WO2019242126A1 - 具有高金属质感的聚酰胺树脂组合物及其制备方法 - Google Patents

具有高金属质感的聚酰胺树脂组合物及其制备方法 Download PDF

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WO2019242126A1
WO2019242126A1 PCT/CN2018/105917 CN2018105917W WO2019242126A1 WO 2019242126 A1 WO2019242126 A1 WO 2019242126A1 CN 2018105917 W CN2018105917 W CN 2018105917W WO 2019242126 A1 WO2019242126 A1 WO 2019242126A1
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Prior art keywords
special effect
polyamide resin
resin composition
servings
screw
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PCT/CN2018/105917
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English (en)
French (fr)
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刘星
季得运
罗明华
辛敏琦
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上海锦湖日丽塑料有限公司
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Priority to EP18923643.3A priority Critical patent/EP3789456B1/en
Publication of WO2019242126A1 publication Critical patent/WO2019242126A1/zh

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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
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/223—Packed additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/20—Compounding polymers with additives, e.g. colouring
    • C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
    • C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
    • 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
    • C08K2003/0812—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
    • 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
    • C08K2003/0856—Iron
    • 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
    • C08K2003/0893—Zinc
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of 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
    • C08K3/38—Boron-containing compounds
    • C08K2003/387—Borates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Definitions

  • the invention relates to a polyamide resin composition with high metal texture and a preparation method thereof, and belongs to the technical field of polymer materials.
  • Spray-free aesthetic plastic by adding pigments with special effects such as aluminum powder, pearl powder, copper-zinc powder, glass flakes to the matrix resin, or by controlling the microstructure of the substrate, the material has high-gloss, metal-like, rock-like aesthetics Exterior.
  • the special color effect with beautiful appearance can be achieved through one molding, eliminating post-processing steps such as spraying and silk screen, high production efficiency, low cost, no environmental pollution, low energy consumption, 100% recyclable. Based on the above advantages, spray-free aesthetic plastic has become an important modification direction of contemporary materials.
  • Nylon material has high strength, excellent abrasion resistance, high heat resistance, good chemical stability and fluidity, and has a very wide range of applications in the fields of automobiles, electronics and home appliances. These advantages also give nylon materials a very good application prospect as a spray-free aesthetic plastic substrate. However, due to the opacity of the nylon material due to crystallinity, the simple addition of special effect toner will greatly reduce the aesthetic effect. At the same time, special effect pigments with poor compatibility with the matrix are added, and the toughness of the material will be significantly reduced. In addition, nylon materials generally have problems of high hygroscopicity and high molding shrinkage.
  • Patent CN201310446502 discloses a polyamide resin composition with a metallic effect, including a polymerization reaction process of a copolymer in the presence of a swellable layered silicate, mainly for improving the welding resistance of the product. Resilience is not considered.
  • the invention adopts the method of in situ polymerization, and the control of the preparation equipment and process is very complicated and the cost is high.
  • CN201611014288 discloses a toughened nylon 66 material suitable for spray-free welding masks and a preparation method thereof.
  • the invention improves the toughness and fluidity of ordinary dyed nylon materials without considering the realization of special effect toner in the material.
  • Patent CN201710593044 discloses a nano-polyamide composition with metallic luster and a preparation method thereof.
  • the invention mainly uses a homemade nano-polyamide masterbatch as a reinforcing material and interacts with a core-shell dispersant, supplemented by corresponding processing aid Agent to improve the dispersion and enhancement of nano particles, the surface gloss is improved, without considering the metal texture of the final product, a large number of inorganic fillers will mask the metal special effect toner.
  • CN201611079305 uses a coupling agent and zinc stearate to synergistically improve the dispersion of metallic pigments without considering the physical properties of the material.
  • an object of the present invention is to provide a polyamide aesthetic resin composition with high metal texture and a preparation method thereof.
  • the present invention provides a polyamide resin composition having a high metallic texture, which includes the following components in parts by weight:
  • Polyamide resin 70 to 95 parts
  • Polymethyl methacrylate grafted maleic anhydride / styrene 5 to 30 parts;
  • Additives 0.1 to 2 servings: 0.1 to 2 servings.
  • the polyamide includes at least one of PA6, PA66, PA46, PA610, PA68, PAMXD6, PA10, PA12, PA11, PA6T, PA10T, PA1010, PA1212, PA9T.
  • the weight average molecular weight of the polymethyl methacrylate grafted maleic anhydride / styrene (referred to as PMMA-g-MAH / S) is 40,000 to 140,000, and the maleic anhydride content is 0.05 to 1 wt%.
  • the particle diameter of the special effect toner is 1 to 200 ⁇ m.
  • the special effect toner is selected from the group consisting of bismuth oxychloride crystalline metal pigment, mica-coated metal pigment, silica-coated metal pigment, aluminum borate salt-coated metal pigment, and artificial mica.
  • the additive is dibutyltin maleate-methyl methacrylate-sodium methacrylate copolymer (abbreviated as DBTM-MMA-NaMA).
  • the weight average molecular weight of the dibutyltin maleate-methyl methacrylate-sodium methacrylate copolymer is 1,000 to 40,000, wherein the content of dibutyltin maleate is 0.5 to 2 wt. %, Sodium methacrylate copolymer 2-15% by weight.
  • the auxiliary agent is selected from at least one of a pigment, a heat stabilizer, an antioxidant, a weathering agent, a plasticizer, a lubricant, a release agent, an antistatic agent, and an inorganic filler.
  • the present invention also provides a method for preparing a polyamide resin composition with high metal texture as described above, which includes the following steps:
  • Polymethyl methacrylate grafted with maleic anhydride / styrene and additives are extruded through a twin-screw extruder to obtain a melt; a special-effect toner is added to the melt and extruded. Special effect toner masterbatch is obtained; the temperature of the extruder used is 190-250 ° C, the aspect ratio of the screw is 40-60, and the speed of the screw is 400-600 rpm;
  • the melt is extruded through a twin-screw extruder.
