案，基于所述电镀尼龙材料的总重量为100份，所述电镀尼龙材料按重量份计包括以下组分：
Figure PCTCN2020115200-appb-000001
第二方面，本申请提供一种如第一方面所述的电镀尼龙材料的制备方法，所述制备方法为：将配方量的聚酰胺、改性矿物和相容剂混合后加入挤出机中熔融共混，挤出后冷却、干燥并切粒得到的所述电镀尼龙材料。
可选地，所述配方量的各组分物料混合所用的时间为5-10min，例如可以是5min、6min、7min、8min、9min或10min等。
可选地，所述挤出机为双螺杆挤出机。
可选地，所述挤出机的工作温度为210-330℃，例如可以是210℃、220℃、230℃、240℃、250℃、255℃、260℃、270℃、280℃、290℃、300℃、310℃、320℃或330℃等。
可选地，所述挤出机的螺杆转速为300-1000转/分钟，例如可以300转/分钟、400转/分钟、450转/分钟、500转/分钟、550转/分钟、600转/分钟、650转/分钟、700转/分钟、750转/分钟、800转/分钟、850转/分钟或1000转/分钟等。
可选地，所述物料在挤出机中的停留时间为1-3min，例如可以是1min、1.5min、2min、2.5min或3min等。
与现有技术相比，本申请至少具有以下有益效果：
本申请提供的电镀尼龙材料，添加了偶联剂处理和稀土离子处理的改性矿物和相容剂，通过偶联剂和稀土离子化的协同作用，改善了矿物的分散能力，同时提升了尼龙材料的各项性能，所得电镀尼龙材料的常温缺口冲击强度为8.1-15.1kJ/m 2，低温缺口冲击强度为4.9-10.3kJ/m 2，拉伸强度为可达93.6MPa，弯曲模量为可达6500MPa；且该材料适合电镀，其电镀合格率为78％-90％。
具体实施方式
为便于理解本申请，本申请列举实施例如下。本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
以下实施例中所用的实验材料，如无特殊说明，均为自常规试剂材料厂商购买得到。以下实施例中，所用相容剂POE-g-MAH可以使用如下制备方法得到：
将三口烧瓶置于120℃的油浴锅中，加入100ml的甲苯和20质量份的POE，加热使POE充分溶解后，加入0.5质量份的引发剂过氧化二异丙苯(DCP,dicumyl peroxide)和10质量份的马来酸酐(MAH)，通入氮气保护，充分反应4-8h，冷却到室温过滤后得到POE-g-MAH；取5质量份的POE-g-MAH，用滤纸包好，放入索氏抽提器中，用丙酮抽提36h，以充分除去未反应的引发剂、接枝单体及可能生成的MAH均聚物，将抽提后POE-g-MAH在60℃烘箱中干燥10h，然后在真空干燥箱干燥至恒重，保存待用。
实施例1
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000002
上述电镀尼龙材料的制备方法为：
将上述配方中的组分用高速混合机均匀混合5min，而后将混合物加入到双螺杆挤出机中进行熔融共混，挤出机的工作参数如下：一区温度为210℃，二区温度为220℃，三区温度为230℃，四区温度为240℃，五区温度为240℃，六区温度为240℃，七区温度为240℃，八区温度为240℃，九区温度为240℃，十区温度240℃，十一区温度235℃，螺杆转速为350转/分钟，停留时间为3min，挤出后冷却、干燥、切粒，得到所述电镀尼龙材料。
其中，改性矿物的制备方法包括如下步骤：
(1)首先将100重量份的矿物，所述矿物为蒙脱土，在120℃条件下进行 抽真空干燥4小时，然后在真空条件下冷却到25℃；
(2)将0.8重量份的矿物加入到20mL甲苯中，25℃超声分散60min得均匀悬浮液；再将0.364重量份硅烷偶联剂KH-550加入到悬浮液中，超声混合5min；90℃恒温槽中反应8h；反应液常温12000r/min离心分离；再用无水乙醇洗涤3次，真空干燥8h得经偶联剂改性的矿物；将10重量份的经偶联剂改性的矿物加入去离子水中，搅拌，过滤，再加入无水乙醇中，搅拌，静置20h，过滤，烘干待用；
(3)配置1％质量浓度的醋酸铥去离子水溶液，静置24h，然后将经偶联剂改性的矿物加入，超声波分散2h，静置36h，过滤后真空干燥至恒重，制得改性矿物。
