CN109575562B - Stain-resistant PC/ABS alloy and preparation method thereof - Google Patents
Stain-resistant PC/ABS alloy and preparation method thereof Download PDFInfo
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- CN109575562B CN109575562B CN201811630189.7A CN201811630189A CN109575562B CN 109575562 B CN109575562 B CN 109575562B CN 201811630189 A CN201811630189 A CN 201811630189A CN 109575562 B CN109575562 B CN 109575562B
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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
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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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
- C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
- C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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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
- 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
Abstract
The invention relates to a stain-resistant PC/ABS alloy and a preparation method thereof, wherein the stain-resistant PC/ABS alloy is prepared from the following raw materials in parts by weight: 40-80 parts of polycarbonate, 10-50 parts of polyacrylonitrile-butadiene-styrene copolymer, 5-45 parts of stain-resistant PBT master batch, 0.5-3 parts of compatilizer, 0.1-1 part of antioxidant and 0.1-1 part of lubricant, placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, mixing for 5-30 min to obtain a mixed material, finally placing the mixed material in a double-screw extruder, feeding the stain-resistant PBT master batch from the side, performing melt extrusion, and granulating to obtain product particles. The PC/ABS alloy with stain resistance prepared by the invention can produce products with higher surface stain resistance through an industrialized method while maintaining better processing performance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a stain-resistant PC/ABS alloy and a preparation method thereof.
Background
The PC/ABS alloy is widely used engineering plastic, has excellent impact strength, heat resistance and other properties, and is widely used in the fields of automobiles, electronics, household appliances and the like. However, as the number of applications increases and consumer demand increases, new demands are being made on the stain resistance of such materials. Because PC/ABS has poor pollution resistance, the PC/ABS alloy needs to be modified to meet the requirement of pollution resistance, at present, a plurality of PC/ABS alloy patents exist, but no pollution-resistant PC/ABS alloy is reported all the time.
Great dawn et al describe in CN103469361A that the fluorine-containing PBT-PET blend fiber is prepared by introducing fluorine-containing synthetic monomer to synthesize fluorine-containing PBT and a preparation method thereof. The method adopts a synthetic mode to add fluorine-containing groups, so that the process is complicated and more side reactions are generated. Zhang Bo et al, CN108285707A, describes the preparation of an anticorrosive and antifouling paint with high heat insulation by using titanium-plate type nano titanium dioxide and a preparation method thereof. According to the method, the ceramic crystal micro powder, the brookite type nanometer titanium dioxide, the common graphene and other formulas are compounded, so that a certain heat insulation and water isolation effect is achieved, but the stain resistance and the hydrophobicity are not very good. Leersin, CN105670077A, describes a method for producing an antibacterial and stain resistant plastic by a process comprising a silver ion-containing inorganic antibacterial agent and a fluorosilicone resin. The fluorine-silicon resin plays a role in hydrophobic stain resistance, but the fluorine-silicon resin alone cannot play a good hydrophobic effect, and the surface of the fluorine-silicon resin cannot reach a due micro-nano structure.
Although there are some patents in other fields in the aspect of stain resistance, the application range is limited, the performance requirements of engineering plastics cannot be met, and industrialization is not easy to realize.
Chinese patent CN103540250A discloses a coating composition for plastics, which can obtain a coating film excellent in adhesion to plastic materials, stain resistance (oil acid resistance and lactic acid resistance), and finishing properties even by one-time coating. The coating composition for plastics comprises a hydroxyl group-containing acrylic resin (A) having a weight-average molecular weight of 3,000 to 20,000 and a hydroxyl value of 100 to 200mgKOH/g, a polyisocyanate compound (B), a curing catalyst (C), and a surface conditioner (D) which is essential for both of the silicon-based surface conditioner (D-1) and the acrylic surface conditioner (D-2), and is applied so that the dry film thickness is 30 + -5 [ mu ] m, and the glass transition temperature of the cured film when cured by baking at 80 ℃ for 20 minutes is 100 ℃ or higher and the molecular weight between the crosslinking points is 900g/mol or lower. This patent uses a silicon-based or acrylic surface conditioner to coat the surface and protect the substrate, and has the effect of oleic acid resistance and lactic acid resistance, but is substantially far from this patent. The patent does not utilize the change of hydrophobicity to achieve the effect of reducing the adhesion of stains, but only avoids polluting substances from damaging the surface, and the final evaluation method of the patent also shows that the two patents have larger difference.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a stain-resistant PC/ABS alloy and a preparation method thereof.