  • special effect master batches are added to the melt through side feeding.
  • the temperature of the extruder used is 190-290 ° C
  • the aspect ratio of the screw is 40-60
  • the rotation speed of the screw is 400-600 rpm.
  • the present invention has the following beneficial effects:
  • Blending PMMA-g-MAH / S can improve the water absorption and scratch resistance of polyamide resin
  • the additive DBTM-MMA-NaMA has very good compatibility with the special effect toner and PMMA-g-MAH / St copolymer. It is adsorbed on the toner surface to help the special effect toner in PMMA-g-MAH / St. Disperse evenly to avoid mutual accumulation of special effect toners;
  • Examples 1 to 5 were prepared by the following process: grafting polymethyl methacrylate with maleic anhydride / styrene, adding additives, pre-mixing according to the mixing ratio, extruding through a twin-screw extruder, and feeding through side
  • the special effect toner is added to the melt according to the mixing ratio, and the special effect toner masterbatch is obtained by extrusion.
  • the temperature of the extruder used is 190-250 ° C, the aspect ratio of the screw is 40-60, and the speed of the screw is 400-600 rpm.
  • Examples 6 to 8 were prepared by the following process: polymethyl methacrylate grafted with maleic anhydride / styrene, additives were added after pre-mixing according to the ratio and extruded through a twin-screw extruder, and simultaneously fed through side
  • the method adds the special effect toner to the melt according to the mixing ratio, and performs extrusion to obtain the special effect toner master batch.
  • the temperature of the extruder used is 190-250 ° C, the aspect ratio of the screw is 40-60, and the speed of the screw is 400-600 rpm.
  • PA PA6
  • DBTM-MMA-NaMA polymethyl methacrylate grafted maleic anhydride / styrene
  • DBTM-MMA-NaMA The PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m; the PMMA-g-MAH / St Mw is 140,000 and the MAH content is 1 wt%; The described DBTM-MMA-NaMA Mw is 40,000, wherein the DBTM content is 2% by weight and the NaMA content is 15% by weight.
  • PA 95phr PA, 0.5phr special effect toner, 5phr polymethyl methacrylate grafted maleic anhydride / styrene, 0.1phr DBTM-MMA-NaMA.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m; the PMMA-g-MAH / St Mw is 40,000, and the MAH content is 0.05 wt%;
  • the DBTM-MMA-NaMA Mw is 1000, wherein the DBTM content is 0.5 wt%, and the NaMA content is 2 wt%.
  • PA PA6
  • DBTM-MMA-NaMA DBTM-MMA-NaMA
  • the PA is PA6 and the intrinsic viscosity is 2.8;
  • the special effect toner is a silica-coated metal pigment having an average particle diameter of 100 ⁇ m;
  • the PMMA-g-MAH / St Mw is 140,000 and the MAH content It is 1 wt%;
  • the DBTM-MMA-NaMA Mw is 40,000, wherein the DBTM content is 2 wt% and the NaMA content is 15 wt%.
  • PA PA6
  • DBTM-MMA-NaMA polymethyl methacrylate grafted maleic anhydride / styrene
  • the PA is PA6 and the intrinsic viscosity is 2.8
  • the special effect toner is 9 phr copper zinc powder with an average particle diameter of 50 ⁇ m and 9 phr aluminum borate salt with an average particle diameter of 200 ⁇ m coated metal pigment
  • the PMMA- The g-MAH / St Mw is 140,000 and the MAH content is 1 wt%
  • DBTM-MMA-NaMA Mw is 40,000, wherein the DBTM content is 2 wt% and the NaMA content is 15 wt%.
  • PA PA6
  • DBTM-MMA-NaMA PA6
  • the intrinsic viscosity is 2.8
  • the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m
  • the PMMA-g-MAH / St Mw is 90,000, and the MAH content is 0.5 wt%
  • the DBTM-MMA-NaMA Mw is 5000, wherein the DBTM content is 1% by weight and the NaMA content is 9% by weight.
  • PA PA66
  • the intrinsic viscosity is 2.5
  • the special effect toner is an aluminum powder having an average particle diameter of 20 ⁇ m
  • the PMMA-g-MAH / St Mw is 80,000, and the MAH content is 0.5 wt%
  • the DBTM-MMA-NaMA Mw is 8000, wherein the DBTM content is 1.5 wt% and the NaMA content is 7 wt%.
  • PA 85phr PA, 18phr special effect toner, 15phr polymethyl methacrylate grafted maleic anhydride / styrene, 2phr DBTM-MMA-NaMA.
  • the PA is PA610 and the intrinsic viscosity is 2.3; the special effect toner is an aluminum powder having an average particle diameter of 30 ⁇ m; the PMMA-g-MAH / St Mw is 140,000 and the MAH content is 0.8 wt%;
  • the DBTM-MMA-NaMA Mw is 30,000, wherein the DBTM content is 1.8 wt% and the NaMA content is 12 wt%.
  • PA 90phr PA, 8phr special effect toner, 10phr polymethyl methacrylate grafted maleic anhydride / styrene, 2phr DBTM-MMA-NaMA.
  • the PA is 40 wt% PA46 and 60 wt% PA12, the intrinsic viscosity of PA46 is 2.9, and the intrinsic viscosity of PA12 is 1.9;
  • the special effect toner is an aluminum powder having an average particle diameter of 50 ⁇ m; and the PMMA-g-MAH / St Mw is 50,000, and the MAH content is 0.3 wt%; the DBTM-MMA-NaMA Mw is 20,000, wherein the DBTM content is 0.8 wt% and the NaMA content is 5 wt%.