实施例2
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000003
上述电镀尼龙材料的制备方法为：
将上述配方中的组分用高速混合机均匀混合8min，而后将混合物加入到双螺杆挤出机中进行熔融共混，挤出机的工作参数如下：一区温度为240℃，二区温度为250℃，三区温度为260℃，四区温度为260℃，五区温度为260℃，六区温度为260℃，七区温度为260℃，八区温度为260℃，九区温度为260℃，十区温度260℃，十一区温度255℃，螺杆转速为500转/分钟，停留时间为1.5min，挤出后冷却、干燥、切粒，得到所述电镀尼龙材料。
其中，改性矿物的制备方法包括如下步骤：
(1)首先将100重量份的矿物，所述矿物为蒙脱土，在110℃条件下进行抽真空干燥5小时，然后在真空条件下冷却到25℃；
(2)将0.8重量份的矿物加入到20mL甲苯中，常温超声分散50min得均匀悬浮液；再将0.364重量份硅烷偶联剂KH-550加入到悬浮液中，超声混合8min；80℃恒温槽中反应8h；反应液常温12000r/min离心分离得到经偶联剂改性的矿物；再用无水乙醇洗涤3次，真空干燥8h；将10重量份的经偶联剂改性的矿物加入去离子水中，搅拌，过滤，再加入无水乙醇中，搅拌，静置20h，过滤，烘干，待用；
(3)配置1％质量浓度的醋酸镝去离子水溶液，静置24h，然后将经偶联剂改性的矿物加入，超声波分散1.5h，静置36h，过滤后真空干燥至恒重，制得改性矿物。
实施例3
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000004
Figure PCTCN2020115200-appb-000005
上述电镀尼龙材料的制备方法为：
将上述配方中的组分用高速混合机均匀混合10min，而后将混合物加入到双螺杆挤出机中进行熔融共混，挤出机的工作参数如下：一区温度为240℃，二区温度为250℃，三区温度为260℃，四区温度为260℃，五区温度为260℃，六区温度为260℃，七区温度为260℃，八区温度为260℃，九区温度为260℃，十区温度260℃，十一区温度255℃，螺杆转速为850转/分钟，停留时间为3min，挤出后冷却、干燥、切粒，得到所述电镀尼龙材料。
其中，改性矿物的制备方法包括如下步骤：
(1)首先将100重量份的矿物，所述矿物为滑石粉，在120℃条件下进行抽真空干燥6小时，然后在真空条件下冷却到常温；
(2)将0.8重量份的矿物加入到20mL甲苯中，常温超声分散60min得均匀悬浮液；再将0.364重量份硅烷偶联剂KH-540加入到悬浮液中，超声混合10min；90℃恒温槽中反应8h；反应液常温12000r/min离心分离；再用无水乙醇洗涤3次，真空干燥8h得经偶联剂改性的矿物。将10重量份的经偶联剂改性的矿物加入去离子水中，搅拌，过滤，再加入无水乙醇中，搅拌，静置20h， 过滤，烘干，待用；
(3)配置1.5％质量浓度的硝酸铽去离子水溶液，静置24h，然后将经偶联剂改性的矿物加入，超声波分散2.5h，静置36h，过滤后真空干燥至恒重，制得改性矿物。
实施例4
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000006
上述电镀尼龙材料的制备方法同实施例2。
实施例5
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000007
Figure PCTCN2020115200-appb-000008
上述电镀尼龙材料的制备方法同实施例2。
实施例6
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000009
上述电镀尼龙材料的制备方法同实施例2。
实施例7
本实施例提供一种电镀尼龙材料，按重量份计包含如下组分：
Figure PCTCN2020115200-appb-000010
Figure PCTCN2020115200-appb-000011
上述电镀尼龙材料的制备方法同实施例2。
对比例1
