CN102399424A - Polycarbonate/acrylonitrile-styrene-acrylate copolymer alloy material and preparation method thereof - Google Patents
Polycarbonate/acrylonitrile-styrene-acrylate copolymer alloy material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a polycarbonate/acrylonitrile-styrene-acrylate copolymer alloy material and a preparation method thereof, wherein the polycarbonate/acrylonitrile-styrene-acrylate copolymer alloy material is prepared by melting, blending and extruding 40-70 parts by weight of Polycarbonate (PC), 20-50 parts by weight of acrylonitrile-styrene-acrylate copolymer (ASA), 2-10 parts by weight of compatilizer, 3-15 parts by weight of toughener, 0.1-0.8 part by weight of antioxidant, 0.5-5 parts by weight of lubricant, 0.2-1 part by weight of ultraviolet absorbent and 0.2-1.5 parts by weight of polytetrafluoroethylene. The polycarbonate/acrylonitrile-styrene-acrylate copolymer alloy material prepared by the invention has good comprehensive mechanical property, processability and weather resistance, and is particularly suitable for manufacturing internal and external ornaments of automobiles.
Description
Technical field
The present invention relates to a kind of alloy material and preparation method thereof, particularly relate to a kind of polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy material and preparation method thereof.
Background technology
Polycarbonate (PC) is the superior engineering plastics of a kind of over-all properties, has advantages such as excellent toughness, dimensional stability, thermotolerance, the transparency, is widely used in fields such as automobile, electronics, building at present.But also there are some shortcomings in polycarbonate resin,, goods easy stress cracking poor like processing fluidity, to shortcomings such as breach sensitivities.
Preparation polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy is an effective way of effectively improving the polycarbonate shortcoming; The acrylonitrile-styrene-acrylic ester copolymer resin can reduce the viscosity of polycarbonate; Improve the stress cracking resistance of polycarbonate; Document has been introduced the preparation of a kind of polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy; As compatilizer, the polycarbonate/acrylonitrile of gained-copolymer in cinnamic acrylic ester alloy has favorable mechanical performance and processing characteristics with acrylonitrile-butadiene-styrene terpolymer (ABS)/polypropylene grafted maleic anhydride (PP-g-MAH) for it.Yet; Because the butadiene unit in the acrylonitrile-styrene-acrylic ester copolymer resin contains undersaturated pair of key; Make that polycarbonate/acrylonitrile-the copolymer in cinnamic acrylic ester alloy receives uviolizing easily and flavescence is unfavorable for life-time service under outdoor or photoenvironment.
The acrylonitrile-styrene-acrylic ester copolymer resin is propenoate rubber like body and vinyl cyanide, cinnamic graft copolymer; Realized industriallization in 1962 by German BASF AG the earliest; The acrylonitrile-styrene-acrylic ester copolymer resin not only has good mechanical performance, processing characteristics, chemical resistant properties; And (ABS) compares with acrylonitrile-butadiene-styrene terpolymer; Replace divinyl rubber owing to introduced not double bond containing acrylic elastomer, so weathering resistance there has been essential improvement, exceeded 10 times than acrylonitrile-butadiene-styrene terpolymer (ABS).Therefore; With polycarbonate resin and acrylonitrile-styrene-acrylic ester copolymer resin (ASA) blend; And add certain compatilizer and can prepare the polycarbonate/acrylonitrile of good comprehensive mechanical properties, processing characteristics-copolymer in cinnamic acrylic ester alloy material, be specially adapted to the manufacturing of inner and outer decorative parts of automobile.
Summary of the invention
The invention provides a kind of polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy material and preparation method thereof; Overcome the polycarbonate resin processing fluidity poor, easily stress cracking, to shortcomings such as breach sensitivities; On the other hand, improved the shortcoming of general modified polycarbonate alloy (PC/ABS alloy) weathering resistance difference.
The present invention relates to a kind of polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy material; It is characterized in that; In parts by weight, it consists of: 40～70 parts of polycarbonate (PC), 20～50 parts of acrylonitrile-styrene-acrylic ester copolymers (ASA), 2～10 parts of compatilizers, 3～15 parts of toughner, 0.1～0.8 part of oxidation inhibitor, 0.5～5 part of lubricant, 0.2～1 part of uv-absorbing agent and 0.2～1.5 part of tetrafluoroethylene combination melt blending make.
Described polycarbonate is the bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 18000～35000g/mol; Described acrylonitrile-styrene-acrylic ester copolymer (ASA) resin melting index (220 ℃ 10kg) are 8～20g/10min; Described compatilizer is styrene-maleic anhydride copolymer (SMA) or maleic anhydride graft styrene-acrylonitrile copolymer (SAN-g-MAH); Described toughner is ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA) or ethylene-butyl acrylate copolymer (E-BA); Described oxidation inhibitor is four [β-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Described lubricant is Zinic stearas, polyethylene wax, OPE or ethylene bis stearic amide; Described uv-absorbing agent is the benzotriazole category uv-absorbing agent.