  • PA 100phr PA, 18phr special effect toner.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder with an average particle diameter of 10 ⁇ m.
  • the temperature of the extruder used for the extrusion is 190-290 ° C
  • the screw aspect ratio 40-60
  • the screw speed 400-600 rpm.
  • PA 100phr PA, 0.5phr special effect toner.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder with an average particle diameter of 10 ⁇ m.
  • the temperature of the extruder used for the extrusion is 190-290 ° C
  • the screw aspect ratio 40-60
  • the screw speed 400-600 rpm.
  • PA 95phr PA, 18phr special effect toner, 2phr coupling agent Z-601, 0.2phr zinc stearate, 5phr lubricant EBS, 0.2phr antioxidant 168, 0.1phr antioxidant 1010.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder with an average particle diameter of 10 ⁇ m.
  • the metallic toner, the coupling agent and the zinc stearate are mixed with a high-speed mixer according to the formula amount, and blended at a rotation speed of 220 to 260 r / min for 3 to 5 minutes to obtain a first mixture.
  • the polyamide, lubricant and antioxidant are mixed in a high-speed mixer, and blended at a rotation speed of 320 to 380 r / min for 2 to 10 minutes to obtain a second mixture.
  • the first hot zone The temperature is 210-225 ° C
  • the second hot zone is 225-235 ° C
  • the third hot zone is 235-245 ° C
  • the fourth hot zone temperature is 240-250 ° C
  • the fifth hot zone temperature is 240-250 ° C.
  • the temperature in the six hot zones is 245 to 260 ° C
  • the temperature in the seventh hot zone is 245 to 265 ° C
  • the temperature in the eighth hot zone is 250 to 265 ° C
  • the temperature in the ninth hot zone is 250 to 270 ° C.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m; the PMMA-g-MAH / St Mw is 140,000 and the MAH content is 1 wt%.
  • the above PMMA-g-MAH / St is pre-mixed according to the ratio and then extruded through a twin-screw extruder. At the same time, the special effect toner is added to the melt according to the ratio by side feeding. Effect toner masterbatch.
  • the temperature of the extruder used is 190-250 ° C, the aspect ratio of the screw is 40-60, and the speed of the screw is 400-600 rpm.
  • the temperature of the extruder used is 190-290 ° C, the aspect ratio of the screw is 40-60, and the speed of the screw is 400-600 rpm.
  • PA PA6
  • the intrinsic viscosity is 2.8
  • the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m
  • the PMMA Mw is 140,000
  • the DBTM-MMA-NaMA Mw is 4W, where The DBTM content was 2 wt% and the NaMA content was 15 wt%.
  • the above-mentioned PMMA and additives are premixed according to the ratio and then extruded through a twin-screw extruder.
  • the special effect toner is added to the melt according to the ratio by the side feeding method, and the special effect toner is extruded to obtain the special effect toner.
  • Masterbatch The temperature of the extruder used is 190-250 ° C, the aspect ratio of the screw is 40-60, and the speed of the screw is 400-600 rpm.
  • PA PA6
  • the intrinsic viscosity is 2.8
  • the special-effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m
  • the AN content of the AS is 24% by weight
  • the melt index at 220 ° C * 10kg is 30.
  • each component by weight uses a high-speed mixer to mix the components according to the ratio, add it from the main feed port of the twin-screw extruder, at a temperature of 210-280 ° C, a vacuum of 0.05-0.08MPA, and a rotation speed of 300- Under the conditions of 500 rp / min, it is melt extruded and granulated by a twin-screw extruder.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m; the AN content of the AS is 24% by weight, and the melt index at 220 ° C * 10kg is 30;
  • the MAH content in the AS-MAH is 1.2 wt%;
  • the toughening agent is an ethylene propylene maleic anhydride copolymer;
  • the dispersing agent is a spherical carboxyl-terminated polymer having an acid value of 200-300 mgKOH;
  • the processing aid is lubricant EBS.
  • each component by weight uses a high-speed mixer to mix the components according to the ratio, add it from the main feed port of the twin-screw extruder, at a temperature of 210-280 ° C, a vacuum of 0.05-0.08MPA, and a speed of 300- Under the conditions of 500 rp / min, it is melt extruded and granulated by a twin-screw extruder.
  • the PA is PA6 and the intrinsic viscosity is 2.8; the special effect toner is an aluminum powder having an average particle diameter of 10 ⁇ m; the AN content of the AS is 24% by weight, and the melt index at 220 ° C * 10kg is 30;
  • the MAH content in the AS-MAH is 1.2 wt%;
  • the toughening agent is an ethylene propylene maleic anhydride copolymer;
  • the dispersing agent is a spherical carboxyl-terminated polymer having an acid value of 200 to 300 mg KOH;
  • the processing aid is lubricant EBS.
  • each component by weight uses a high-speed mixer to mix the components according to the ratio, add it from the main feed port of the twin-screw extruder, at a temperature of 210-280 ° C, a vacuum of 0.05-0.08MPA, and a rotation speed of 300- Under the conditions of 500 rp / min, it is melt extruded and granulated by a twin-screw extruder.
  • PA6 95phr, polyamide resin is a copolymer composed of 6-aminohexanoic acid units and 11-aminoundecanoic acid units, and the content of 6-aminohexanoic acid units in the polyamide resin is 60 to 90% by weight.
  • a method for polymerizing an aminocarboxylic acid (lactam) in the presence of a swellable layered silicate (B), a swellable layered silicate (B) and an aminocarboxylic acid (lactam) can be used.
  • the pellets of the polyamide resin be refined with hot water.
  • the polyamide resin can be heated in hot water at 90 to 100 ° C. The treatment is performed for 8 hours or more.
