CN109796740B - Stain-resistant PC/PET alloy and preparation method thereof - Google Patents
Stain-resistant PC/PET alloy and preparation method thereof Download PDFInfo
- Publication number
- CN109796740B CN109796740B CN201811647423.7A CN201811647423A CN109796740B CN 109796740 B CN109796740 B CN 109796740B CN 201811647423 A CN201811647423 A CN 201811647423A CN 109796740 B CN109796740 B CN 109796740B
- Authority
- CN
- China
- Prior art keywords
- pet
- parts
- stain
- resistant
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
The invention discloses a stain-resistant PC/PET alloy and a preparation method thereof, wherein the alloy comprises the following components in parts by weight: PC: 40-80 parts of PET: 10-40 parts of stain-resistant PET master batch: 0.1-15 parts of a compatilizer: 0.5-3 parts of toughening agent, 2-15 parts of antioxidant, 0.1-1 part of lubricant and 0.1-1 part of plasticizer; preparing the components according to the weight parts, placing the materials except the stain-resistant PET 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, controlling the rotating speed of a screw to be 180-600 rpm, feeding the stain-resistant PET master batch from the side, and carrying out melt extrusion and granulation to obtain the product. Compared with the prior art, the PC/PET alloy provided by the invention has higher surface hydrophobicity and stain resistance while keeping better processing performance.
Description
Technical Field
The invention relates to the field of high polymer materials, in particular to a stain-resistant PC/PET alloy and a preparation method thereof.
Background
The PC/PET alloy is a semi-crystalline engineering plastic, has excellent performances such as impact strength, heat resistance, oil resistance and solvent resistance, and is widely used in the fields of automobiles, electronics, household appliances and the like.
Through the search of the prior patent documents, the following results are found: guabin in the patent CN 101007893 describes PC/PET alloy products obtained by mixing milled PC pellets, PET chips and auxiliaries and then performing die forming after mixing, and the products are used for switch films of electric appliances, instrument panels of automobiles and the like.
Heqixin et al in the CN 101712794 patent describe the use of MBS and silicon based tougheners to improve the low temperature toughness of PC/PET alloys.
Yupeng et al describe in CN 101570627 the preparation of a transparent PC/PET alloy from a pyrinol compound by using aryl phosphates.
Although there are many reports of PC/PET alloy materials at present, there is no report of a pollution-resistant PC/PET alloy.
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.
Zhang Bo et al in CN108285707A describe that the brookite titanium type nanometer titanium dioxide is used to prepare an anti-corrosion and anti-fouling high heat insulation coating and a preparation method thereof
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.
Although there are some other patents in the field of stain resistance, the application range is limited, and the performance requirements of engineering plastics cannot be met.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a stain-resistant PC/PET alloy and a preparation method thereof.
The PC/PET alloy is a common engineering plastic and is widely used in the fields of automobiles, household appliances and office supplies. 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/PET has poor pollution resistance, the PC/PET alloy is modified to meet the requirement of pollution resistance.
The purpose of the invention can be realized by the following technical scheme:
the invention relates to a stain-resistant PC/PET alloy which comprises the following components in parts by weight:
PC (polycarbonate): 40-80 parts of (A) a water-soluble polymer,
PET (polyethylene terephthalate): 10 to 25 parts of (A) a water-soluble polymer,
stain-resistant PET master batch: 5 to 30 parts of a water-soluble polymer,
a toughening agent: 2 to 15 parts of (a) a water-soluble polymer,
a compatilizer: 0.5 to 3 parts by weight of a stabilizer,
antioxidant: 0.1 to 1 part by weight of a surfactant,
lubricant: 0.1 to 1 portion.
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 viscosity of the PET is 0.65-0.9 dl/g.
Preferably, the toughening agent comprises methyl methacrylate/butadiene/styrene copolymer, methyl methacrylate/acrylic polymer, acrylic toughening agent, acrylic-silicone rubber toughening agent, ethylene-methyl acrylate, ethylene-butyl acrylate, ethylene-acrylate-glycidyl methacrylate terpolymer or ethylene-vinyl acetate copolymer-functionalized maleic anhydride.