相比于实施例3，本对比例中聚酰胺的重量份数为100份，不含改性矿物和相容剂POE-g-MAH，其余组分和制备方法同实施例3。
对比例2
相比于实施例3，本对比例中聚酰胺的重量份数为70份，同时将改性矿物替换为未处理的矿物，所述矿物的重量份数为30份，不含相容剂POE-g-MAH，其余组分和制备方法同实施例3。
对比例3
相比于实施例3，本对比例中聚酰胺的重量份数为70份，同时将改性矿物替换为经偶联剂处理的矿物，所述经偶联剂处理的矿物的重量份数为30份，不含相容剂POE-g-MAH，其余组分和制备方法同实施例3；
对比例4
相比于实施例3，本对比例中聚酰胺的重量份数为100份，不含相容剂POE-g-MAH，其余组分和制备方法同实施例3。
对比例5
相比于实施例3，本对比例中聚酰胺的重量份数为100份，不含改性矿物，其余组分和制备方法同实施例3。
对比例6
相比于实施例3，本对比例中聚酰胺的重量份数为70份，同时将改性矿物替换为经过稀土离子处理的矿物，经过稀土离子处理的矿物的重量份数为30份，其余组分和制备方法同实施例3；
所述经过稀土离子处理的矿物的制备方法为：首先将100重量份的矿物在100℃条件下进行抽真空干燥4小时，所述矿物为滑石粉，然后在真空条件下冷却到常温；配置1％质量浓度的稀土醋酸盐去离子水溶液，静置24h，然后将所述矿物加入，超声波分散2h，静置36h，过滤后真空干燥至恒重，制得仅经过稀土离子处理的矿物。
对比例7
相比于实施例3，本对比例中聚酰胺的重量份数为70份，同时将改性矿物替换为未处理的矿物，所述矿物的重量份数为30份，其余组分和制备方法同实施例3。
对比例8
相比于实施例3，本对比例中聚酰胺的重量份数为70份，同时将改性矿物替换为经偶联剂处理的矿物，经偶联剂处理的矿物的重量份数为30份，其余组分和制备方法同实施例3。
性能测试
1.将实施例1-7与对比例1-8制备的电镀尼龙材料进行性能测试，性能指标 包括拉伸强度、弯曲模量、23℃和-30℃下简支梁缺口冲击强度，测试的具体数据如下表1所示：
表1
Figure PCTCN2020115200-appb-000012
由表1数据可知，实施例中所得的尼龙材料各项性能参数相比于对比例都有明显的提升，说明本申请提供的电镀尼龙材料性能优异，拉伸强度和弯曲模量较高，刚性较好且常低温韧性佳。
其中，由实施例3与对比例5可知，不添加改性矿物，所得材料的拉伸强度和弯曲模量较低；由实施例3与对比例1-4可知，不含相容剂时无论矿物是否经过改性，所得材料的常低温冲击韧性都较低；由实施例3与对比例6-8比较可知，矿物在经过偶联剂和稀土离子处理后，所得材料的常低温韧性明显优于未改性的矿物以及偶联剂和稀土离子单独改性的矿物。
2.将实施例1-7与对比例1-8制备的电镀尼龙材料注塑成140×90×3mm的样板，将样板按照电镀工艺进行电镀，评估其电镀合格率，其结果如表2所示。
表2
性能指标 电镀合格率(％)
测试标准 奔驰电镀件外观标准
实施例1 78
实施例2 81
实施例3 87
实施例4 86
实施例5 79
实施例6 83
实施例7 90
对比例1 0
对比例2 40
对比例3 66
对比例4 84
对比例5 0
对比例6 73
对比例7 70
对比例8 75
由表2数据可知，当电镀尼龙材料中含有改性矿物时，即实施例1-7与对比例4，所得尼龙材料适用于电镀，且电镀合格率为78％-90％。当不含任何矿物时，如对比例1和5，所得的尼龙材料不能用于电镀，电镀合格率为0；当添加的矿物仅偶联剂或仅经过稀土离子处理时，相比于改性矿物，所得尼龙材料的电镀合格率较低，说明偶联剂与稀土离子在处理矿物时起到了协同作用。
申请人声明，以上所述仅为本申请的具体实施方式，但本申请的保护范围并不局限于此。

Claims (12)

  1. 一种电镀尼龙材料，其中，基于所述电镀尼龙材料的总重量为100份，所述电镀尼龙材料按重量份计包括以下组分：
    聚酰胺                  50-80份
    改性矿物                20-50份
    相容剂                  2-8份。
  2. 根据权利要求1所述的电镀尼龙材料，其中，所述改性矿物为改性剂改性的矿物；且所述改性剂为偶联剂和稀土离子。
