CN102532853B - High-hardness and scratch-resistant modified PC (Poly Carbonate) material and preparation method thereof - Google Patents

High-hardness and scratch-resistant modified PC (Poly Carbonate) material and preparation method thereof Download PDF

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CN102532853B
CN102532853B CN201210005100.4A CN201210005100A CN102532853B CN 102532853 B CN102532853 B CN 102532853B CN 201210005100 A CN201210005100 A CN 201210005100A CN 102532853 B CN102532853 B CN 102532853B
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raw material
preparation
scratch
pmma
hardness
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CN102532853A (en
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韩丽燕
刘波
王长明
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SUZHOU TAIKAN MACHINERY Co.,Ltd.
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Janus Dongguan Precision Components Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/92—Measuring, controlling or regulating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
    • B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/9258—Velocity
    • B29C2948/9259—Angular velocity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92504—Controlled parameter
    • B29C2948/92704—Temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92885—Screw or gear
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00—Indexing scheme relating to extrusion moulding
    • B29C2948/92—Measuring, controlling or regulating
    • B29C2948/92819—Location or phase of control
    • B29C2948/92857—Extrusion unit
    • B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
    • B29C2948/92895—Barrel or housing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Abstract

The invention provides a high-hardness and scratch-resistant modified PC (Poly Carbonate) material and a preparation method thereof. The preparation method comprises the following steps of: blast-drying a PC material for 4-6 hours at a temperature of 100 DEG C and blast-drying a PMMA (Polymethyl Methacrylate) material for 2-4 hours at a temperature of 80 DEG C; weighing the dried PC material, the dried PMMA material, a scratch-resistant modifier, a compatilizer, a coupling agent, a toughening agent, a lubrication and dispersion agent and an antioxidant according to a weight ratio and putting in a high-speed mixer for mixing for 3-5 minutes at a high speed; and adding a raw material mixture premixed in the high-speed mixer into a double-screw extruder hopper for fusing, mixing, extruding, cooling, drying, pelletizing and packing. The modified PC material prepared by the preparation method is equivalent with a PC raw material in mechanical property and higher in heat resistance and has higher surface hardness and better scratch resistance. The high-hardness and scratch-resistant modified PC material is suitable for finished mobile phone shells and various electronic product shells and has the advantage of free spraying compared with the PC raw material and a PC/ABS material.

Description

A kind of high rigidity scratch resistance modification PC material and preparation method thereof
Technical field:
The present invention relates to technical field of polymer materials, relate in particular to a kind of high rigidity scratch resistance modification PC material and preparation method thereof.
Background technology:
PC is a kind of armorphous thermoplastic resin of high comprehensive performance, has excellent electrical insulating property, dimensional stability and chemical resistance, higher intensity, thermotolerance and winter hardiness.Its intensity can meet the various needs from mobile phone to splinter-proof glass.
Its Application Areas is very extensive at present, can be applicable to the fields such as electronic product, household electrical appliance, office appliance and automobile.But because its surperficial pencil hardness only has 2B left and right, use at ordinary times the goods of PC forming materials, in order to protect outward appearance to prevent from scratching, coating processing need be done in surface.No. 201010153417.3 patent of People's Republic of China's patent application discloses a kind of at polycarbonate (Polycarbonate, PC) in material, add polymethylmethacrylate (Polymethyl methacrylate, PMMA) obtain a kind of high rigidity, high strength, PC/PMMA alloy that chemicals-resistant is good, the defects such as this alloy has improved polycarbonate and PC/ABS alloy chemicals-resistant is poor, and hardness and intensity are low.Yet, in disclosed content, be mainly to have solved chemically-resistant erosion resistance, fail reasonably to solve the scratch resistant performance of PC material, thereby on the product after forming materials, carry out coating processing to increase the adhesion strength of product, thus the production cycle of having strengthened product.And in process of production, owing to having increased spray treatment, so increased the generation of volatile organic compounds, increased the weight of the healthy harm of operator and the pollution to environment.
Summary of the invention:
Object of the present invention be exactly the deficiency existing for prior art and provide that a kind of mechanical strength is high, good toughness, high surface hardness and scratch resistant PC material, also provide this PC material modified preparation method simultaneously.
To achieve these goals, the technical solution used in the present invention is:
A high rigidity scratch resistance modification PC material, it comprises the raw material of following weight part:
Figure BDA0000129475170000021
Described scratch resistance properties-correcting agent is one or more the composition in carbon fiber, glass fibre, wollastonite, talcum powder, process white, copper powder.
Described compatilizer is a kind of in phenylethylene-maleic anhydride-vinylformic acid shrink ester terpolymer (GMA-g-SMA), styrene-maleic anhydride copolymer (SMA), maleic anhydride grafted ABS (ABS-g-MAH), maleic anhydride grafted polyethylene (PE-g-MAH), maleic anhydride inoculated polypropylene (PP-g-MAH).
Described coupling agent is a kind of in silane coupling agent or titanate coupling agent.
Described toughner is a kind of in chlorinatedpolyethylene (CPE), Methylacrylate-Acrylate Copolymer (ACR), MBS ternary graft copolymer (MBS resin), ethylene-vinyl acetate copolymer (EVA resin).
Described lubrication dispersing agent is a kind of in PETS (pentaerythritol stearate), PE wax, OP wax, stearic acid.
Described oxidation inhibitor is one or both the mixture in hindered phenol antioxygen 1010, phosphorous acid kind antioxidant 168.
Preferably, it comprises the raw material of following weight part:
Figure BDA0000129475170000031
The present invention also discloses a kind of preparation method of high-performance scratch resistance modification PC material, and it includes following steps:
A, by the forced air drying 4～6 hours under 100 ℃ of conditions of PC raw material, the forced air drying 2～4 hours under 80 ℃ of conditions of PMMA raw material;
B, take dried PC material, PMMA material, scratch resistance properties-correcting agent, compatilizer, coupling agent, toughner, lubrication dispersing agent, oxidation inhibitor by weight ratio and put into high-speed mixer high speed and mix 3～5 minutes;
C, by pre-mixed raw mixture in high-speed mixer join in twin screw extruder hopper, carry out melting, mixing, extrude, cooling, dry, pelletizing, packing.
The extruder temperature of described twin screw extruder is controlled between 230～240 ℃, 140～180 revs/min of screw speeds.
Beneficial effect of the present invention is: the present invention has good mechanical property and resistance toheat by the PC material of the method modification, higher surface hardness and adhesion strength, and owing to having added PMMA and the scratch resistance filler of part in material, than common PC raw material, more there is price advantage.For electronic product casing, removed the postprocessing working procedures that product applies from, can greatly enhance productivity.
Accompanying drawing explanation:
Fig. 1 is the preparation method's of high rigidity scratch resistance modification PC material of the present invention schematic flow sheet.
Embodiment:
For more detailed description summary of the invention of the present invention, below in conjunction with specific embodiment, further illustrate.
Embodiment 1
Refer to Fig. 1, first weigh the PC raw material of 550g, the forced air drying 5 hours under 100 ℃ of conditions of PC raw material, weighs the PMMA raw material of 150g, the forced air drying 4 hours under 80 ℃ of conditions of PMMA raw material; Weigh the wollastonite powder of 200g, the KH-560 of the GMA-g-SMA of 40g, 8g, the PETS of the MBS of 40g, 5g, 2g 1010,5g 168, then dried PC raw material, PMMA raw material are put into high-speed mixer high speed pre-mixing 5 minutes together with raw materials such as various above auxiliary agents, by pre-mixed raw mixture in high-speed mixer join in twin screw extruder hopper, carry out melting, mixing, extrude, cooling, dry, pelletizing, packing, the extruder temperature of twin screw extruder is controlled between 230～240 ℃, and screw speed is 160 revs/min.Wherein, GMA-g-SMA is that compatilizer, KH-560 are that coupling agent, MBS are toughner, and PETS is lubrication dispersing agent, and 1010,168 are all oxidation inhibitor.
Embodiment 2
Refer to Fig. 1, first weigh the PC raw material of 450g, the forced air drying 5 hours under 100 ℃ of conditions of PC raw material, weighs the PMMA raw material of 250g, the forced air drying 4 hours under 80 ℃ of conditions of PMMA raw material; Weigh the wollastonite powder of 200g, the KH-550 of the GMA-g-SMA of 50g, 6g, the PE wax of the MBS of 30g, 6g, 2g 1010,6g 168, then dried PC raw material, PMMA raw material are put into high-speed mixer high speed pre-mixing 5 minutes together with raw materials such as various above auxiliary agents, by pre-mixed raw mixture in high-speed mixer join in twin screw extruder hopper, carry out melting, mixing, extrude, cooling, dry, pelletizing, packing, the extruder temperature of twin screw extruder is controlled between 230～240 ℃, and screw speed is 180 revs/min.Wherein, GMA-g-SMA is that compatilizer, KH-550 are that coupling agent, MBS are toughner, and PE wax is lubrication dispersing agent, and 1010,168 are all oxidation inhibitor.
Embodiment 3
Refer to Fig. 1, first weigh the PC raw material of 500g, the forced air drying 5 hours under 100 ℃ of conditions of PC raw material, weighs the PMMA raw material of 150g, the forced air drying 4 hours under 80 ℃ of conditions of PMMA raw material; Weigh the wollastonite powder of 250g, the KH-560 of the GMA-g-SMA of 40g, 10g, the PETS of the MBS of 38g, 5g, 2g 1010,5g 168, then dried PC raw material, PMMA raw material are put into high-speed mixer high speed pre-mixing 5 minutes together with raw materials such as various above auxiliary agents, by pre-mixed raw mixture in high-speed mixer join in twin screw extruder hopper, carry out melting, mixing, extrude, cooling, dry, pelletizing, packing, the extruder temperature of twin screw extruder is controlled between 230～240 ℃, and screw speed is 170 revs/min.Wherein, GMA-g-SMA is that compatilizer, KH-560 are that coupling agent, MBS are toughner, and PETS is lubrication dispersing agent, and 1010,168 are all oxidation inhibitor.
Composition and the performance of table 1 high rigidity scratch resistance modification PC material:
Embodiment 1 Embodiment 2 Embodiment 3
PC raw material (%) 55 45 50
PMMA raw material (%) 15 25 15
Scratch resistance properties-correcting agent (%) 20 20 25
Compatilizer (%) 4 5 4
Coupling agent (%) 0.8 0.6 1
Toughner (%) 4 3 3.8
Lubrication dispersing agent (%) 0.5 0.6 0.5
1010(％) 0.2 0.2 0.2
168(％) 0.5 0.6 0.5
Tensile strength (MPa) 56.4 67.8 62.4
Flexural strength (MPa) 81.0 89.2 87.5
Shock strength (KJ/m 2) 55.1 45.5 49.3
Surface pencil hardness (1Kg) 2H 3H 2H
Wherein, performance test adopts following standard:
Tensile property test: the mensuration part 2 of GB/T1040.2-2006 plastic tensile: the test conditions of molding and extrusion molding plastics;
Bending property test: the mensuration of GB/T9341-2008 plastics bending property;
Impact property test: the mensuration of GB/T1843-2008 plastics cantilever beam impact strength;
Surface pencil hardness test: GB/T6739-1996 hardness of film pencil assay method.
In sum, by the test result of upper table, can be found out, PC that the present invention makes is material modified has good mechanical property and surface hardness, and damage resistant ability is stronger.Be applied to electronic product casing, can remove the postprocessing working procedures of coating from, shorten life cycle of the product, cost-saving.Owing to having removed spray treatment from, so eliminated the pollution to physical environment, there is good economic benefit and social benefit.
Certainly, the above is only preferred embodiment of the present invention, and the equivalence of doing according to structure, feature and principle described in patent claim of the present invention therefore all changes or modifies, and is included in patent claim of the present invention.

Claims (2)

1. a preparation method for high rigidity scratch resistance modification PC material, is characterized in that, first weighs the PC raw material of 450g, and the forced air drying 5 hours under 100 ℃ of conditions of PC raw material weighs the PMMA raw material of 250g, the forced air drying 4 hours under 80 ℃ of conditions of PMMA raw material, weigh the wollastonite powder of 200g, the GMA-g-SMA of 50g, the KH-550 of 6g, the MBS of 30g, the PE wax of 6g, 1010 of 2g, 168 of 6g, then by dried PC raw material, PMMA raw material is put into high-speed mixer high speed pre-mixing 5 minutes together with various above auxiliary agents, pre-mixed raw mixture in high-speed mixer is joined and in twin screw extruder hopper, carries out melting, mixing, extrude, cooling, dry, pelletizing, packing, the extruder temperature of twin screw extruder is controlled between 230～240 ℃, screw speed is 180 revs/min, wherein, GMA-g-SMA is compatilizer, KH-550 is coupling agent, MBS is toughner, PE wax is lubrication dispersing agent, 1010, 168 are all oxidation inhibitor.
2. a high rigidity scratch resistance modification PC material, is characterized in that using preparation method as claimed in claim 1 to make.
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Address after: 523878 Changan City, Guangdong Province town on the corner management area

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