The preparation method of described polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy material; It is characterized in that: may further comprise the steps; With bisphenol A-type aromatic copolycarbonate, acrylonitrile-styrene-acrylic ester copolymer resin, styrene-maleic anhydride copolymer, ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA) or ethylene-butyl acrylate copolymer (E-BA), four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), polyethylene wax,, benzotriazole category uv-absorbing agent (UV 5411), tetrafluoroethylene be after under the 75-85 ℃ of temperature dry 3-5 hour; Taking by weighing above-mentioned raw materials by weight ratio places high-speed mixer to mix 2～10 minutes; Then the gained mixture is added parallel double-screw extruder, under 210 ℃～280 ℃, screw speed 200～500rpm, melt extrude and promptly get target compound.
The preparation method of described polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy material; It is characterized in that: may further comprise the steps; With bisphenol A-type aromatic copolycarbonate, acrylonitrile-styrene-acrylic ester copolymer resin, styrene-maleic anhydride copolymer, ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA) or ethylene-butyl acrylate copolymer (E-BA), four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), polyethylene wax, benzotriazole category uv-absorbing agent (UV 5411), tetrafluoroethylene are after under 80 ℃ of temperature dry 4 hours; Taking by weighing above-mentioned raw materials by weight ratio places high-speed mixer to mix 10 minutes; Then the gained mixture is added parallel double-screw extruder, under 210 ℃～280 ℃, screw speed 300rpm, melt extrude and promptly get target compound.
Characteristics of the present invention are acrylonitrile-styrene-acrylic ester copolymer resin and polycarbonate resin blend; Improved the processing fluidity of polycarbonate; Improved the stress cracking resistance of polycarbonate; And the excellent weather resistance of acrylonitrile-styrene-acrylic ester copolymer resin has guaranteed the environmental applications of polycarbonate alloy material in the high-weatherability requirement.
Embodiment
Following embodiment can help further to understand the present invention, but does not limit the present invention.
Embodiment 1
With 7000 gram polycarbonate resins, 2000 gram acrylonitrile-styrene-acrylic ester copolymer resins, 500 gram styrene-maleic anhydride copolymers (SMA), 500 gram ethylene-butyl acrylate copolymers (E-BA), 15g four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), 15g three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), 100g OPE, 50g benzotriazole category uv-absorbing agent (UV 5411); The 50g tetrafluoroethylene; After high-speed mixer mixes 10 minutes, in length-to-diameter ratio 40, extruding pelletization in the twin screw extruder of diameter 35mm; 220 ℃～280 ℃ of extrusion temperatures, screw speed 300rpm.
Embodiment 2
With 4000 gram polycarbonate resins, 5000 gram acrylonitrile-styrene-acrylic ester copolymer resins, 500 gram styrene-maleic anhydride copolymers (SMA), 500 gram ethylene-butyl acrylate copolymers (E-BA), 15 grams, four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), 15 the gram three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), 100 gram OPEs, 50 gram benzotriazole category uv-absorbing agents (UV 5411), 50 gram tetrafluoroethylene; After high-speed mixer mixes 10 minutes; In length-to-diameter ratio 40; Extruding pelletization in the twin screw extruder of diameter 35mm, 210 ℃～270 ℃ of extrusion temperatures, screw speed 300rpm.
Embodiment 3
With 4000 gram polycarbonate resins, 5000 gram acrylonitrile-styrene-acrylic ester copolymer resins, 500 gram SAN-g-MAH, 500 gram ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA), 15 grams, four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), 15 the gram three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), 100 gram OPEs, 50 gram benzotriazole category uv-absorbing agents (UV 5411), 50 gram tetrafluoroethylene; After high-speed mixer mixes 10 minutes; In length-to-diameter ratio 40; Extruding pelletization in the twin screw extruder that diameter is 35 millimeters, 210 ℃～270 ℃ of extrusion temperatures, screw speed 300rpm.
Embodiment 4
With 4000 gram polycarbonate resins, 4400 gram acrylonitrile-styrene-acrylic ester copolymer resins, 800 gram maleic anhydride graft styrene-acrylonitrile copolymers (SAN-g-MAH), 800 gram ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA), 15 grams, four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010), 15 the gram three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), 100 gram OPEs, 50 gram benzotriazole category uv-absorbing agents (UV 5411), 50 gram tetrafluoroethylene; After high-speed mixer mixes 10 minutes; In length-to-diameter ratio 40; Extruding pelletization in the twin screw extruder of diameter 35mm, 210 ℃～265 ℃ of extrusion temperatures, screw speed 300rpm.
85 ℃ of dryings of PC/ASA particle of embodiment 1-4 gained are injected into the standard testing batten after 6 hours, carry out tensile property, bending property, impact property test.Tensile property is tested by GB/T 1040-2006 requirement, draw speed 50 mm/min; Bending property is by GB/T 9341-2000 requirement test, test speed 2 mm/min; Socle girder notch shock performance is by GB/T 1843-2008 requirement test, test result such as table 1.
Table 1 embodiment performance
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | |
| Tensile strength (MPa) | ?58.3 | ?51.2 | ?53.8 | ?52.6 |
| Flexural strength (MPa) | ?90.4 | ?83.7 | ?85.5 | ?83.6 |
| Modulus in flexure (MPa) | ?2450 | ?2216 | ?2350 | ?2298 |
| Notched Izod impact strength (kJ/m 2) | ?498 | 527 | ?563 | ?585 |
Can find out that from table 1 acrylonitrile-styrene-acrylic ester copolymer content increases, tensile strength and bending property decrease, and impelling strength improves; The effect of compatilizer maleic anhydride graft styrene-acrylonitrile copolymer (SAN-g-MAH) is better; Toughner content improves, and the impelling strength of polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy improves.
Claims (4)
1. polycarbonate/acrylonitrile-copolymer in cinnamic acrylic ester alloy material; It is characterized in that; In parts by weight, it consists of: 40～70 parts of polycarbonate (PC), 20～50 parts of acrylonitrile-styrene-acrylic ester copolymers (ASA), 2～10 parts of compatilizers, 3～15 parts of toughner, 0.1～0.8 part of oxidation inhibitor, 0.5～5 part of lubricant, 0.2～1 part of uv-absorbing agent and 0.2～1.5 part of tetrafluoroethylene.
2. polycarbonate/acrylonitrile according to claim 1-copolymer in cinnamic acrylic ester alloy material is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 18000～35000g/mol; Described acrylonitrile-styrene-acrylic ester copolymer (ASA) resin melting index (220 ℃ 10kg) are 8～20g/10min; Described compatilizer is styrene-maleic anhydride copolymer (SMA) or maleic anhydride graft styrene-acrylonitrile copolymer (SAN-g-MAH); Described toughner is ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA) or ethylene-butyl acrylate copolymer (E-BA); Described oxidation inhibitor is four [β-(3 ', 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester, N, N '-two [3-(3, the 5-di-tert-butyl-hydroxy phenyl) propionyl] hydrazine and three (2, the 4-di-tert-butyl-phenyl) phosphorous acid ester; Described lubricant is Zinic stearas, polyethylene wax, OPE or ethylene bis stearic amide; Described uv-absorbing agent is the benzotriazole category uv-absorbing agent.
3. the preparation method of polycarbonate/acrylonitrile according to claim 1 and 2-copolymer in cinnamic acrylic ester alloy material; It is characterized in that: may further comprise the steps; With bisphenol A-type aromatic copolycarbonate, acrylonitrile-styrene-acrylic ester copolymer resin, styrene-maleic anhydride copolymer, ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA) or ethylene-butyl acrylate copolymer (E-BA), four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), polyethylene wax,, benzotriazole category uv-absorbing agent (UV 5411), tetrafluoroethylene be after under the 75-85 ℃ of temperature dry 3-5 hour; Taking by weighing above-mentioned raw materials by weight ratio places high-speed mixer to mix 2～20 minutes; Then the gained mixture is added parallel double-screw extruder, under 210 ℃～280 ℃, screw speed 200～500rpm, melt extrude and promptly get target compound.
4. the preparation method of polycarbonate/acrylonitrile according to claim 3-copolymer in cinnamic acrylic ester alloy material; It is characterized in that: may further comprise the steps; With bisphenol A-type aromatic copolycarbonate, acrylonitrile-styrene-acrylic ester copolymer resin, styrene-maleic anhydride copolymer, ethylene-acrylate-propenoate glycidyl ester copolymer (E-MA-GMA) or ethylene-butyl acrylate copolymer (E-BA), four [β-(3 '; 5 '-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester (antioxidant 1010) and three (2; The 4-di-tert-butyl-phenyl) phosphorous acid ester (oxidation inhibitor 168), polyethylene wax, benzotriazole category uv-absorbing agent (UV 5411), tetrafluoroethylene are after under 80 ℃ of temperature dry 4 hours; Taking by weighing above-mentioned raw materials by weight ratio places high-speed mixer to mix 10 minutes; Then the gained mixture is added parallel double-screw extruder, under 210 ℃～280 ℃, screw speed 300rpm, melt extrude and promptly get target compound.
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Application publication date: 20120404 |