The purpose of the invention can be realized by the following technical scheme:
the stain-resistant PC/ABS alloy is prepared from the following raw materials in parts by weight:
PC (polycarbonate): 40 to 80 parts by weight
ABS (polyacrylonitrile-butadiene-styrene copolymer): 10 to 50
Stain-resistant PBT master batch: 5 to 45
A compatilizer: 0.5 to 3
Antioxidant: 0.1 to 1
Lubricant: 0.1 to 1
Preferably, the PC is bisphenol A polycarbonate with the number average molecular weight of 17000-30000 g/mol, and the glass transition temperature of the polycarbonate is 145-150 ℃.
Preferably, the particle size range of the ABS is 150 nm-2 um.
Preferably, the compatilizer is AS-g-MAH (acrylonitrile-styrene copolymer grafted maleic anhydride), AS-g-GMA (acrylonitrile-styrene copolymer grafted glycidyl methacrylate) or PMMA-g-MAH (polymethyl methacrylate grafted maleic anhydride).
Preferably, the lubricant comprises one or more of silicone powder, pentaerythritol ester and ethylene bisstearylamide.
Preferably, the antioxidant comprises one or more of commercially available antioxidant 245, antioxidant 1076 and antioxidant 168.
The stain-resistant PBT master batch comprises the following components in parts by weight:
the viscosity of the PBT is 0.6-1.0 dl/g.
The modified graphite fluoride comprises the following components in parts by weight:
graphite fluoride 95-99.5
Glycidyl methacrylate and its derivative 0.5-5
Preferably, the carbon-fluorine ratio of the graphite fluoride is 0.5-1.25
Preferably, the particle size of the calcium carbonate ranges from 500 meshes to 8000 meshes
Preferably, the glycidyl methacrylate and the derivatives thereof comprise one or more of glycidyl methacrylate, bisphenol A bis-glycidyl methacrylate, acrylonitrile-styrene-glycidyl methacrylate block copolymer and styrene-glycidyl methacrylate block copolymer
Preferably, the coupling agent is a fluorine-containing acrylate block copolymer, a fluorine-containing acrylonitrile-styrene block copolymer or a composition thereof
A method for producing modified graphite fluoride, comprising the steps of:
a. preparing the following components in parts by weight:
graphite fluoride 95-99.5
0.5-5 parts of glycidyl methacrylate and derivatives thereof;
b. putting other components of the prepared material into a mixer, and mixing for 5-30 min to obtain a mixed material;
c. and (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃ to obtain the modified graphite fluoride.
The manufacturing method of the stain-resistant PBT master batch comprises the following steps:
(1) preparing the following components in parts by weight:
(2) putting other components of the prepared material into a mixer, and mixing for 5-30 min to obtain a mixed material;
(3) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 180-600 rpm, and performing melt extrusion and granulation to obtain the master batch.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section.
The stain-resistant PC/ABS alloy is prepared by the following method:
(1) preparing the following components in parts by weight:
PC (polycarbonate): 40 to 80 parts by weight
ABS (polyacrylonitrile-butadiene-styrene copolymer): 10 to 50
Stain-resistant PBT master batch: 5 to 45
A compatilizer: 0.5 to 3
Antioxidant: 0.1 to 1
Lubricant: 0.1 to 1;
(2) placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) and (2) putting the mixed material into a double-screw extruder, controlling the rotating speed of a screw to be 180-600 rpm, feeding the stain-resistant PBT master batch from the side, carrying out melt extrusion and granulation to obtain a product, carrying out post-processing (such as injection molding or compression molding) on the product to obtain a product, and carrying out surface treatment by using hydrochloric acid to obtain the PC/ABS product with high stain resistance.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
Compared with the prior art, the invention has the following advantages:
(1) through the processing to graphite fluoride, through mechanical shear force and high temperature, graft GMA functional group to graphite fluoride, make graphite fluoride when having fine hydrophobic oleophobic property, still can react with the end carboxyl of PET base member to can stabilize in PET resin matrix well.
