CN105860479A - Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition - Google Patents

Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition Download PDF

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Publication number
CN105860479A
CN105860479A CN201610272319.9A CN201610272319A CN105860479A CN 105860479 A CN105860479 A CN 105860479A CN 201610272319 A CN201610272319 A CN 201610272319A CN 105860479 A CN105860479 A CN 105860479A
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China
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district
abs
temperature
accounts
butadiene
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CN201610272319.9A
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Chinese (zh)
Inventor
陈勇文
艾军伟
佟伟
何继辉
李明昆
岑茵
张现军
陶四平
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Tianjin Kingfa Advanced Materials Co Ltd
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Tianjin Kingfa Advanced Materials Co Ltd
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Priority to CN201610272319.9A priority Critical patent/CN105860479A/en
Publication of CN105860479A publication Critical patent/CN105860479A/en
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04Particle-shaped
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/92Measuring, controlling or regulating
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C2948/00Indexing scheme relating to extrusion moulding
    • B29C2948/92Measuring, controlling or regulating
    • B29C2948/92504Controlled parameter
    • B29C2948/92704Temperature
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2055/00Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 - B29K2049/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend

Abstract

The invention relates to a low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene graft copolymer) composition which comprises PC, a phosphorus-containing flame retardant, ABS and a toughening modifier. The preparation method comprises the following steps: preparing a one-step material from the ABS and toughening modifier by physical extrusion, and mixing the one-step material with the rest materials to prepare the PC/ABS composition. The preparation method has the advantages of simple and accessible one-step material, simple preparation technique and low cost, can effectively remove small-molecule substances in the material molecules, and can obviously enhance the mechanical properties of the material. The material can be used in automobiles, refrigerators, televisions and other industries.