  • the obtained polyamide had an intrinsic viscosity of 2.5.
  • the extruder temperature was set at 190-250 ° C.
  • Pencil hardness test The prepared particles are injection molded at a temperature of 250 ° C. into a high-gloss color plate with a thickness of 3 mm, and subjected to a hardness test. The pencil hardness test is performed according to GB / T 6739-1996, and the weight is 500g.
  • Visual metal feeling refer to the appearance of metallic aluminum, the closer the ⁇ obtained to the appearance of the reference object, the higher the metal texture.
  • Molding shrinkage refer to GB / T 17037.4-2003, test after 24h at 23 °C.
  • the active functional groups in PMMA-g-MAH / S and DBTM-MMA-NaMA cooperate with each other to help PMMA-g-MAH / S disperse, control the morphology of two phases, accelerate crystallization, refine grains, and improve the toughness and rigidity of materials And special effects. It can be seen from the comparison between Example 1 and Comparative Example 4 that the present invention can significantly improve the metal feeling, toughness and other properties of the material compared with the general dispersant.
  • the results of Example 1 and Comparative Examples 5/6/7 show that the active functional groups in PMMA-g-MAH / S and DBTM-MMA-NaMA cooperate with each other to help PMMA-g-MAH / S disperse and control the morphology of the two phases.
  • Example 1 and Comparative Example 8/9 the technology used in the present invention greatly improves the metallic feel of the material. It can be known from the results of Example 5 and Comparative Example 10 that the present technology has a certain improvement in gloss and toughness compared with the in-situ polymerization of nanomaterials and the blending materials with special effect toner, and the technology of the present invention is simpler and more convenient. Compared with other technologies, the present invention better solves the problems of weak metal feeling and low toughness when preparing metal effect nylon materials in the prior art.

Abstract

本发明涉及一种具有高金属质感的聚酰胺美学树脂组合物，由以下组分组成：聚酰胺(PA)70～95份，助剂0～5份，特殊效果母粒5.6～50份。特殊效果母粒由以下成分组成：聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯(PMMA-g-MAH/St)5～30份，特殊效果色粉0.5～18份，添加剂0.1～2份。所述的添加剂为顺丁烯二酸二丁基锡—甲基丙烯酸甲酯—甲基丙烯酸钠共聚物。本发明还提供上述组合物的制备方法。与现有技术相比，本发明采用一种全新的技术方案对用于免喷涂美学塑料的尼龙材料进行改性，获得一种具有高金属质感、良好的机械性能和表面性能的聚酰胺美学质感组合物。

Description

具有高金属质感的聚酰胺树脂组合物及其制备方法 技术领域
本发明涉及一种具有高金属质感的聚酰胺树脂组合物及其制备方法，属于高分子材料技术领域。
背景技术
随着消费者对产品外观品质要求越来越高，具有金属质感的外观设计越来越流行。目前主流的金属效果材料是通过喷漆或者电镀来达到金属质感、闪烁等美学效果。但喷漆、电镀等工艺有预处理、涂装、转运等复杂工序，成本较高；生产过程复杂，良品率不高，还存在严重的污染问题；成品中因含有不同材质的涂层，使塑料不可回收、造成大量浪费。
免喷涂美学塑料，通过在基体树脂中添加具有特殊效果的颜料如铝粉、珠光粉、铜锌粉、玻璃片，或者通过基材的微观结构控制实现材料具有高光、类金属、类岩石等美学外观。通过一次成型即可实现外观靓丽的特殊色彩效果，免除了喷涂、丝印等后加工工序，生产效率高、成本低、无环境污染、低能耗、100％可回收利用。基于以上的优势，免喷涂美学塑料已成为当代材料的重要改性方向。