(2) By using the coupling agent, the compatibility of the graphite fluoride and the PBT matrix is better, so that the graphite fluoride has better dispersibility
(3) By adding the calcium carbonate, the calcium carbonate can be etched away by acid treatment at the later stage to form a micron nano structure on the surface, so that the aim of greatly improving hydrophobicity is fulfilled, and the pollution resistance is increased.
(4) Through the addition of glycerine, can migrate on the surface, when meetting acid solution, dissolve to aquatic fast to expose the substrate for calcium carbonate is by the sculpture, improves production efficiency, increases the hydrophobicity.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
In the following examples and comparative examples, bisphenol A polycarbonate with the number average molecular weight of 17000-30000 g/mol is selected, the glass transition temperature is 145-150 ℃, specifically L-1225Y, Tao's PC-201-10, Hunan petrochemical PC-1100 and PC-1220 are produced by Di-transformation, and the Hunan petrochemical PC-1100 and Di-transformation L-1225Y are preferably used; the PBT is a commercially available injection molding grade PBT, and the viscosity of the PBT is 0.6-1.0 dl/g; the ABS is commercially available ABS, and the particle size range of the rubber phase of the ABS is 150 nm-2 um; the compatilizer is Polyscope XIRANSZ23110, XIRAN SZ28110, Modiper C L130D, Shanghai Ri Sheng SAG-002; the antioxidant is 245, 1010 and 168 produced by CIBA company; MODIPER @ F600 with NOF as coupling agent; the graphite fluoride is commercially available graphite fluoride, the carbon-fluorine ratio of the graphite fluoride is 0.5-1.25, and the calcium carbonate is commercially available calcium carbonate, and the particle size of the calcium carbonate is 500-8000 meshes.
Comparative example 1
(1) Weighing the following components in parts by weight: 60Kg of PC, 39Kg of ABS, 0.1Kg of compatilizer XIRANSZ 231101 Kg, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate) and 0.5g of silicone powder.
(2) Placing the prepared components in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and carrying out melt extrusion and granulation to obtain the product. The double-screw extruder comprises ten temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃. The twin-screw extruder is also provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section and the starting end of the melting section, and the other vacuumizing position is positioned at the metering section.
Comparative example 2
(1) Weighing the following components in parts by weight: PC60Kg, 30Kg of ABS, 9Kg of PBT, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate) and 0.5g of silicone powder as compatilizer XIRAN SZ 231101 Kg.
(2) Placing the prepared components in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and carrying out melt extrusion and granulation to obtain the product. The double-screw extruder comprises ten temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃. The twin-screw extruder is also provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section and the starting end of the melting section, and the other vacuumizing position is positioned at the metering section.
Comparative example 3
(1) Weighing the following components in parts by weight: 60Kg of PC-1100 (polycarbonate), 34Kg of ABS, 5Kg of graphite fluoride, 0.1Kg of antioxidant 245, 0.1Kg of compatilizer XIRAN SZ 231101 Kg, 0.5Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate) and 0.5g of silicone powder.
(2) Placing the prepared components in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and carrying out melt extrusion and granulation to obtain the product. The double-screw extruder comprises ten temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃. The twin-screw extruder is also provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section and the starting end of the melting section, and the other vacuumizing position is positioned at the metering section.
Comparative example 4
(1) Weighing the following components in parts by weight: 60Kg of PC-1100 (polycarbonate), 25Kg of ABS, 15Kg of graphite fluoride, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate) and 0.5g of silicone powder.