  3. 根据权利要求1或2所述的电镀尼龙材料，其中，所述聚酰胺选自PA6、PA46、PA56、PA66、PA610、PA612、PA613、PA11、PA12、PA1010、PA1012、PA1111、PA1313、PA6T、PA9T、PA10T、PA6I或PA6I/6T中任意一种或两种以上的组合。
  4. 根据权利要求2所述的电镀尼龙材料，其中，所述矿物选自硅酸盐矿物、碳酸盐矿物、硼酸盐或金属氧化物中的任意一种或两种以上组合；
    可选地，所述矿物选自硅灰石、辉石、地开石、蛭石、埃洛石、海泡石、蒙脱土、膨润土、高岭土、滑石、珍珠云母、金云母、绢云母、黑云母、白云母、石灰石、苏打石、重碳酸钾石、方解石、白云石、铁白云石、碳酸钙镁石、碳酸钾钙石、碳酸钠钙石、碳酸铈钠石、水碳镁石、天然碱、斜钠钙石、水菱镁矿、硼镁石、硼镁铁矿、硼铁矿、白硼钙石、氧化铝、氧化铁、氧化镁、氧化锌、氧化铜或氧化钙中任意一种或两种以上的组合；
    可选地，所述偶联剂选自硅烷偶联剂、酞酸酯偶联剂、铝酸酯偶联剂或锆酸酯偶联剂中任意一种或两种以上的组合；
    可选地，所述偶联剂选自γ-氨丙基三甲氧基硅烷、γ-氨丙基三乙氧基硅烷、γ-缩水甘油醚氧丙基三甲氧基硅烷、γ-缩水甘油醚氧丙基三乙氧基硅烷、N-(β- 氨乙基)-γ-氨丙基三甲氧基硅烷、N-(β-氨乙基)-γ-氨丙基甲基二甲氧基硅烷、γ-脲丙基三乙氧基硅烷、N-氨乙基-γ-氨丙基三乙氧基硅烷、γ-氨丙基甲基二乙氧基硅烷、N-(β-氨乙基)-γ-氨丙基三乙氧基硅烷、多氨基烷基三烷氧基硅烷、苯胺甲基三甲氧基硅烷、三(二辛基磷酰氧基)钛酸异丙酯、三异硬脂酸钛酸异丙酯、异丙基二油酸酰氧基(二辛基磷酸酰氧基)钛酸酯、异丙基三(二辛基磷酸酰氧基)钛酸酯、异丙基三油酸酰氧基钛酸酯、异丙基三(二辛基焦磷酸酰氧基)钛酸酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯、双(二辛氧基焦磷酸酯基)乙撑钛酸酯和三乙醇胺的螯合物、四异丙基二(二辛基亚磷酸酰氧基)钛酸酯、二硬脂酰氧异丙基铝酸酯、异丙氧基二硬脂酸酰氧基铝酸酯、铝酸三甲酯、铝酸三异丙酯、铝酸三苄酯、烷氧基三(乙烯基-乙氧基)锆酸酯、烷氧基三(对氨基苯氧基)锆酸酯、双(柠檬酸二乙酯)二丙氧基锆螯合物或四(三乙醇胺)锆酸酯中的任意一种或两种以上的组合；
    可选地，所述稀土离子选自锆离子、钴离子、镧离子、镨离子、钐离子、铕离子、钆离子、钬离子、铒离子、镱离子、镥离子、钪离子、铟离子、钕离子、铈离子、钇离子、铥离子、镝离子或铽离子中任意一种或两种以上的组合。
  5. 根据权利要求1-4中任一项所述的电镀尼龙材料，其中，所述改性矿物的制备方法包括如下步骤：
    (1)将矿物真空干燥后分散于溶剂中；
    (2)将所述矿物与偶联剂混合反应，分离得到经偶联剂改性的矿物；
    (3)将所述经偶联剂改性的矿物分散于含有稀土离子的溶液中得到所述改性矿物。
  6. 根据权利要求1-5任一项所述的电镀尼龙材料，其中，步骤(1)中所述 真空干燥的温度为100-120℃，时间为4-6h；
    可选地，步骤(1)中所述溶剂为甲苯；
    可选地，步骤(2)中所述反应温度为80-100℃，时间为6-8h；
    可选地，步骤(3)中所述含有稀土离子的溶液选自稀土醋酸盐溶液、稀土硝酸盐溶液或稀土硫酸盐溶液中任意一种；
    可选地，步骤(3)中所述含有稀土离子的溶液中稀土离子的质量浓度为0.5-1.5％；
    可选地，步骤(3)中所述分散的方法为超声波分散，分散时间为1.5-2.5h。
  7. 根据权利要求1-6任一项所述的电镀尼龙材料，其中，所述相容剂选自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或IA中的任意一种或两种以上的组合，可选为POE-g-MAH。
  8. 根据权利要求1-7任一项所述的电镀尼龙材料，其中，所述电镀尼龙材料按重量份计还包括0.1-1.0份的抗氧化剂；
    可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份的紫外吸收剂；
    可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份的光稳定剂；