Preferably, the grain size of the toughening agent is 50-700 nm, and the glue content of the toughening agent is 40-90 wt%.
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 an antioxidant 245, an antioxidant 1076 and an antioxidant 168.
Preferably, the stain-resistant PET master batch comprises the following components in parts by weight:
preferably, the viscosity of the PET in the stain-resistant PET master batch is 0.65-0.9 dl/g. In the system of the present invention, when the viscosity is too low, the maintenance of physical and mechanical properties is not facilitated, and when the viscosity is too high, the processability is also limited.
Preferably, the coupling agent is a fluorine-containing acrylate block copolymer, a fluorine-containing acrylonitrile-styrene block copolymer, or a combination thereof. The compatibility of the modified graphite fluoride of the invention with the base material can be well enhanced by selecting the coupling agent, and the use of other coupling agents (such as PE-g-MAH) can possibly cause the effect of improving the compatibility to be limited and even bring reverse effect.
Preferably, the stain-resistant PET masterbatch is prepared by a method comprising the following steps:
a1, placing the PET, the modified graphite fluoride, the coupling agent and the antioxidant into a mixer, and mixing for 5-30 min to obtain a mixed material;
a2, putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 180-160 rpm, and carrying out melt extrusion and granulation to obtain the stain-resistant PET master batch.
Preferably, in the step A2, the twin-screw extruder comprises 10 temperature control zones, wherein the temperature of the temperature control zone 1-2 is 180-260 ℃, the temperature of the temperature control zone 3-4 is 180-260 ℃, the temperature of the temperature control zone 5-6 is 180-260 ℃, the temperature of the temperature control zone 7-8 is 180-260 ℃, and the temperature of the temperature control zone 9-10 is 180-260 ℃.
Preferably, the twin-screw extruder is provided with two evacuation points, one at the end of the conveying section, the beginning of the melting section and the other at the metering section.
Preferably, the modified graphite fluoride comprises the following components in parts by weight:
95 to 99.5 parts of graphite fluoride,
0.5-5 parts of glycidyl methacrylate and derivatives thereof.
Preferably, the carbon-fluorine ratio of the graphite fluoride is 0.5-1.25. When the fluorocarbon ratio is too low, the hydrophobicity is affected, the fluorocarbon ratio is too high, the processing process is very difficult, the cost performance is reduced, and the industrial process is not facilitated.
Preferably, 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 and styrene-glycidyl methacrylate block copolymer.
Preferably, the modified graphite fluoride is prepared by a method comprising the following steps:
b1, placing the graphite fluoride, the glycidyl methacrylate and the derivatives thereof in a mixer, and mixing for 5-30 min to obtain a mixed material;
and B2, putting the mixed materials 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.
The invention also relates to a preparation method of the stain-resistant PC/PET alloy, which comprises the following steps:
s1, placing the PC, the PET, the toughening agent, the compatilizer, the antioxidant and the lubricant into a mixer, and mixing for 5-30 min to obtain a mixed material;
and S2, putting the mixed material into a double-screw extruder, controlling the rotating speed of the screws to be 180-600 rpm, feeding the pollution-resistant PET master batches from the side, and carrying out melt extrusion and granulation to obtain the pollution-resistant PC/PET alloy.
Preferably, 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 ℃.
Preferably, 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 beneficial effects:
(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 PET matrix is better, so that the graphite fluoride has better dispersibility.
(3) The prepared PC/PET alloy is convenient to process, has higher stain resistance and better mechanical strength.