(2) Placing the prepared components in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and carrying out melt extrusion and granulation to obtain the product. The double-screw extruder comprises ten temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃. The twin-screw extruder is also provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section and the starting end of the melting section, and the other vacuumizing position is positioned at the metering section.
Example 1
(1) Weighing the following components in parts by weight: graphite fluoride: 95 parts of glycidyl methacrylate and 5 parts of
(2) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(3) And (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃, and granulating to obtain the modified graphite fluoride.
(4) Weighing the following components in parts by weight: 90 portions of PBT (0.9dl/g), 9 portions of modified graphite fluoride, 1 portion of coupling agent MODIPER @ F600, 0.1Kg of antioxidant 245 and 0.1Kg of antioxidant 168
(5) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(6) And (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and carrying out melt extrusion and granulation to obtain the stain-resistant PBT master batch.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section.
(7) Weighing the following components in parts by weight: 60Kg of PC-1100 (polycarbonate), 23Kg of ABS, 15Kg of stain-resistant PBT master batch, 2Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate), 0.5Kg of silicone powder
(8) Placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(9) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, feeding the stain-resistant PBT master batch from the side, and carrying out melt extrusion and granulation to obtain the product.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
Example 2
(1) Weighing the following components in parts by weight: graphite fluoride: 99 parts of glycidyl methacrylate and 1 part of
(2) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(3) And (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃, and granulating to obtain the modified graphite fluoride.
(4) Weighing the following components in parts by weight: 80 parts of PBT (0.65dl/g), 15 parts of modified graphite fluoride, 4 parts of calcium carbonate (5000 meshes), 1 part of coupling agent MODIPER @ F600, 0.1Kg of antioxidant 245 and 0.1Kg of antioxidant 168
(5) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(6) And (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and performing melt extrusion and granulation to obtain the master batch.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section.
(7) Weighing the following components in parts by weight: 70Kg of PC-1100 (polycarbonate), 23Kg of ABS, 5Kg of stain-resistant PBT master batch, 2Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate), 0.5Kg of silicone powder
(8) Placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(9) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, feeding the stain-resistant PBT master batch from the side, and carrying out melt extrusion and granulation to obtain the product.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
Example 3
(1) Weighing the following components in parts by weight: graphite fluoride: 99 parts of glycidyl methacrylate and 1 part of
(2) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(3) And (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃, and granulating to obtain the modified graphite fluoride.
(4) Weighing the following components in parts by weight: 40 portions of PBT (0.9dl/g), 47 portions of modified graphite fluoride, 10 portions of calcium carbonate (8000 meshes), 3 portions of coupling agent MODIPER @ F600, 0.1Kg of antioxidant 245 and 0.1Kg of antioxidant 168
(5) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(6) And (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and performing melt extrusion and granulation to obtain the master batch.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section.
(7) Weighing the following components in parts by weight: 70Kg of PC-1100 (polycarbonate), 23Kg of ABS, 5Kg of stain-resistant PBT master batch, 2Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate), 0.5Kg of silicone powder
(8) Placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(9) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, feeding the stain-resistant PBT master batch from the side, and carrying out melt extrusion and granulation to obtain the product.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
Example 4
(1) Weighing the following components in parts by weight: graphite fluoride: 97 parts of glycidyl methacrylate and 3 parts of
(2) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(3) And (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃, and granulating to obtain the modified graphite fluoride.
(4) Weighing the following components in parts by weight: 49 parts of PBT (0.6dl/g), 29 parts of modified graphite fluoride, 15 parts of calcium carbonate (8000 meshes), 4 parts of calcium carbonate (2000 meshes), 1 part of glycerol, 2 parts of coupling agent MODIPER @ F600, 0.1Kg of antioxidant 245 and 0.1Kg of antioxidant 168
(5) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(6) And (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and performing melt extrusion and granulation to obtain the master batch.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section.
(7) Weighing the following components in parts by weight: 65Kg of PC-1100 (polycarbonate), 19Kg of ABS, 10Kg of stain-resistant PBT master batch, 1Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate), 0.5Kg of silicone powder
(8) Placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(9) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, feeding the stain-resistant PBT master batch from the side, and carrying out melt extrusion and granulation to obtain the product.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
Example 5
(1) Weighing the following components in parts by weight: graphite fluoride: 99 parts of glycidyl methacrylate and 1 part of
(2) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(3) And (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃, and granulating to obtain the modified graphite fluoride.
(4) Weighing the following components in parts by weight: 49 parts of PBT (0.6dl/g), 29 parts of modified graphite fluoride, 14 parts of calcium carbonate (8000 meshes), 3 parts of calcium carbonate (2000 meshes), 3 parts of glycerol, 2 parts of coupling agent MODIPER @ F600, 0.1Kg of antioxidant 245 and 0.1Kg of antioxidant 168
(5) Putting other prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material
(6) And (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, and performing melt extrusion and granulation to obtain the master batch.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section.
(7) Weighing the following components in parts by weight: 40Kg of PC-1100 (polycarbonate), 29Kg of ABS, 30Kg of stain-resistant PBT master batch, 1Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate), 0.5Kg of silicone powder
(8) Placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(9) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 500rpm, feeding the stain-resistant PBT master batch from the side, and carrying out melt extrusion and granulation to obtain the product.
The double-screw extruder comprises 10 temperature control areas, wherein the temperature of the temperature control area 1-2 is 180-260 ℃, the temperature of the temperature control area 3-4 is 180-260 ℃, the temperature of the temperature control area 5-6 is 180-260 ℃, the temperature of the temperature control area 7-8 is 180-260 ℃, and the temperature of the temperature control area 9-10 is 180-260 ℃.
The double-screw extruder is provided with two vacuumizing positions, one vacuumizing position is positioned at the tail end of the material conveying section, the melting section is started, and the other vacuumizing position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
The results of dyne value, stain resistance and water stain resistance are shown in Table 1 for comparison of each comparative example and example.
The surface tension test passed the ACCU's dyne pen test, and the dyne values were recorded.
Stain resistance test the surface was scribed using a TOYO WB528 marker to simulate staining, the marker was observed for ink and wiped with a paper towel to observe the wipe.
It is the antifouling layer surface repelling ink and can be wiped off
O is ink repellent to the surface of the antifouling layer, but cannot be wiped off
Delta is that the surface of the antifouling layer does not repel ink and cannot be wiped off
Water stain resistance was tested by spraying tap water, drying at 40 deg.C for 24h, observing attached water stain, wiping with a paper towel, and observing wiping condition
It is supposed to wipe off water stain
O. failure to completely wipe off water stains
Delta. is not substantially capable of wiping off water stains
TABLE 1
As can be seen from Table 1: from comparative examples 1, 2, 3 and 4, it can be seen that the dyne values for the typical PC/ABS materials are all greater than 40. The PC/ABS alloy has poor stain resistance and water resistance, and after the addition of vinylidene fluoride or graphite, although the dyne value is reduced and the surface energy is changed, the stain resistance and water resistance effects are still poor. It can be seen from comparative examples 3, 4 and example 1 that by using a stain resistant PBT masterbatch, very good results are soon achieved, although less graphite fluoride is used. Because the modified graphite fluoride and the PET are well fused together through reactive extrusion, the modified graphite fluoride and the PET can have better compatibility with the whole matrix, and simultaneously, the graphite fluoride can be more easily transferred to the surface due to the flowing behavior of the master batch, so that the hydrophobic and oleophobic effects are achieved. Through the embodiments 1-2, the PBT with lower viscosity and the modified graphite fluoride with higher content are used in the master batch, so that the hydrophobic and oleophobic effects are more favorably embodied.