    可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份的热稳定剂；
    可选地，所述电镀尼龙材料按重量份计还包括0.1-1.0份的润滑剂。
  9. 根据权利要求1-8任一项所述的电镀尼龙材料，其中，所述抗氧化剂选自三(2,4-二叔丁基苯基)亚磷酸酯、四[β-(3,5-二叔丁基-4-羟基苯基)丙酸]季戊四醇酯、N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺、双(2,4-二叔丁基苯 基)季戊四醇二亚磷酸酯、β-(3,5-二叔丁基-4-羟基苯基)丙酸正十八碳醇酯、亚磷酸三(2,4-二叔丁基)酯、受阻酚(3,5-二丁基-4-羟基-苯基丙酸十八烷基)酯、1,3,5-三(3,5-二叔丁基,4-羟基苄基)均三嗪、2,4,6-(1H,3H,5H)三酮、N,N'-双-(3-(3,5-二叔丁基-4-羟基苯基)丙酰基)己二胺、二缩三乙二醇双[β-(3-叔丁基-4-羟基-5-甲基苯基)丙酸酯]或季戊四醇二亚磷酸二硬脂基酯中的任意一种或两种以上的组合；
    可选地，所述紫外吸收剂选自苯甲酸酯类、水杨酸酯类、二苯甲酮类、苯并三唑类或三嗪类紫外吸收剂中的任意一种或两种以上的组合；
    可选地，所述紫外吸收剂选自2,4-二羟基二苯甲酮、2-羟基-4-甲氧基二苯甲酮、2-羟基-4-正辛氧基二苯甲酮、2-(2-羟基-5-甲基苯基)苯并三氮唑、2-(2'-羟基-3',5'双(α,α-二甲基苄基)苯基)苯并三唑、2-(2-羟基-3-特丁基-5-甲基苯基)-5-氯苯并三唑、2-(2'-羟基-3',5'-二叔苯基)-5-氯化苯并三唑、2-(2-羟基-3,5-二特戊基苯基)苯并三唑、2-(2'-羟基-4'-苯甲酸基苯基)-5氯-2H-苯并三唑、单苯甲酸间苯二酚酯、2-(4,6-双(2,4-二甲基苯基)-1,3,5-三嗪-2-基)-5-辛氧基酚、2,4,6-三(2'-羟基-4'-正丁氧基苯基)-1,3,5-三嗪、2-(4,6-二苯基-1,3,5-三嗪-2)-5-正己烷氧基苯酚、水杨酸苯酯、水杨酸-4异丙基苄酯、水杨酸-2-乙基己基酯或六甲基磷酰三胺中的任意一种或两种以上的组合；
    可选地，所述光稳定剂选自4-苯甲酰氧基-2,2,6,6-四甲基哌啶、癸二酸双(1,2,2,6,6-五甲基哌啶醇)酯、苯甲酸2,2,6,6-四甲基哌啶脂、丁二酸与4-羟基-2,2,6,6-四甲基-1-哌啶乙醇的聚合物、双(2,2,6,6-四甲基-4-哌啶基)癸二酸酯或聚{[6-[(1,1,3,3-四甲基丁基)亚氨基]-1,3,5-三嗪-2,4-二基][2-(2,2,6,6-四甲基哌啶基)-次氨基]-六亚甲基-[4-(2,2,6,6-四甲基哌啶基)-次氨基]}中的任意一种或两种以上的组合；
    可选地，所述热稳定剂选自卤化亚铜类、铜盐磷酸盐类或磷酸盐类中的任意一种或两种以上的组合；
    可选地，所述润滑剂选自硅烷聚合物、固体石蜡、液体石蜡、脂肪酸盐、硬脂酸钙、硬脂酸锌、脂肪酰胺、甲撑双硬脂酸酰胺、油酸酰胺、硬脂酰胺、乙撑双硬酯酰胺或N,N-乙撑双硬脂酸酰胺中的任意一种或两种以上的组合。
  10. 根据权利要求1-9任一项所述的电镀尼龙材料，其中，基于所述电镀尼龙材料的总重量为100份，所述电镀尼龙材料按重量份计包括以下组分：
    Figure PCTCN2020115200-appb-100001
  11. 一种如权利要求1-10中任一项所述的电镀尼龙材料的制备方法，其中，所述制备方法为：
    将配方量的聚酰胺、改性矿物和相容剂混合后加入挤出机中熔融共混，挤出后冷却、干燥并切粒得到的所述电镀尼龙材料。
  12. 根据权利要求11所述的制备方法，其中，配方量的聚酰胺、改性矿物和相容剂混合所用的时间为5-10min；
    可选地，所述挤出机为双螺杆挤出机；
    可选地，所述挤出机的工作温度为210-330℃；
    可选地，所述挤出机的螺杆转速为300-1000转/分钟；
    可选地，所述物料在挤出机中的停留时间为1-3min。
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