Detailed Description
The present invention will be described in detail with reference to 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 it would be apparent to those skilled in the art that several modifications and improvements can be made without departing from the inventive concept. 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 PET is commercially available injection molding grade PET, and the viscosity of the PET is 0.65-0.9 dl/g; the grain size of the toughening agent is 50-700 nm, the glue content is 40-90%, and the toughening agent is specifically used for EM 500 produced by LG, M521 produced by Brillouin, EXL-2620 produced by Rohm and Haas and AX 8900 produced by Achima; the compatilizer is Polyscope XIRAN SZ23110, XIRAN SZ28110, Modiper C L130D, Shanghai Ri Sheng SAG-002; the antioxidant is 245, 1010 and 168 produced by CIBA company; the coupling agent is a fluorine-containing acrylate block copolymer, a fluorine-containing acrylonitrile-styrene block copolymer or a composition thereof; MODIPER @ F600 for NOF was selected in the following examples; the graphite fluoride is commercially available graphite fluoride, and has a carbon-fluorine ratio of 0.5 to 1.25.
Comparative example 1
(1) Weighing the following components in parts by weight: 60Kg of PC-1100 (polycarbonate), 35Kg of PET (0.9dl/g), MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ 231101 Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 g.
(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: 60Kg of PC-1100 (polycarbonate), 25Kg of PET (0.9dl/g) and 10Kg of fluorosilicone resin, wherein the ratio of the fluororesin to the silicone resin is 1: 0.8, MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ 231101 Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 g.
(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), 30Kg of PET (0.9dl/g), 5Kg of graphite fluoride, MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ 231101 Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 g.
(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), 20Kg of PET (0.65dl/g), 15Kg of graphite fluoride, MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ 231101 Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 g.
(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 5
(1) Weighing the following components in parts by weight: 60Kg of PC-1100 (polycarbonate), 33.5Kg of PET (0.65dl/g), 1.5Kg of graphite fluoride, 0.1Kg of glycidyl methacrylate, 0.2Kg of the coupling agent MODIPER @ F600, MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ 231101 Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 g.
(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 glycidyl methacrylate;
(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 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 parts of PET (0.9dl/g), 9 parts of modified graphite fluoride, 1 part of coupling agent MODIPER @ F600, 0.1 part of antioxidant 245 and 0.1 part of antioxidant 168;
(5) putting other components of the prepared material 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 PET 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), 20Kg of PET (0.9dl/g), 15Kg of stain-resistant PET master batch, MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ23110 is 1Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 Kg;
(8) placing the materials except the stain-resistant PET 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 PET 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 glycidyl methacrylate;
(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 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 PET (0.65dl/g), 19 parts of modified graphite fluoride, 1 part of coupling agent MODIPER @ F600, 0.1 part of antioxidant 245 and 0.1 part of antioxidant 168;
(5) putting other components of the prepared material 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 PET 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), 18Kg of PET (0.9dl/g), 5Kg of stain-resistant PET master batch, MBS (methyl methacrylate-butadiene-styrene copolymer): 5Kg of EM 500, 2Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate) and 0.5Kg of silicone powder;
(8) placing the materials except the stain-resistant PET 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 PET 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: 99.5 parts of glycidyl methacrylate and 0.5 part of glycidyl methacrylate;
(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 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 parts of PET (0.9dl/g), 57 parts of modified graphite fluoride, 3 parts of coupling agent MODIPER @ F600, 0.1 part of antioxidant 245 and 0.1 part of antioxidant 168;
(5) putting other components of the prepared material 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 PET 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), 18Kg of PET (0.9dl/g), 5Kg of stain-resistant PET master batch, MBS (methyl methacrylate-butadiene-styrene copolymer): 5Kg of EM 500, 2Kg of compatilizer XIRAN SZ23110, 0.1Kg of antioxidant 245, 0.1Kg of antioxidant 168, 0.5Kg of lubricant PETS (pentaerythritol stearate) and 0.5Kg of silicone powder;
(8) placing the materials except the stain-resistant PET 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 PET 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 glycidyl methacrylate;
(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 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 PET (0.65dl/g), 49 parts of modified graphite fluoride, 2 parts of coupling agent MODIPER @ F600, 0.1 part of antioxidant 245 and 0.1 part of antioxidant 168;
(5) putting other components of the prepared material 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 PET 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), 15Kg of PET (0.9dl/g), 10Kg of stain-resistant PET master batch, MBS (methyl methacrylate-butadiene-styrene copolymer): EM 500 is 4Kg, compatilizer XIRAN SZ23110 is 1Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 Kg;
(8) placing the materials except the stain-resistant PET 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 PET 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 glycidyl methacrylate;
(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 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 PET (0.65dl/g), 49 parts of modified graphite fluoride, 2 parts of coupling agent MODIPER @ F600, 0.1 part of antioxidant 245 and 0.1 part of antioxidant 168;
(5) putting other components of the prepared material 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 PET 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), 25Kg of PET (0.9dl/g), 30Kg of stain-resistant PET masterbatch, MBS (methyl methacrylate-butadiene-styrene copolymer): AX 8900 is 4Kg, compatilizer XIRAN SZ23110 is 1Kg, antioxidant 245 is 0.1Kg, antioxidant 168 is 0.1Kg, lubricant PETS (pentaerythritol stearate) is 0.5Kg, and silicone powder is 0.5 Kg;
(8) placing the materials except the stain-resistant PET 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 PET 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 6, Performance test
The results of comparing the above comparative examples with those of the examples are shown in Table 1.