And (3) injection molding the finished product particles into a plate, soaking the plate in 20% hydrochloric acid solution for 3min, taking out, drying the plate at 80 ℃ for 6h, taking out, and testing to obtain:
from the above results, it can be seen that the addition of calcium carbonate further reduced the dyne value after hydrochloric acid post-treatment, and it was found that the hydrophobicity was greatly improved. This is because in the acid solution, calcium carbonate can be removed to form the surface micron nano structure, achieving good hydrophobic effect, and it can be seen from examples 3, 4 and 5 that the addition of glycerol, because glycerol can be dissolved in water, so that hydrochloric acid can better etch away calcium carbonate, can obtain more uniform surface structure, thus further improving hydrophobicity, and from the results of resisting stain and water stain, also has better performance.
Example 6
The stain-resistant PC/ABS alloy is prepared from the following raw materials in parts by weight:
PC (polycarbonate) 40, ABS (polyacrylonitrile-butadiene-styrene copolymer) 50, stain-resistant PBT master batch 5, compatilizer 0.5, antioxidant 0.1 and lubricant 0.1. The PC used was a bisphenol A polycarbonate with a number average molecular weight of 17000, a glass transition temperature of 145 ℃ and a particle size of 150nm for ABS. The compatilizer is AS-g-MAH (acrylonitrile-styrene copolymer grafted maleic anhydride), the lubricant is silicone powder, and the antioxidant is a commercially available antioxidant 245.
The stain-resistant PBT master batch is one of the key components of the application, and comprises the following components in parts by weight: PBT40 with the viscosity of 0.6dl/g, modified graphite fluoride 40, calcium carbonate 2 and antioxidant 0.1. In the components, the particle size of the calcium carbonate is 500 meshes, and the antioxidant is a commercially available antioxidant 245. The modified graphite fluoride comprises the following components in parts by weight: graphite fluoride 95, glycidyl methacrylate and a derivative thereof 5, wherein the carbon-fluorine ratio in the graphite fluoride is 0.5, the glycidyl methacrylate and the derivative thereof adopt glycidyl methacrylate, and the graphite fluoride is prepared by the following method: and (3) placing other prepared components into a mixer, mixing for 5min to obtain a mixed material, then placing the mixed material into an internal mixer, carrying out internal mixing for 30s at the temperature of 150 ℃ to obtain the modified graphite fluoride. The manufacturing method of the stain-resistant PBT master batch comprises the following steps:
(1) preparing materials according to the content of the components;
(2) placing the other components in the mixer, and mixing for 5min to obtain a mixed material;
(3) the mixed material is put into a double-screw extruder, the double-screw extruder comprises 10 temperature control areas, the temperature of the temperature control area 1-2 is 180 ℃, the temperature of the temperature control area 3-4 is 180 ℃, the temperature of the temperature control area 5-6 is 180 ℃, the temperature of the temperature control area 7-8 is 180 ℃, the temperature of the temperature control area 9-10 is 180 ℃, two vacuumizing parts are arranged, one vacuumizing part is positioned at the tail end of a material conveying section, the beginning of a melting section, the other vacuumizing part is positioned at a metering section, the rotating speed of a screw of the screw extruder is controlled to be 180rpm, and the master batch is obtained through melting extrusion and granulation.
A preparation method of a stain-resistant PC/ABS alloy is characterized by comprising the following steps:
(1) preparing the components according to the formula disclosed in the embodiment;
(2) placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) putting the mixed material into a double-screw extruder, wherein the used double-screw extruder comprises 10 temperature control areas, the temperature of the temperature control area 1-2 is 180 ℃, the temperature of the temperature control area 3-4 is 180 ℃, the temperature of the temperature control area 5-6 is 180 ℃, the temperature of the temperature control area 7-8 is 180 ℃, the temperature of the temperature control area 9-10 is 180 ℃, the double-screw extruder is provided with two vacuumizing parts, one vacuumizing part is positioned at the tail end of a material conveying section, the beginning of a melting section, and the other vacuumizing part is positioned at a metering section; and the position of the side feeding port is in a temperature control 5 area, the rotating speed of a screw extruder is controlled to be 180rpm, the stain-resistant PBT master batch is fed from the side, and the product is obtained through melt extrusion and granulation.
Example 7
The stain-resistant PC/ABS alloy is prepared from the following raw materials in parts by weight:
PC (polycarbonate) 80, ABS (polyacrylonitrile-butadiene-styrene copolymer) 10, stain-resistant PBT master batch 45, compatilizer 3, antioxidant 1 and lubricant 1. The PC used is bisphenol A polycarbonate with the number average molecular weight of 30000, the glass transition temperature of the polycarbonate is 150 ℃, the particle size of ABS is 2um, the compatilizer is PMMA-g-MAH (polymethyl methacrylate grafted maleic anhydride), the lubricant is a mixture of pentaerythritol ester and ethylene distearamide, and the antioxidant is commercially available antioxidant 168.
The stain-resistant PBT master batch is one of the key components of the application, and comprises the following components in parts by weight: PBT 95 with the viscosity of 1.0dl/g, modified graphite fluoride 2, calcium carbonate 20, glycerol 10, a coupling agent 3 and an antioxidant 1. The particle size of the used calcium carbonate is 8000 meshes, the coupling agent is a fluorine-containing acrylate block copolymer, the antioxidant is antioxidant 158, and the modified graphite fluoride comprises the following components in parts by weight: 99.5 parts of graphite fluoride and 0.5 part of glycidyl methacrylate and derivatives thereof, wherein the carbon-fluorine ratio of the graphite fluoride is 1.25, and the glycidyl methacrylate and the derivatives thereof are a mixture of bisphenol A bis glycidyl methacrylate and acrylonitrile-styrene-glycidyl methacrylate block copolymer.
The method for producing the modified graphite fluoride comprises the following steps: and (3) placing other components of the prepared material into a mixer, mixing for 30min to obtain a mixed material, then placing the mixed material into an internal mixer, carrying out internal mixing at the temperature of 230 ℃ for 10min to obtain the modified graphite fluoride.
The manufacturing method of the stain-resistant PBT master batch comprises the following steps:
(1) preparing materials according to the content of the components;
(2) placing other components in the mixer, and mixing for 30min to obtain a mixed material;
(3) the mixed material is put into a double-screw extruder, the double-screw extruder comprises 10 temperature control areas, the temperature of the temperature control area 1-2 is 260 ℃, the temperature of the temperature control area 3-4 is 260 ℃, the temperature of the temperature control area 5-6 is 260 ℃, the temperature of the temperature control area 7-8 is 260 ℃, the temperature of the temperature control area 9-10 is 260 ℃, the double-screw extruder is provided with two vacuumizing parts, one vacuumizing part is positioned at the tail end of a material conveying section, the beginning of a melting section, the other vacuumizing part is positioned at a metering section, the rotating speed of a screw is controlled to be 600rpm, and the master batch is obtained through melting extrusion and granulation.
The preparation method of the stain-resistant PC/ABS alloy comprises the following steps:
(1) preparing the components according to the formula disclosed in the embodiment;
(2) placing the materials except the stain-resistant PBT master batch in a medium-speed mixer, and mixing for 20min to obtain a mixed material;
(3) putting the mixed material into a double-screw extruder, wherein the used double-screw extruder comprises 10 temperature control areas, the temperature of the temperature control area 1-2 is 260 ℃, the temperature of the temperature control area 3-4 is 260 ℃, the temperature of the temperature control area 5-6 is 260 ℃, the temperature of the temperature control area 7-8 is 260 ℃, the temperature of the temperature control area 9-10 is 260 ℃, the double-screw extruder is provided with two vacuumizing parts, one vacuumizing part is positioned at the tail end of a material conveying section, the beginning of a melting section, and the other vacuumizing part is positioned at a metering section; and the position of the side feeding port is in a temperature control 5 area, the rotating speed of a screw extruder is controlled to be 600rpm, the stain-resistant PBT master batch is fed from the side, and the product is obtained through melt extrusion and granulation.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (7)
1. The stain-resistant PC/ABS alloy is characterized by being prepared from the following raw materials in parts by weight:
40-80 parts of polycarbonate, 10-50 parts of polyacrylonitrile-butadiene-styrene copolymer, 5-45 parts of stain-resistant PBT master batch, 0.5-3 parts of compatilizer, 0.1-1 part of antioxidant and 0.1-1 part of lubricant,
the stain-resistant PBT master batch comprises the following components in parts by weight:
PBT 40～95
2-40 parts of modified graphite fluoride
2-20 parts of calcium carbonate
0-10% of glycerol
1 to 3 coupling agents
0.1 to 1 part of an antioxidant,
the modified graphite fluoride comprises the following components in parts by weight:
95 to 99.5 percent of graphite fluoride,
0.5 to 5 parts of glycidyl methacrylate and derivatives thereof,
the carbon-fluorine ratio of the graphite fluoride is 0.5 to 1.25,
the glycidyl methacrylate and the derivative thereof comprise one or a mixture of more of glycidyl methacrylate, bisphenol A bis-glycidyl methacrylate, acrylonitrile-styrene-glycidyl methacrylate block copolymer or styrene-glycidyl methacrylate block copolymer;
the coupling agent is a fluorine-containing acrylate block copolymer, a fluorine-containing acrylonitrile-styrene block copolymer or a composition thereof, and the particle size of the calcium carbonate is 500-8000 meshes.
2. A stain resistant PC/ABS alloy as claimed in claim 1 wherein the PBT has a viscosity of 0.6-1.0 dl/g.
3. The stain resistant PC/ABS alloy of claim 1, wherein the modified graphite fluoride is prepared by the following method:
a. preparing the components according to the formula and the weight parts;
b. placing the prepared components into a mixer, and mixing for 5-30 min to obtain a mixed material;
c. and (3) putting the mixed material into an internal mixer, carrying out internal mixing for 30 s-10 min at the temperature of 150-230 ℃, and granulating to obtain the modified graphite fluoride.
4. The stain resistant PC/ABS alloy of claim 1, wherein the stain resistant PBT master batch is prepared by the following method:
(1) preparing the components according to the formula and the weight parts;
(2) placing the raw materials in a mixer, and mixing for 5-30 min to obtain a mixed material;
(3) and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 180-600 rpm, and carrying out melt extrusion and granulation to obtain the stain-resistant PBT master batch.
5. The stain resistant PC/ABS alloy according to claim 4, wherein the twin screw extruder comprises 10 temperature control zones, the temperature of temperature control zone 1-2 is 180-260 ℃, the temperature of temperature control zone 3-4 is 180-260 ℃, the temperature of temperature control zone 5-6 is 180-260 ℃, the temperature of temperature control zone 7-8 is 180-260 ℃, the temperature of temperature control zone 9-10 is 180-260 ℃, the twin screw extruder is provided with two vacuum pumping parts, one vacuum pumping part is located at the end of the material conveying section, the melting section is started, and the other vacuum pumping part is located at the metering section.
6. The method of claim 1 for preparing a stain resistant PC/ABS alloy, wherein the method comprises the steps of:
a. preparing the components according to the formula and the weight parts;
b. placing components except the stain-resistant PBT master batch in a mixer, and mixing for 5-30 min to obtain a mixed material;
c. and (3) putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 180-600 rpm, feeding the stain-resistant PBT master batch from a side feeding port, and carrying out melt extrusion and granulation to obtain the product.
7. The preparation method of the stain resistant PC/ABS alloy according to claim 6, wherein the twin screw extruder comprises 10 temperature control zones, the temperature of the temperature control 1-2 zone is 180-260 ℃, the temperature of the temperature control 3-4 zone is 180-260 ℃, the temperature of the temperature control 5-6 zone is 180-260 ℃, the temperature of the temperature control 7-8 zone is 180-260 ℃, the temperature of the temperature control 9-10 zone is 180-260 ℃, two vacuum pumping positions are arranged on the twin screw extruder, one vacuum pumping position is positioned at the tail end of the conveying material section and the beginning end of the melting section, and the other vacuum pumping position is positioned at the metering section; the position of the side feeding opening is in one of the temperature control areas 5-9.
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