Description

A kind of low precipitation high-performance refractory PC/ABS compositions
Technical field
The invention belongs to macromolecule modified technical field, particularly relate to a kind of low precipitation high-performance refractory PC/ABS compositions.
Background technology
Merlon (PC) is a kind of thermoplastic engineering plastic with desirable physical mechanical performance, and it is transparent and fire-retardant Property is excellent, has wide application;But owing to Merlon (PC) strand rigidity is big, melt viscosity is high, easily Producing stress cracking, solvent resistance is poor, meets the shortcomings such as water easily decomposition under high temperature, limits it to a certain extent and uses model Enclose.General by modification technology, improve it by the addition of acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) and add Work and internal stress, add impact improving agent and improve the toughness of Merlon (PC) compositions.But due to acrylonitrile- Butadiene-styrene graft copolymer (ABS) and toughness reinforcing improving agent, when synthesis, can introduce dispersant or other auxiliary agents, After making fire retardation PC/ABS compositions, due to the feature of Merlon (PC) molecular structure, these small-molecule substances can draw Playing the degraded of Merlon (PC), small-molecule substance the most easily separates out simultaneously, thus the defect such as spray and residual mold deposit, Have a strong impact on the outward appearance of product and the continuous production of product.
Summary of the invention
Present invention aim at providing a kind of low precipitation high-performance refractory PC/ABS compositions, said composition passes through a step material Preparation, injection moulding process can be significantly reduced and produce spray and the chance of mold deposit.
The present invention finds under study for action, by the production of a step material, by it with fire retardant, Merlon (PC) suitably The collocation of ratio, can effectively solve acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) and anti-impact modifier The problems such as spray that small molecular material causes and film dirt, significantly improve the outward appearance of product, improve material property simultaneously.Its The concrete technical scheme used is as follows:
A kind of low precipitation high-performance refractory PC/ABS compositions, including Merlon (PC), phosphonium flame retardant, propylene Nitrile-butadiene-styrene graft copolymer (ABS), plasticized modifier, first by acrylonitrile-butadiene-styrene (ABS) grafting altogether Polymers (ABS) makes a step material with plasticized modifier by the method that physics is extruded, then is mixed with leftover materials by a step material Close and prepare.
Further, the number-average molecular weight of described Merlon (PC), between 20000-40000, preferably exists Between 25000-37000.
Further, described acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) selects emulsion method or substance law to prepare Acrylonitrile-butadiene-phenylethene grafted copolymer (ABS).
Further, described plasticized modifier uses MBS graft copolymer (MBS), Core is organosilicon/acrylic acid, and shell is the silicon system anti-impact modifier of the nucleocapsid structure of methyl methacrylate.
Further, described phosphonium flame retardant is bisphenol-A bis phosphoric acid diphenyl ester (BDP), the double diphenylphosphoric acid of resorcinol The mixture of one or more in ester (RDP) or triphenyl phosphate (TPP).
Further, in described compositions, Merlon (PC) accounts for 50-90%, phosphonium flame retardant by weight percentage Account for 5-25%, a step material accounts for 5-35%.
Further, in described compositions, Merlon (PC) accounts for 60-80%, phosphonium flame retardant by weight percentage Account for 9-15%, a step material accounts for 7-25%.
Further, in a described step material, acrylonitrile-butadiene-phenylethene grafted copolymer (ABS) by weight percentage Account for 50%-80%, anti-impact modifier accounts for 20%-50%.
Further, the production method of a described step material is:
(1) by weight percentage acrylonitrile-butadiene-phenylethene grafted copolymer (ABS), plasticized modifier are put into height Uniformly mix 1-3min, mix homogeneously in mixed machine, obtain premix material;
(2) premix material is put into from the main spout of double screw extruder, described in the condition that melt extrudes be: district's temperature 180-210 DEG C, two district's temperature 190-220 DEG C, three district's temperature 190-230 DEG C, four district's temperature 190-240 DEG C, five district's temperature 190-240 DEG C, six district's temperature 190-240 DEG C, seven district's temperature 190-240 DEG C, eight district's temperature 190-240 DEG C, nine district's temperature 190-240 DEG C, ten district's temperature 190-240 DEG C, 11 district's temperature 190-240 DEG C, engine speed 250-600 rev/min, Preparing a step material plastic grain, the screw slenderness ratio of described double screw extruder is 48:1;
In (3) one step material production processes, it is 5%-30% liquid in the 3rd district of barrel and the 5th district implantation quality mark respectively Water, SECTOR-SEVEN and the tenth district at barrel arrange double vacuum equipment simultaneously.
The present invention is by the extrusion of a step material, owing to aqueous water at high temperature volatilizees, dissolve take out of acrylonitrile-butadiene- Small-molecule substance in phenylethene grafted copolymer (ABS) and plasticized modifier, coordinates the effect of double vacuum simultaneously, has Effect volatile matter is taken out of barrel, produce and obtain a step material, produced to dry and re-use;The method can be effectively by third Alkene nitrile-butadiene-styrene graft copolymer (ABS) separates with the small-molecule substance of plasticized modifier, particularly acrylonitrile The alkalescence dispersant added in-butadiene-styrene graft copolymer (ABS) and plasticized modifier building-up process, so The degraded of Merlon in modifying process (PC) can be prevented effectively from, little point during subsequent forming can be prevented effectively from simultaneously The problems such as sub-material precipitation;Due to detaching of step material small-molecule substance in process of production, improve to a certain extent The fire resistance of material.
The invention has the beneficial effects as follows: the step material that the present invention uses is simple and easy to get, preparation technology is simple, low cost, energy While effectively removing material molecule small molecular material, the mechanical performance of material can be significantly improved again;Material can be used for Automobile, refrigerator, the industry such as television set.
Detailed description of the invention
For the technological means making the present invention realize, creation characteristic, reach purpose and be easy to understand with effect, below to this The detailed description of the invention of invention is described further, but does not limit protection scope of the present invention, it should be noted that not In the case of conflict, the embodiment in the invention and the feature in embodiment can be mutually combined.
Embodiment 1:
One of the present invention low precipitation high-performance refractory PC/ABS compositions, first prepares a step material, first will be by weight The amount ABS of 60% of percentages, the anti-impact modifier MBS of 40% uniformly mix 1-3min in high mixer, To premix material;According to the method for the invention, premix material is put into double screw extruder, prepare a step material plastic grain.Press PC described in percentage by weight meter accounts for 69.3%, and a step material accounts for 18%, and BDP accounts for 12%, and other auxiliary agents account for 0.7%, Other auxiliary agents described include antioxidant and anti-dripping agent, and by the method for the invention, above-mentioned material is prepared low precipitation high-performance Fire retardation PC/ABS compositions.
Embodiment 2:
One of the present invention low precipitation high-performance refractory PC/ABS compositions, first prepares a step material, first will be by weight The amount ABS of 60% of percentages, the anti-impact modifier MBS of 40% uniformly mix 1-3min in high mixer, To premix material;According to the method for the invention, premix material is put into double screw extruder, prepare a step material plastic grain.Press PC described in percentage by weight meter accounts for 79.3%, and a step material accounts for 12%, and BDP accounts for 8%, and other auxiliary agents account for 0.7%, institute State other auxiliary agents and include antioxidant and anti-dripping agent, above-mentioned material is prepared the resistance of low precipitation high-performance by the method for the invention Combustion PC/ABS compositions.
Embodiment 3:
One of the present invention low precipitation high-performance refractory PC/ABS compositions, first prepares a step material, first will be by weight The amount ABS of 60% of percentages, the anti-impact modifier MBS of 40% uniformly mix 1-3min in high mixer, To premix material;According to the method for the invention, premix material is put into double screw extruder, prepare a step material plastic grain.Press PC described in percentage by weight meter accounts for 59.3%, and a step material accounts for 25%, and BDP accounts for 15%, and other auxiliary agents account for 0.7%, Other auxiliary agents described include antioxidant and anti-dripping agent, and by the method for the invention, above-mentioned material is prepared low precipitation high-performance Fire retardation PC/ABS compositions.
Comparative example 1:
A kind of PC/ABS compositions with compositions of the present invention contrast, PC by weight percentage accounts for 69.3%, ABS accounts for 10.8%, and MBS accounts for 7.2%, and BDP accounts for 12%, and other auxiliary agents account for 0.7%, and other auxiliary agents described include resisting Oxygen agent and anti-dripping agent, be blended above material, prepares a kind of PC/ABS compositions.
Comparative example 2:
A kind of PC/ABS compositions with compositions of the present invention contrast, PC by weight percentage accounts for 79.3%, ABS accounts for 7.2%, and MBS accounts for 4.8%, and BDP accounts for 8%, and other auxiliary agents account for 0.7%, and other auxiliary agents described include antioxygen Agent and anti-dripping agent, be blended above material, prepares a kind of PC/ABS compositions.
Comparative example 3:
A kind of PC/ABS compositions with compositions of the present invention contrast, PC by weight percentage accounts for 59.3%, ABS accounts for 15%, and MBS accounts for 10%, and BDP accounts for 15%, and other auxiliary agents account for 0.7%, and other auxiliary agents described include antioxygen Agent and anti-dripping agent, be blended above material, prepares a kind of PC/ABS compositions.
To above example 1, embodiment 2, embodiment 3, comparative example 1, comparative example 2, comparative example 3, described PC/ABS Compositions carries out performance test:
Mold deposit evaluation methodology: the square plate of injection 40*60*2mm, injection 100 moulds, can scrape off from fixing air vent continuously Mold deposit weight.
Hot strength: testing standard ASTM D638, tests on Zwick electronic universal tester;
Izod notched impact: testing standard ASTM D256, tests on Zwick electronic universal tester;
Flame retardant rating: testing standard UL94.
Table 1PC/ABS composition properties test result
It can be seen that use the formula of a step material from table 1 result, the chance producing mold deposit can be significantly reduced, simultaneously Mechanical property and fire resistance are more preferable.The addition of other auxiliary agents can more effectively improve the every of compositions Performance, but be added without other auxiliary agents and have no effect on the technique effect of compositions of the present invention.
PC/ABS compositions of the present invention is described by specific embodiment.Those skilled in the art can Suitably changing the link such as composition components, proportioning with reference present disclosure and realize other purpose corresponding, it is correlated with Change all without departing from present disclosure, within all spirit in the invention and principle, any amendment of being made, Equivalent, improvement etc., within should be included in the protection domain of the invention.

Claims (9)

1. a low precipitation high-performance refractory PC/ABS compositions, including Merlon, phosphonium flame retardant, acrylic nitrile-butadiene two Alkene-phenylethene grafted copolymer, plasticized modifier, it is characterised in that first by acrylonitrile-butadiene-styrene (ABS) graft copolymerization Thing makes a step material with plasticized modifier by the method that physics is extruded, then is mixed to prepare with leftover materials by a step material.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described The number-average molecular weight of Merlon is between 20000-40000, preferably between 25000-37000.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described The acrylonitrile-butadiene-styrene (ABS) that acrylonitrile-butadiene-phenylethene grafted copolymer selects emulsion method or substance law to prepare connects Graft copolymer.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described Plasticized modifier uses MBS graft copolymer, and core is organosilicon/acrylic acid, and shell is The silicon system anti-impact modifier of the nucleocapsid structure of methyl methacrylate.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described Phosphonium flame retardant be the one in bisphenol-A bis phosphoric acid diphenyl ester, the double diphenyl phosphoester of resorcinol or triphenyl phosphate or Several mixture.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described In compositions, Merlon accounts for 50-90% by weight percentage, phosphonium flame retardant accounts for 5-25%, a step material accounts for 5-35%.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described In compositions, Merlon accounts for 60-80% by weight percentage, phosphonium flame retardant accounts for 9-15%, a step material accounts for 7-25%.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described In one step material, acrylonitrile-butadiene-phenylethene grafted copolymer by weight percentage accounts for 50%-80%, impact modification Agent accounts for 20%-50%.
One the most according to claim 1 low precipitation high-performance refractory PC/ABS compositions, it is characterised in that described The production method of one step material is:
(1) by weight percentage acrylonitrile-butadiene-phenylethene grafted copolymer, plasticized modifier are put in high mixer uniform Mixing 1-3min, mix homogeneously, obtain premix material;
(2) premix material is put into from the main spout of double screw extruder, described in the condition that melt extrudes be: district's temperature 180-210 DEG C, two district's temperature 190-220 DEG C, three district's temperature 190-230 DEG C, four district's temperature 190-240 DEG C, five district's temperature 190-240 DEG C, six district's temperature 190-240 DEG C, seven district's temperature 190-240 DEG C, eight district's temperature 190-240 DEG C, nine district's temperature 190-240 DEG C, ten district's temperature 190-240 DEG C, 11 district's temperature 190-240 DEG C, engine speed 250-600 rev/min, Preparing a step material plastic grain, the screw slenderness ratio of described double screw extruder is 48:1;
In (3) one step material production processes, it is 5%-30% aqueous water in the 3rd district of barrel and the 5th district implantation quality mark respectively, SECTOR-SEVEN and the tenth district at barrel arrange double vacuum equipment simultaneously.
CN201610272319.9A 2016-04-27 2016-04-27 Low-precipitation high-performance flame-retardant PC/ABS (polycarbonate/acrylonitrile-butadiene-styrene) composition Pending CN105860479A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101173090A (en) * 2006-10-31 2008-05-07 佛山市顺德区汉达精密电子科技有限公司 PC/ABS alloy
CN102325827A (en) * 2009-02-19 2012-01-18 拜尔材料科学股份公司 Compounding process to produce polymer compositions having reduced levels of volatile organic compounds

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN101173090A (en) * 2006-10-31 2008-05-07 佛山市顺德区汉达精密电子科技有限公司 PC/ABS alloy
CN102325827A (en) * 2009-02-19 2012-01-18 拜尔材料科学股份公司 Compounding process to produce polymer compositions having reduced levels of volatile organic compounds

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Application publication date: 20160817