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 believed that the stain repellent layer surface repels ink and can be wiped off,
o is that the surface of the antifouling layer repels ink but cannot be wiped off,
delta is that the surface of the antifouling layer does not repel ink and can not 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 believed that in order to wipe off water stains,
o is not able to completely wipe off water stains,
the delta is basically incapable of wiping off water stains,
TABLE 1
As can be seen from Table 1: from comparative examples 1-4 it can be seen that the dyne values for the typical PC/PET materials are all greater than 40. The PC/PET alloy has poor stain resistance and water resistance, and after the addition of fluorosilicone resin or graphite fluoride, 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, 5 and example 1 that by using the stain resistant PET master batch, good results are soon achieved although less graphite fluoride is used. The modified graphite fluoride and PET are well fused together through reactive extrusion through surface treatment, and the modified graphite fluoride and PET are fed through an extruder side, so that the modified graphite fluoride and PET have better compatibility with the whole matrix, and meanwhile, due to the flowing behavior of master batches, the graphite fluoride is more easily transferred to the surface, the hydrophobic and oleophobic effect is achieved, and the use efficiency of the graphite fluoride is greatly improved. Through the embodiments 1-2, the PET with lower viscosity and higher modified graphite fluoride content are used in the master batch, so that the hydrophobic and oleophobic effects are more favorably embodied. By improving the concentration of graphite fluoride in the master batch and the addition amount of the master batch, the extremely low surface energy is achieved, and meanwhile, the excellent hydrophobic and oleophobic properties are achieved, so that the good stain resistant effect is achieved.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes and modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention.
Claims (7)
1. The stain-resistant PC/PET alloy is characterized by comprising the following components in parts by weight:
PC: 40-80 parts of (A) a water-soluble polymer,
PET: 10 to 25 parts of (A) a water-soluble polymer,
stain-resistant PET master batch: 5 to 30 parts of a water-soluble polymer,
a toughening agent: 2 to 15 parts of (a) a water-soluble polymer,
a compatilizer: 0.5 to 3 parts by weight of a stabilizer,
antioxidant: 0.1 to 1 part by weight of a surfactant,
lubricant: 0.1-1 part;
the stain-resistant PET master batch comprises the following components in parts by weight:
40-95 parts of PET (polyethylene terephthalate),
2-60 parts of modified graphite fluoride,
0.1 to 3 parts of a coupling agent,
antioxidant: 0.1-1 part;
the coupling agent is a fluorine-containing acrylate block copolymer, a fluorine-containing acrylonitrile-styrene block copolymer or a composition thereof;
the modified graphite fluoride comprises the following components in parts by weight:
95 to 99.5 parts of graphite fluoride,
0.5-5 parts of glycidyl methacrylate and derivatives thereof.
2. The stain resistant PC/PET alloy according to claim 1 wherein the viscosity of the PET in the stain resistant PET masterbatch is 0.65 to 0.9 dl/g.