尼龙材料具有高强度、优异的耐磨性、高耐热性、良好的化学稳定性和流动性，在汽车、电子电器、家电等领域有非常广泛的应用。这些优点也赋予尼龙材料在作为免喷涂美学塑料基材有着非常好的应用前景。然而由于结晶性导致的尼龙材料的不透明，简单的添加特殊效果色粉，最后呈现的美学效果会大打折扣。同时添加了和基体相容性差的特殊效应颜料，材料的韧性会明显降低。另外尼龙材料普遍具有吸湿性大、成型收缩率高的问题。因此，在作为免喷涂美学塑料时需要对尼龙材料的美学效果实现能力加以提升，同时对尼龙材料的耐冲击性能、吸湿性、成型收缩率进行改进。目前尚未见针对于提升尼龙基材美学效果的技术方案，尤其是可以同时改进上述性能的技术方案报道。专利CN201310446502公布一种具有金属效果的聚酰胺树脂组合物，包括在膨润性层状硅酸盐的存在下进行的共聚物的聚合反应工序，主要是为了改善产品的耐焊接强度，对材料的韧性没有做考量。该发明采用原位聚合的方式，对制备设备和工艺的控制非常复 杂，成本很高。CN201611014288公开了一种适用于免喷涂电焊面罩用增韧尼龙66材料及其制备方法，该发明改善了普通染色尼龙材料的韧性和流动性，没有考虑特殊效果色粉的在该材料的实现情况。专利CN201710593044公开了一种具有金属光泽的纳米聚酰胺组合物及其制备方法，该发明主要选用自制的纳米聚酰胺母粒为增强材料，同核壳型分散剂相互作用，辅以相应的加工助剂，改善纳米粒子的分散和增强作用，表面光泽度得到改善，没有考量最后产品的金属质感，大量的无机填料会对金属特殊效果色粉起遮蔽作用。CN201611079305采用偶联剂和硬脂酸锌协效改善金属色颜料的分散，没有考量材料的物性。
发明内容
针对现有技术中的缺陷，本发明的目的是提供一种具有高金属质感的聚酰胺美学树脂组合物及其制备方法。
本发明是通过以下技术方案实现的：
第一方面，本发明提供了一种具有高金属质感的聚酰胺树脂组合物，其包括按重量份数计的如下组分：
聚酰胺树脂：                                70～95份；
助剂：                                      0～5份；
特殊效果母粒：                              5.6～50份；
所述特殊效果母粒由以下成分组成：
聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯：       5～30份；
特殊效果色粉：                              0.5～18份；
添加剂：                                    0.1～2份。
作为优选方案，所述聚酰胺包括PA6、PA66、PA46、PA610、PA68、PAMXD6、PA10、PA12、PA11、PA6T PA10T、PA1010、PA1212、PA9T中的至少一种。
作为优选方案，所述聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯(简称PMMA-g-MAH/S)的重均分子量为40000～140000，马来酸酐含量为0.05～1wt％。
作为优选方案，所述特殊效果色粉的粒径为1～200μm。
作为优选方案，所述特殊效果色粉选所述特殊效果色粉选自氯氧化铋结晶金属颜料、云母涂覆金属颜料、二氧化硅涂覆金属颜料、硼酸铝盐涂覆金属颜料、人造云母涂覆金属颜料、三氧化二铝涂覆金属颜料、氧化铋涂覆金属颜料、铝粉、铜粉、铁粉、锌 粉、铜锌粉等一种或者几种。
作为优选方案，所述添加剂为顺丁烯二酸二丁基锡—甲基丙烯酸甲酯—甲基丙烯酸钠共聚物(简称DBTM-MMA-NaMA)。
作为优选方案，所述顺丁烯二酸二丁基锡—甲基丙烯酸甲酯—甲基丙烯酸钠共聚物的重均分子量为1000～40000，其中，顺丁烯二酸二丁基锡的含量为0.5～2wt％，甲基丙烯酸钠共聚物2～15wt％。
作为优选方案，所述助剂选自颜料、热稳定剂、防氧化剂、耐候剂、增塑剂、润滑剂、脱模剂、防带电剂、无机填料中的至少一种。
第二方面，本发明还提供了一种如前述的具有高金属质感的聚酰胺树脂组合物的制备方法，其包括如下步骤：
将聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、添加剂预混后经双螺杆挤出机挤出，得到熔体；将特殊效果色粉加入到所述的熔体中，进行挤出获得特殊效果色粉母粒；其中所用挤出机温度为190～250℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟；
将聚酰胺树脂和助剂在高速混合机内预混3～10min后，经双螺杆挤出机挤出得到熔体，同时将特殊效果母粒通过侧喂加入到所述的熔体中，进行挤出，所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
与现有技术相比，本发明具有如下的有益效果：
1、共混PMMA-g-MAH/S可改善聚酰胺树脂的吸水性和耐刮擦性；
2、添加剂DBTM-MMA-NaMA与特殊效果色粉和PMMA-g-MAH/St共聚物有非常好的相容性，吸附到色粉表面帮助特殊效果色粉在PMMA-g-MAH/St中均匀分散，避免特殊效果色粉的相互堆积；
3、PMMA-g-MAH/S和DBTM-MMA-NaMA中的活性官能团互相协同，帮助PMMA-g-MAH/St分散、控制两相的形态、加速结晶、细化晶粒，改善材料的韧性、刚性和特殊效果实现情况；
4、通过侧喂方式将特殊效果色粉母粒添加到熔体中可有减轻效应颜料的磨损，更好的解决现有技术中制备金属效果尼龙材料时金属感弱、韧性低的问题。
具体实施方式
下面结合具体实施例对本发明进行详细说明。以下实施例将有助于本领域的技术人 员进一步理解本发明，但不以任何形式限制本发明。应当指出的是，对本领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干变形和改进。这些都属于本发明的保护范围。
实施例1～8和对比例1～10。
其中实施例1～5均是通过以下工艺进行制备：将聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、添加剂添加按配比预混后经双螺杆挤出机挤出，同时通过侧喂的方式将特殊效果色粉按配比加入到所述的熔体中，进行挤出获得特殊效果色粉母粒。其中所用挤出机温度为190～250℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。再将上述除特殊效果色粉母粒外其他原材料在高速混合机内预混3～10分钟，然后预混料经双螺杆挤出机挤出，同时通过侧喂的方式特殊效果色粉预处理按配比加入到所述的熔体中，进行挤出所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
实施例6～8均是通过以下工艺进行制备：将聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、添加剂添加按配比预混后经双螺杆挤出机挤出，同时通过侧喂的方式将特殊效果色粉按配比加入到所述的熔体中，进行挤出获得特殊效果色粉母粒。其中所用挤出机温度为190～250℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。再将上述除特殊效果色粉母粒外其他原材料在高速混合机内预混3～10分钟，然后预混料经双螺杆挤出机挤出，同时通过侧喂的方式特殊效果色粉预处理按配比加入到所述的熔体中，进行挤出所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