3. The stain resistant PC/PET alloy of claim 1 wherein the stain resistant PET masterbatch is prepared by a process comprising the steps of:
a1, placing the PET, the modified graphite fluoride, the coupling agent and the antioxidant into a mixer, and mixing for 5-30 min to obtain a mixed material;
a2, putting the mixed material into a double-screw extruder, controlling the rotating speed of the screw to be 180-160 rpm, and carrying out melt extrusion and granulation to obtain the stain-resistant PET master batch.
4. The stain resistant PC/PET alloy of claim 1 wherein the graphite fluoride has a carbon to fluorine ratio of 0.5 to 1.25.
5. The stain resistant PC/PET alloy of claim 1 wherein the glycidyl methacrylate and its derivatives comprise one or a mixture of glycidyl methacrylate, bisphenol a bis glycidyl methacrylate, acrylonitrile-styrene-glycidyl methacrylate block copolymer, styrene-glycidyl methacrylate block copolymer.
6. The stain resistant PC/PET alloy of claim 1 wherein the modified graphite fluoride is prepared by a process comprising the steps of:
b1, placing the graphite fluoride, the glycidyl methacrylate and the derivatives thereof in a mixer, and mixing for 5-30 min to obtain a mixed material;
and B2, putting the mixed materials 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.
7. A method of making the stain resistant PC/PET alloy of claim 1, comprising the steps of:
s1, placing the PC, the PET, the toughening agent, the compatilizer, the antioxidant and the lubricant into a mixer, and mixing for 5-30 min to obtain a mixed material;
and S2, putting the mixed material into a double-screw extruder, controlling the rotating speed of the screws to be 180-600 rpm, feeding the pollution-resistant PET master batches from a side feeding port, and carrying out melt extrusion and granulation to obtain the pollution-resistant PC/PET alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811647423.7A CN109796740B (en) | 2018-12-30 | 2018-12-30 | Stain-resistant PC/PET alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811647423.7A CN109796740B (en) | 2018-12-30 | 2018-12-30 | Stain-resistant PC/PET alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109796740A CN109796740A (en) | 2019-05-24 |
| CN109796740B true CN109796740B (en) | 2021-05-11 |
Family
ID=66558178
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811647423.7A Active CN109796740B (en) | 2018-12-30 | 2018-12-30 | Stain-resistant PC/PET alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109796740B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109575562B (en) * | 2018-12-28 | 2021-03-30 | 上海锦湖日丽塑料有限公司 | Stain-resistant PC/ABS alloy and preparation method thereof |
| CN111471286B (en) * | 2020-04-07 | 2022-03-08 | 宁波坚锋新材料有限公司 | Friction-resistant stain-resistant fluorenyl polyester master batch and high-transparency scratch-resistant antibacterial high-performance polycarbonate composite material |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5263336A (en) * | 1975-11-20 | 1977-05-25 | Ricoh Co Ltd | Electrophotographic light sensitive material |
| JPS6194706A (en) * | 1984-10-15 | 1986-05-13 | Nok Corp | Mold |
| CN1092742A (en) * | 1992-11-06 | 1994-09-28 | 大金工业株式会社 | Fluorinated carbon particle and method for making thereof and usage |
| CN101982490A (en) * | 2010-10-29 | 2011-03-02 | 华东理工大学 | Preparation method of superhydrophobic self-cleaning material |
| CN104877323A (en) * | 2014-02-28 | 2015-09-02 | 汉达精密电子(昆山)有限公司 | Recovered PC/recovered PET composite material and product thereof |
| CN107245237A (en) * | 2017-06-29 | 2017-10-13 | 上海锦湖日丽塑料有限公司 | A kind of PC compositions resistant to chemical etching and preparation method thereof |
| CN107312307A (en) * | 2017-08-02 | 2017-11-03 | 广东锦湖日丽高分子材料有限公司 | A kind of polycarbonate compositions of high durable and preparation method thereof |
| CN107857994A (en) * | 2017-11-29 | 2018-03-30 | 南方科技大学 | A kind of nylon composite materials and preparation method thereof |