实施例1～8的具体组成见以下说明。
实施例1
70phr PA、18phr特殊效果色粉、30phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯，2phr DBTM-MMA-NaMA。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的PMMA-g-MAH/St Mw为140000，MAH含量为1wt％；所述的DBTM-MMA-NaMA Mw为40000，其中DBTM含量为2wt％，NaMA含量为15wt％。
实施例2
95phr PA、0.5phr特殊效果色粉、5phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、0.1phr DBTM-MMA-NaMA。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的PMMA-g-MAH/St Mw为40000，MAH含量为0.05wt％；所述的DBTM-MMA-NaMA Mw为1000，其中DBTM含量为0.5wt％，NaMA 含量为2wt％。
实施例3
70phr PA、18phr特殊效果色粉、30phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、2phr DBTM-MMA-NaMA。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为100μm的二氧化硅涂覆金属颜料；所述的PMMA-g-MAH/St Mw为140000，MAH含量为1wt％；所述的DBTM-MMA-NaMA Mw为40000，其中DBTM含量为2wt％，NaMA含量为15wt％。
实施例4
70phr PA、18phr特殊效果色粉、30phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、2phr DBTM-MMA-NaMA。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为9phr平均粒径为50μm的铜锌粉和9phr平均粒径为200μm硼酸铝盐涂覆金属颜料；所述的PMMA-g-MAH/St Mw为140000，MAH含量为1wt％；所述的DBTM-MMA-NaMA Mw为40000，其中DBTM含量为2wt％，NaMA含量为15wt％。
实施例5
70phr PA、3phr特殊效果色粉、30phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、2phr DBTM-MMA-NaMA。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的PMMA-g-MAH/St Mw为90000，MAH含量为0.5wt％；所述的DBTM-MMA-NaMA Mw为5000，其中DBTM含量为1wt％，NaMA含量为9wt％。
实施例6
80phr PA、14phr特殊效果色粉、20phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、1.5phr DBTM-MMA-NaMA。所述的PA为PA66，特性粘度为2.5；所述的特殊效果色粉为平均粒径为20μm的铝粉；所述的PMMA-g-MAH/St Mw为80000，MAH含量为0.5wt％；所述的DBTM-MMA-NaMA Mw为8000，其中DBTM含量为1.5wt％，NaMA含量为7wt％。
实施例7
85phr PA、18phr特殊效果色粉、15phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、2phr DBTM-MMA-NaMA。所述的PA为PA610，特性粘度为2.3；所述的特殊效果色粉为平均粒径为30μm的铝粉；所述的PMMA-g-MAH/St Mw为140000，MAH含量为0.8wt％；所述的DBTM-MMA-NaMA Mw为30000，其中DBTM含量为1.8wt％，NaMA 含量为12wt％。
实施例8
90phr PA、8phr特殊效果色粉、10phr聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、2phr DBTM-MMA-NaMA。所述的PA为40wt％PA46和60wt％PA12，PA46特性粘度为2.9，PA12特性粘度为1.9；所述的特殊效果色粉为平均粒径为50μm的铝粉；所述的PMMA-g-MAH/St Mw为50000，MAH含量为0.3wt％；所述的DBTM-MMA-NaMA Mw为20000，其中DBTM含量为0.8wt％，NaMA含量为5wt％。
对比例1
100phr PA6本体，特性粘度为2.8。
对比例2
100phr PA、18phr特殊效果色粉。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉。将上述除特殊效果色粉外其他原材料在高速混合机内预混3～10分钟，然后预混料经双螺杆挤出机挤出，同时通过侧喂的方式特殊效果色粉预处理按配比加入到所述的熔体中，进行挤出所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
对比例3
100phr PA、0.5phr特殊效果色粉。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉。将上述除特殊效果色粉外其他原材料在高速混合机内预混3～10分钟，然后预混料经双螺杆挤出机挤出，同时通过侧喂的方式特殊效果色粉预处理按配比加入到所述的熔体中，进行挤出所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
对比例4
95phr PA、18phr特殊效果色粉、2phr偶联剂Z-601、0.2phr硬脂酸锌、5phr润滑剂EBS、0.2phr抗氧剂168、0.1phr抗氧剂1010。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉。按配方量将金属色粉、偶联剂和硬脂酸锌混合与高速混合机中，在220～260r/min的转速下共混3～5min，得到第一混合料。按配方将量将聚酰胺、润滑剂和抗氧剂混合于高速混合机中，在320～380r/min的转速下共混2～10min，得到第二混合料。将第一混合料和第二混合料加入到双螺杆挤出机中，依次经过九个热区进行熔融共混，设定双螺杆挤出机的转速为400～500r/min，第一热区温度为210～225℃，第二热区为225～235℃，第三热区为235～245℃，第四热 区温度为240～250℃，第五热区温度为240～250℃，第六热区温度为245～260℃，第七热区温度为245～265℃，第八热区温度为250～265℃，第九热区温度为250～270℃，共混1～3min，共混后挤出，冷却，干燥，切粒，得到具有金属效果的聚酰胺树脂。
对比例5
70phr PA、18phr特殊效果色粉、30phr PMMA-g-MAH/St。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的PMMA-g-MAH/St Mw为140000，MAH含量为1wt％。将上述PMMA-g-MAH/St按配比预混后经双螺杆挤出机挤出，同时通过侧喂的方式将特殊效果色粉按配比加入到所述的熔体中，进行挤出获得特殊效果色粉母粒。其中所用挤出机温度为190～250℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。再将上述除特殊效果色粉母粒外其他原材料在高速混合机内预混3～10分钟，然后预混料经双螺杆挤出机挤出，同时通过侧喂的方式特殊效果色粉预处理按配比加入到所述的熔体中，进行挤出。所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
对比例6
70phr PA、18phr特殊效果色粉、30phr PMMA、2phr DBTM-MMA-NaMA。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的PMMA Mw为140000；所述的DBTM-MMA-NaMA Mw为4W，其中DBTM含量为2wt％，NaMA含量为15wt％。将上述PMMA、添加剂添加按配比预混后经双螺杆挤出机挤出，同时通过侧喂的方式将特殊效果色粉按配比加入到所述的熔体中，进行挤出获得特殊效果色粉母粒。其中所用挤出机温度为190～250℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。再将上述除特殊效果色粉母粒外其他原材料在高速混合机内预混3～10分钟，然后预混料经双螺杆挤出机挤出，同时通过侧喂的方式特殊效果色粉预处理按配比加入到所述的熔体中，进行挤出所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
对比例7
70phr PA、18phr特殊效果色粉、30phr丙烯腈-苯乙烯共聚物AS。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的AS的AN含量为24wt％，220℃*10kg的融指为30。按重量称取各组分，使用高速搅拌机将各组分按配比混合均匀，从双螺杆挤出机主喂口加入，在温度为210～280℃，真空度为0.05～0.08MPA，转速300～500rp/min的工艺条件下通过双螺杆挤出机熔融挤出造粒。
对比例8
70phr PA、18phr特殊效果色粉、14phr丙烯腈-苯乙烯共聚物AS、7phr马来酸酐接枝丙烯腈-苯乙烯共聚物AS-MAH、6phr增韧剂、2phr分散剂、2phr加工助剂。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的AS的AN含量为24wt％，220℃*10kg的融指为30；所述的AS-MAH中的MAH含量为1.2wt％；所述的增韧剂为乙烯丙烯马来酸酐共聚物；所述的分散剂为酸值200-300mg KOH的球形端羧基聚合物；所述的加工助剂为润滑剂EBS。按重量称取各组分，使用高速搅拌机将各组分按配比混合均匀，从双螺杆挤出机主喂口加入，在温度为210～280℃，真空度为0.05～0.08MPA，转速300～500rp/min的工艺条件下通过双螺杆挤出机熔融挤出造粒。
对比例9
70phr PA、2phr特殊效果色粉、14phr丙烯腈-苯乙烯共聚物AS、7phr马来酸酐接枝丙烯腈-苯乙烯共聚物AS-MAH、4phr增韧剂、1phr分散剂、1phr加工助剂。所述的PA为PA6，特性粘度为2.8；所述的特殊效果色粉为平均粒径为10μm的铝粉；所述的AS的AN含量为24wt％，220℃*10kg的融指为30；所述的AS-MAH中的MAH含量为1.2wt％；所述的增韧剂为乙烯丙烯马来酸酐共聚物；所述的分散剂为酸值200～300mg KOH的球形端羧基聚合物；所述的加工助剂为润滑剂EBS。按重量称取各组分，使用高速搅拌机将各组分按配比混合均匀，从双螺杆挤出机主喂口加入，在温度为210～280℃，真空度为0.05～0.08MPA，转速300～500rp/min的工艺条件下通过双螺杆挤出机熔融挤出造粒。
对比例10
PA6 95phr、聚酰胺树脂是由6-氨基己酸单元、11-氨基十一烷酸单元构成的共聚物，聚酰胺树脂中的6-氨基己酸单元的含量是60～90wt％。将90％wt％的6-氨基己酸单元和10wt％11-氨基十一烷酸单元，在膨润性层状硅酸盐(MaSi(Al 2-0.5Mg)O 10(OH) 2·nH 2O)的存在下进行聚合反应，将得到的聚合物和膨润性层状硅酸盐(B)的混合物、及金属颜料(C)进行熔融混合而制造聚酰胺树脂组合物。作为在膨润性层状硅酸盐(B)的存在下，将氨基羧酸(内酰胺)聚合的方法，可将膨润性层状硅酸盐(B)和氨基羧酸(内酰胺)投入到压热器后，使用水等引发剂，在温度240～300℃、压力0.2～3MPa、1～15小时的范围内进行熔融缩聚的方法。另外，为了除去聚合后的聚酰胺树脂中残留的氨基羧酸(内酰胺)，优选对聚酰胺树脂的粒料进行利用热水的精炼，作为其条件，可在90～100℃的热水中进 行8小时以上的处理。获得的聚酰胺的特性粘度为2.5。
将聚酰胺树脂(A)100phr、膨润性层状硅酸盐(B)8phr、混合经挤出机上游挤出，金属颜料铝(C)3phr采用侧进料机供给金属颜料(C)，更优选尽量在挤出机下游供给。铝粉含量为聚酰胺(A)共聚物的3wt％，铝粉的纵横比为20，平均粒径为20微米。挤出机温度设定在190～250℃。
实施例1～5和对比例1～10的性能测试如下：
表1 产品的性能对比
样品 实施例1 实施例2 实施例3 实施例4 实施例5 对比例1 对比例2
铅笔硬度 H F 3H 2H H HB HB
Charpy缺口冲击 5 6.5 4.6 4.3 6.1 4 3
Charpy无缺口冲击 55 68 51 45 62 35 29
光泽度60° 101 103 99 98 101 50 70
目视金属感 5☆ 2.5☆ 5☆ 4.5☆ 3☆ 无 2.5☆
平衡吸水率 1.5 2.6 1.8 1.7 1.7 3 2.6
成型收缩率 0.6 1.4 0.7 0.7 0.6 1.6 1.3
表1 产品的性能对比(续)
样品 对比例3 对比例4 对比例5 对比例6 对比例7 对比例8 对比例9 对比例10
铅笔硬度 HB HB F F HB HB HB F
Charpy缺口冲击 3.7 3 2.1 2.5 2.4 4.3 4.5 3.5
Charpy无缺口冲击 33 30 22 25 23 50 52 45
光泽度60° 55 72 65 75 76 83 81 90
目视金属感 1☆ 2☆ 1☆ 2.2☆ 2☆ 2☆ 1.5☆ 2.5☆
平衡吸水率 3 2.5 2.4 2.3 2.1 2.1 2.1 1.7
成型收缩率 1.66 1.3 1.3 1.3 1.3 1.3 1.4 0.6
物理性能测试方法：
铅笔硬度测试：将制备好的粒子在250℃的温度下注塑厚度为3mm的高光色板，进行硬度测试。铅笔硬度测试按照GB/T 6739-1996进行测试，砝码重500g。
冲击性能：按照ISO 179测试，单位kJ/m 2。
光泽度：根据ISO2813。
目视金属感：参照金属单质铝的外观，越接近参照物的外观获得的☆越来，表示金属质感越高
平衡吸水率：23℃，50％HR测试样品的重量增加。
成型收缩率：参照GB/T 17037.4-2003,23℃下24h后测试。
通过表1的结果对比可知，可显而易见本发明优点。通过对比实施例1和对比例2以及对比实施例2和对比例3，可知共混PMMA-g-MAH/S可改善PA的吸水性、成型收缩率、冲击韧性及耐刮擦性，同时可显著提升材料的金属质感及光泽度。添加剂DBTM-MMA-NaMA与特殊效果色粉和PMMA-g-MAH/St共聚物有非常好的相容性，吸附到色粉表面帮助特殊效果色粉在PMMA-g-MAH/S中均匀分散，避免特殊效果色粉的相互堆积。PMMA-g-MAH/S和DBTM-MMA-NaMA中的活性官能团互相协同，帮助PMMA-g-MAH/S分散、控制两相的形态、加速结晶、细化晶粒，改善材料的韧性、刚性和特殊效果实现情况。通过实施例1和对比例4的对比可知，本发明相比用一般的分散剂可显著提升材料的金属感、韧性以及其他性能。实施例1和对比例5/6/7的结果可知PMMA-g-MAH/S和DBTM-MMA-NaMA中的活性官能团互相协同，帮助PMMA-g-MAH/S分散、控制两相的形态，对材料的性能有大幅度提升。实施例1和对比例8/9相比，本发明采用的技术使材料的金属感得到大幅度提升。通过实施例5和对比例10的结果可知本技术相比原位聚合纳米材料再进行和特殊效果色粉的共混材料的光泽和韧性有一定提升，同时本发明的技术更简单方便。相比其他技术，本发明更好的解决现有技术中制备金属效果尼龙材料时金属感弱、韧性低的问题。
以上对本发明的具体实施例进行了描述。需要理解的是，本发明并不局限于上述特定实施方式，本领域技术人员可以在权利要求的范围内做出各种变形或修改，这并不影响本发明的实质内容。

Claims (9)

  1. 一种具有高金属质感的聚酰胺树脂组合物，其特征在于，包括按重量份数计的如下组分：
    聚酰胺树脂：                              70～95份；
    助剂：                                    0～5份；
    特殊效果母粒：                            5.6～50份；
    所述特殊效果母粒由以下成分组成：
    聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯：      5～30份；
    特殊效果色粉：                            0.5～18份；
    添加剂：                                  0.1～2份。
  2. 如权利要求1所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述聚酰胺包括PA6、PA66、PA46、PA610、PA68、PAMXD6、PA10、PA12、PA11、PA6T PA10T、PA1010、PA1212、PA9T中的至少一种。
  3. 如权利要求1所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯的重均分子量为40000～140000，马来酸酐含量为0.05～1wt％。
  4. 如权利要求1所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述特殊效果色粉的粒径为1～200μm。
  5. 如权利要求1或4所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述特殊效果色粉选自氯氧化铋结晶金属颜料、云母涂覆金属颜料、二氧化硅涂覆金属颜料、硼酸铝盐涂覆金属颜料、人造云母涂覆金属颜料、三氧化二铝涂覆金属颜料、氧化铋涂覆金属颜料、铝粉、铜粉、铁粉、锌粉、铜锌粉中的一种或几种。
  6. 如权利要求1所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述添加剂为顺丁烯二酸二丁基锡—甲基丙烯酸甲酯—甲基丙烯酸钠共聚物。
  7. 如权利要求1所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述顺丁烯二酸二丁基锡—甲基丙烯酸甲酯—甲基丙烯酸钠共聚物的重均分子量为1000～40000，其中，顺丁烯二酸二丁基锡的含量为0.5～2wt％，甲基丙烯酸钠共聚物2～15wt％。
  8. 如权利要求1所述的具有高金属质感的聚酰胺树脂组合物，其特征在于，所述助剂选自颜料、热稳定剂、防氧化剂、耐候剂、增塑剂、润滑剂、脱模剂、防带电剂、无机填料中的至少一种。
  9. 一种如权利要求1所述的具有高金属质感的聚酰胺树脂组合物的制备方法，其特征在于，包括如下步骤：
    将聚甲基丙烯酸甲酯接枝马来酸酐/苯乙烯、添加剂预混后经双螺杆挤出机挤出，得到熔体；将特殊效果色粉加入到所述的熔体中，进行挤出获得特殊效果色粉母粒；其中所用挤出机温度为190～250℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟；
    将聚酰胺树脂和助剂在高速混合机内预混3～10min后，经双螺杆挤出机挤出得到熔体，同时将特殊效果母粒通过侧喂加入到所述的熔体中，进行挤出，所用挤出机温度为190～290℃，螺杆长径比为40～60，螺杆转速为400～600转/分钟。
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CN114031934A (zh) * 2021-12-15 2022-02-11 宁波公牛光电科技有限公司 一种高导热系数的聚酰胺复合材料及其制备方法
CN114031934B (zh) * 2021-12-15 2023-07-04 宁波公牛光电科技有限公司 一种高导热系数的聚酰胺复合材料及其制备方法
CN114181525A (zh) * 2021-12-16 2022-03-15 柏力开米复合塑料(昆山)有限公司 一种颜色稳定的橘色pa66的制备方法
CN114181525B (zh) * 2021-12-16 2024-03-19 柏力开米复合塑料(昆山)有限公司 一种颜色稳定的橘色pa66的制备方法
WO2023178880A1 (zh) * 2022-03-25 2023-09-28 江苏新日电动车股份有限公司 一种预防重金属污染的免喷涂复合材料及其制备方法

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