-
2018
- 2018-12-30 CN CN201811647423.7A patent/CN109796740B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5263336A (en) * | 1975-11-20 | 1977-05-25 | Ricoh Co Ltd | Electrophotographic light sensitive material |
| JPS6194706A (en) * | 1984-10-15 | 1986-05-13 | Nok Corp | Mold |
| CN1092742A (en) * | 1992-11-06 | 1994-09-28 | 大金工业株式会社 | Fluorinated carbon particle and method for making thereof and usage |
| CN101982490A (en) * | 2010-10-29 | 2011-03-02 | 华东理工大学 | Preparation method of superhydrophobic self-cleaning material |
| CN104877323A (en) * | 2014-02-28 | 2015-09-02 | 汉达精密电子(昆山)有限公司 | Recovered PC/recovered PET composite material and product thereof |
| CN107245237A (en) * | 2017-06-29 | 2017-10-13 | 上海锦湖日丽塑料有限公司 | A kind of PC compositions resistant to chemical etching and preparation method thereof |
| CN107312307A (en) * | 2017-08-02 | 2017-11-03 | 广东锦湖日丽高分子材料有限公司 | A kind of polycarbonate compositions of high durable and preparation method thereof |
| CN107857994A (en) * | 2017-11-29 | 2018-03-30 | 南方科技大学 | A kind of nylon composite materials and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109796740A (en) | 2019-05-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102617997B (en) | Glass fiber-reinforced PBT/PET (Polybutylece Terephthalate/Polyethyleneglycol Terephthalate) composite material and preparation method thereof | |
| CN107903540A (en) | A kind of polychloroethylene pipes material and preparation method thereof | |
| CN101787195A (en) | Polycarbonate/polyester composition and preparation method thereof | |
| CN105419142B (en) | A kind of plating PC/ABS alloy materials and preparation method thereof | |
| CN109796740B (en) | Stain-resistant PC/PET alloy and preparation method thereof | |
| JP2014503678A (en) | Biodegradable polymer composite | |
| CN113462141A (en) | High-toughness low-floating-fiber-reinforced PC/PBT alloy material and preparation method thereof | |
| CN107523001A (en) | A kind of ABS/PC 3D consumptive material PP Pipe Compounds and preparation method thereof | |
| CN111763383B (en) | Good-touch glass fiber reinforced polypropylene composite and preparation method thereof | |
| CN111117200A (en) | Graphene reinforced polycarbonate conductive composite material and preparation method thereof | |
| CN113444269A (en) | Low-warpage good-appearance glass fiber reinforced polypropylene composite material and preparation method thereof | |
| CN106046643A (en) | High-compatibility PMMA/ASA alloy resin composition and preparation method thereof | |
| CN107298839A (en) | PC/ABS alloy materials of low gloss and preparation method thereof | |
| CN104672756A (en) | ABS composite flame resistant material and preparation method thereof | |
| CN111440409A (en) | Spraying-free plastic and preparation method thereof | |
| CN112442251B (en) | ABS composite material and preparation method and application thereof | |
| CN111393823B (en) | Gn-PET/PC alloy with excellent mechanical property and preparation method thereof | |
| CN110684348B (en) | Polyamide material with metal texture and preparation method thereof | |
| CN105670125A (en) | High-smoothness long-glass-fiber flame-retardant toughened polypropylene blend material and preparation method thereof | |
| CN109575562B (en) | Stain-resistant PC/ABS alloy and preparation method thereof | |
| CN112724586B (en) | High-toughness low-floating-fiber ABS resin composition and preparation method and application thereof | |
| CN105440454B (en) | A kind of heat-proof aging PP composite material and preparation method thereof that surface is highly polar | |
| Duan et al. | The Role of Compatibilizers on the Properties of PC/ABS Alloy | |
| CN111484721A (en) | Low-temperature impact resistant PC/ABS composite material and preparation method thereof | |
| CN109705570A (en) | A kind of Particular thermoplastic's composite material and preparation method suitable for 3D printing |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |