CN107793721A - A kind of polycarbonate compositions and preparation method thereof - Google Patents

A kind of polycarbonate compositions and preparation method thereof Download PDF

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Publication number
CN107793721A
CN107793721A CN201611026960.0A CN201611026960A CN107793721A CN 107793721 A CN107793721 A CN 107793721A CN 201611026960 A CN201611026960 A CN 201611026960A CN 107793721 A CN107793721 A CN 107793721A
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polycarbonate compositions
chromium
parts
polycarbonate
ester
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Inventor
岑茵
田征宇
李明昆
佟伟
丁超
谢湘
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Kingfa Science and Technology Co Ltd
Shanghai Kingfa Science and Technology Co Ltd
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Priority to CN201611026960.0A priority Critical patent/CN107793721A/en
Priority to PCT/CN2017/107745 priority patent/WO2018095188A1/en
Publication of CN107793721A publication Critical patent/CN107793721A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/02—Organic and inorganic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of polycarbonate compositions and preparation method thereof, by weight, including following component：35 parts 85 parts of makrolon；0 part 40 parts of graft copolymer；5 parts 30 parts of fire retardant；5 parts 40 parts of mineral filler；Wherein, the gross weight based on polycarbonate compositions, the weight content of chromium is 10ppm 200ppm.The present invention in polycarbonate compositions by adding with relatively low soluble chromium content containing chromium compound and reduction or avoiding other additions containing chromium compound, the content of chromium in polycarbonate compositions is controlled in the range of 10 200ppm, it can make obtained polycarbonate compositions that there is higher shaping toughness, and with the thermo-oxidative stability being obviously improved.

Description

A kind of polycarbonate compositions and preparation method thereof
Technical field
The present invention relates to engineering plastics technical field, more particularly to a kind of polycarbonate compositions and preparation method thereof.
Background technology
Polycarbonate has compared with characteristics such as high-impact and heat resistances, to improve its processing characteristics and to notch shock The shortcomings that sensitive, it is polymer-modified to may be typically added rubber-like, such as ABS, MBS, particularly using PC and ABS as primary raw material PC/ABS alloys are a kind of important engineering plastics, can integrate both premium properties, accomplish physical property and processing characteristics It is improved, but due to ABS addition, double bond can bring the hidden of long-term thermal-oxidative aging property and weather resistance in system Suffer from, higher occasion particularly is required to use environment, its surface easily forms defect and its color easily changes.
Patent CN102292393 discloses can improve surface quality after the wet storage of heat using salt field trash, therefore It is suitable for preparing the moulded work with ageing-resistant zero defect class-A surfaces；
The present inventor pass through many experiments surprisingly it has been found that, in polycarbonate compositions, by addition there is relatively low solubility Chromium content containing chromium compound and reduction or avoid other additions containing chromium compound, by polycarbonate compositions chromium member The content of element is controlled in the range of 10-200ppm, and obtained polycarbonate compositions can be made to have higher shaping toughness, and With the thermo-oxidative stability being obviously improved.
The content of the invention
The shortcomings that in order to overcome prior art and deficiency, primary and foremost purpose of the invention be to provide it is a kind of have it is higher into Type toughness, and with the polycarbonate compositions for the thermo-oxidative stability being obviously improved.
Another object of the present invention is to provide the preparation method of above-mentioned polycarbonate compositions.
The present invention is achieved by the following technical solutions：
A kind of polycarbonate compositions, by weight, including following component：
35 parts -85 parts of makrolon；
0 part -40 parts of graft copolymer；
5 parts -30 parts of fire retardant；
5 parts -40 parts of mineral filler.
Wherein, the gross weight based on polycarbonate compositions, the weight content of chromium is 10ppm-200ppm.
The weight content of the chromium determines with the following method：200mg polycarbonate compositions samples are weighed, accurately To 0.1mg, into 50ml volumetric flasks, 5ml nitric acid is added, 0.1-1ml hydrogen peroxide, adds water constant volume to cover bottle to assigned scale Lid is put into micro-wave oven resolution.Bottle cap is opened, is cooled to room temperature, 4mlHCL liquid is added, covers bottle cap, be put into secondary in micro-wave oven disappear Solution, after be cooled to room temperature, filter, digestion solution is taken into ICP-s of the 1ml by the series of Agilent Tcechnologies 700 MS mixes mark method and tested, and finally measures the chromium content in polycarbonate compositions, and detection is limited to 2ppm.
The present invention has found by research, by adding containing with relatively low soluble chromium content in polycarbonate compositions Chromium compound, and reduce or avoid other additions containing chromium compound, and chromium in polycarbonate compositions is contained In the range of 10ppm-200ppm, chromium is the maximum metal of hardness, can be dissolved in strong base solution, a small amount of chromic salts class is deposited for amount control Contributing to the ph stability sexual balance of system in composition system, can have obtained polycarbonate compositions higher Shaping toughness, and with the thermo-oxidative stability that is obviously improved.When the content of chromium is higher than 200ppm, it is attached on mineral and fills out There can be destruction to processing screw rod on material, when the content of chromium is less than 10ppm, acid-base balance be acted on small.
Preferably, the gross weight based on polycarbonate compositions, the weight content of chromium is 30ppm-150ppm, more excellent Elect 60ppm-120ppm as.
Wherein, the chromium, which derives from, contains chromium compound, the pH value containing chromium compound in 60 DEG C of pure water The halide of the compound containing chromium, preferably chromium not less than 5.5 and no more than 8.5（Such as chromium chloride, charomic fluoride）, chromium sulphur Compound（Such as chromium sulfate, chromium sulfonate etc.）Or the one or more in the organic complex of chromium.
Wherein, the makrolon is selected from aromatic copolycarbonate, fatty poly-ester carbonate, the poly- carbon of aromatic-aliphatic One or more in acid esters, branching polycarbonate, siloxane copolycarbonate；Preferably aromatic copolycarbonate.
The makrolon is viscosity average molecular weigh 13000-40000 aromatic copolycarbonate, more preferably glues equal molecule Measure 16000-28000 aromatic copolycarbonate.When viscosity average molecular weigh within the above range, mechanical strength is good and can keep Excellent mouldability.Wherein, viscosity average molecular weigh is tested by viscosimetry：Using dichloromethane as solvent, test temperature is 25 DEG C.
The preparation method of above-mentioned makrolon can be made by interfacial polymerization and ester-interchange method, and can be in process The content of middle control terminal hydroxy group.
Wherein, the graft copolymer connects selected from prepared by mass polymerization, emulsion polymerization, bulk-suspension polymerization method The one or more of graft copolymer.
Mass polymerization：Including colloidal sol, prepolymerization, polymerization, five steps of devolatilization and granulation：By rubber solution in ethylbenzene and In styrene, add monomer according to formula ratio and be made into material liquid, the material liquid prepared is inputted in prepolymerization kettle and carries out prepolymerization, In polymerization process, grafting rubbers monomer, while monomer copolymerization, separated from solution, formation is dispersed in material liquid continuous Discontinuous phase in phase, after with enough monomer polymerizations, the copolymer of discontinuous phase becomes continuous phase, the rubber of grafting Form discontinuous phase to be dispersed in continuous copolymer phase, complete phase in version, finally by further polymerization, vacuum outgas, squeeze Go out, cooling and pelletizing obtain end article；
Bulk-suspension polymerization method：According to formula regulation rubber and monomer solution, and notify that adding polymerization regulator and free radical draws Agent is sent out, monomer mixture is stirred continuously in 80 DEG C of -120 DEG C of progress polymerisation in bulks, polymerization process, and by deionized water and hangs Floating agent is added in mixture, is disperseed mixture, then carries out suspension polymerisation using free radical catalyst, is obtained certain By cohesion after the degree of polymerization, filtering, washing, it is dehydrated and acquisition product is granulated after drying；
Emulsion polymerization：Rubber in initiator, deionized water, emulsifying agent and crosslinking agent, polymerization temperature by controlling at 50 DEG C -80 DEG C, monomer mixture is added to elastomer latex and is grafted, is finally washed, is granulated after being dehydrated and drying and obtains product.
The graft copolymer is selected from acrylonitritrile-styrene resin AS, acrylonitrile-butadiene-styrene (ABS) graft copolymerization Thing ABS, methyl methacrylate-nitrile-butadiene-styrene copolymer MABS, acrylonitrile-styrene-acrylic acid ternary are total to One or more in polymers ASA, MBS graft copolymer MBS；Wherein MBS particle diameter It is preferred that 0.1um-0.5um, the preferred 0.1um-2um of mass polymerization ABS particle diameters, the preferred 0.05um- of emulsion polymerization ABS particle diameters 0.2um。
More preferably acrylonitrile-butadiene-phenylethene grafted copolymer ABS, wherein butadiene rubber matter polymer Weight fraction in ABS is 5wt%-50wt%, and particle diameter distribution can be uniform either with two or with upward peak More distributions.
Wherein, the fire retardant is selected from halogenated flame retardant or halogen-free flame retardants, preferably halogen-free flame retardants；The halogen system is fire-retardant Agent be selected from brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, Brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, brominated polycarbonate, the cyclopentadecane of perbromo- three Or the one or more of brominated aromatic cross-linked polymer, preferably brominated Polystyrene；The halogen-free flame retardants is selected from nitrogenous One or more in fire retardant, phosphonium flame retardant or nitrogenous and phosphorus fire retardant, preferably phosphonium flame retardant.
Preferably, the phosphonium flame retardant is selected from Triphenyl phosphate, lindol, tricresyl phosphate base diphenyl Ester, tricresyl phosphate dimethylbenzene base ester, tricresyl phosphate (2,4,6- trimethylphenyls) ester, tricresyl phosphate (2,4- di-tert-butyl-phenyls) ester, phosphorus It is sour three (2,6- di-tert-butyl-phenyls) esters, resorcinol double (diphenyl phoshates), hydroquinones double (diphenyl phoshates), double Phenol A- double (diphenyl phoshates), resorcinol double (2,6- di-tert-butyl-phenyls phosphates), double (the 2,6- dimethyl of hydroquinones Phenyl phosphate ester) one or more.
The mineral filler, it is specifically as follows talcum powder, wollastonite, kaolin, clay, whisker, diatomite etc., mineral Filler can be coated without any surface treatment or coating processing, such as alkyl surface, at epoxy-surface The processing such as reason, amide surface processing, hydroxy silicon oil, alkyl silane, methoxy silane, sulfonic group.
According to different purposes needs, the other of 0-20 parts by weight can also be included in polycarbonate compositions of the invention Auxiliary agent, such as selected from stabilizer, anti-dripping agent, lubricant, releasing agent, plasticizer, the one or more of colouring agent.
Suitable stabilizer includes organic phosphite, such as triphenyl phosphite, and phosphorous acid three-（2,6- 3,5-dimethylphenyls） Ester, phosphorous acid three-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphate etc., pentaerythrite diphosphate ester（Such as double (2,6- Di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphate）, organic phosphite, the monohydric phenol or polyhydric phenols of alkylation, The butylation product of the alkylation reaction product of polyhydric phenols and diene, paracresol or bicyclopentadiene, the hydrogen of alkylation Quinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyalcohol esters, benzotriazole, hexichol One or more kinds of combinations of ketone class.
Suitable anti-dripping agent is preferably fluorinated polyolefin, such as polytetrafluoroethylene (PTFE).
Suitable plasticizer is phthalic acid ester.
The lubricant is one in talcum powder, ethylene bis stearamide EBS, erucyl amide, zinc stearate, silicone oil, C waxes Kind or two kinds and the above mixture.
Suitable releasing agent includes metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, stone Wax, lignite wax etc..
Suitable colouring agent includes various pigment, such as dyestuff, carbon black.
The preparation method of above-mentioned polycarbonate compositions, comprises the following steps：
1）The alcohol suspending liquid that mass fraction is 12.5ppm-2000ppm will be made into containing chromium compound and ethanol；
2）By 1）Alcohol suspending liquid is at the uniform velocity sprayed to enter in the high mixer containing quantitative makrolon and mineral filler with liquid pump Row blending, the polycarbonate blend pre-processed；
3）After the polycarbonate blend of pretreatment, graft copolymer, fire retardant, other auxiliary agents are proportionally weighed, pass through High mixer or mixer complete blending, and extrusion crosses water cooling, and granulation obtains the polycarbonate compositions of cylindrical particle.
The present invention compared with prior art, has the advantages that：
The present invention contains chromium compound and reduction in polycarbonate compositions, by adding with relatively low soluble chromium content Or other additions containing chromium compound are avoided, the content of chromium in polycarbonate compositions is controlled in 10-200ppm models In enclosing, it can make obtained polycarbonate compositions that there is higher shaping toughness, and with the thermo-oxidative stability being obviously improved.
Embodiment
The present invention is further illustrated below by embodiment, following examples are the preferable embodiment party of the present invention Formula, but embodiments of the present invention are not limited by following embodiments.
The makrolon used in the present invention：
PC viscoelastic elements amount is 24000（Mitsubishi）；；
The graft copolymer used in the present invention：
ABS emulsion polymerization particle diameter 0.05um-0.2um, wherein weight fraction of the butadiene rubber matter polymer in ABS are 25wt%, 757（Taiwan is very beautiful）；
MBS particle diameters 0.1um-0.5um, EM500（South Korea LG）；
The fire retardant used in the present invention：
BDP, bisphenol-A-bis- (diphenyl phoshate)（Ai Dike）；
Mineral filler：Talcum powder H30,（Lin Huacheng）；
Being derived from containing chromium compound for being used in the present invention is purchased in market；
Chromium chloride, the pH in 60 DEG C of pure water are 6.5；
Charomic fluoride, the pH in 60 DEG C of pure water are 6.8；
Chromium sulfate, the pH in 60 DEG C of pure water are 6.0；
Chromium sulfonate, the pH in 60 DEG C of pure water are 5.8；
The other auxiliary agents used in the present invention：
Stabilizer：PEP-36（Double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates）；
Lubricant：C waxes；
Anti-dripping agent：PTFE（Polytetrafluoroethylene (PTFE)）；
Colouring agent：Carbon black M717.
The testing standard or method of each performance：
The method of testing of chromium content：Weigh 200mg polycarbonate compositions（It is accurate to 0.1mg）Into 50ml volumetric flasks, 5ml nitric acid is added, 0.1-1ml hydrogen peroxide, adds water constant volume to cover bottle cap to assigned scale and be put into micro-wave oven resolution.Open bottle Lid, is cooled to room temperature, adds 4mlHCL liquid, covers bottle cap, be put into secondary resolution in micro-wave oven, after be cooled to room temperature, filter, will Digestion solution takes 1ml to mix mark method by the series of Agilent Tcechnologies 700 ICP-MS and tested, and finally surveys The chromium content gone out in composition, detection are limited to 2ppm.；
The assay method of thermo-oxidative stability：The particle of extrusion is shaped to 100mm*100mm*2mm's under 270 DEG C of injection temperatures Sheet material to be tested, is placed on after injection under the constant-temperature constant-humidity environment of 25 DEG C of temperature and 25% humidity after 48h, record YI values are YI0, Taken out after test board is put in into 85 DEG C of constant temperature oven baking 200h afterwards, be placed on the constant temperature and humidity of 25 DEG C of temperature and 25% humidity Under environment after 48h, record YI values are YI, and grade, calculated value are calculated by formula YI-YI0<3 be grade 1,3<Calculated value<5 are Grade 2；5<Calculated value<8 be grade 3；Calculated value>8 be class 4；
It is molded the testing standard of toughness：According to ASTM D256 standard I type battens, 2mm is finely polished to, being put in span is On 40mm tester, test speed 2mm/min, active force of the record displacement at 6mm, active force is bigger, is molded toughness Higher, if having occurred and that fracture at 6mm, record active force is 0.
Embodiment 1-16 and comparative example 1-2：The preparation of polycarbonate compositions
The alcohol suspending liquid that mass fraction is 12.5ppm-2000ppm will be made into containing chromium compound and ethanol；By alcohol suspending liquid At the uniform velocity sprayed with liquid pump and be blended in the high mixer containing quantitative makrolon and mineral filler, what is pre-processed is poly- Carbonic ester；The makrolon of pretreatment, graft copolymer, fire retardant, other auxiliary agents are proportionally weighed by the formula of table 1 Afterwards, blending is completed by high mixer or mixer, extrusion crosses water cooling, and granulation obtains the polycarbonate composition of cylindrical particle Thing；Performance test is carried out to polycarbonate compositions, data are shown in Table 1.
The embodiment 1-16 of table 1 and comparative example 1-2 specific proportioning（Parts by weight）And its test performance result
It can be seen that from the comparison of the embodiment and comparative example of table 1：By in polycarbonate compositions add have it is relatively low can Dissolubility chromium content contains chromium compound, and the content of chromium in polycarbonate compositions is controlled in the range of 10-200ppm, can So that obtained polycarbonate compositions have higher shaping toughness, and with the thermo-oxidative stability being obviously improved, comparative example In 1-2, in polycarbonate compositions the content of chromium less than 10ppm or during higher than 200ppm, polycarbonate compositions into Type toughness is relatively low, and thermo-oxidative stability is poor.

Claims (12)

  1. A kind of 1. polycarbonate compositions, it is characterised in that by weight, including following component：
    35 parts -85 parts of makrolon；
    0 part -40 parts of graft copolymer；
    5 parts -30 parts of fire retardant；
    5 parts -40 parts of mineral filler.
  2. 2. polycarbonate compositions according to claim 1, it is characterised in that the gross weight based on polycarbonate compositions Amount, the weight content of chromium is 10ppm-200ppm.
  3. 3. polycarbonate compositions according to claim 2, it is characterised in that the weight content of the chromium is using such as Lower method measure：200mg polycarbonate compositions samples are weighed, are accurate to 0.1mg, into 50ml volumetric flasks, add 5ml nitre Acid, 0.1-1ml hydrogen peroxide, water constant volume is added to cover bottle cap to assigned scale and be put into micro-wave oven resolution.Bottle cap is opened, is cooled to Room temperature, add 4mlHCL liquid, cover bottle cap, be put into secondary resolution in micro-wave oven, after be cooled to room temperature, filter, digestion solution is taken 1ml mixes mark method by the series of Agilent Tcechnologies 700 ICP-MS and tested, and finally measures poly- carbonic acid Chromium content in ester composition, detection are limited to 2ppm.
  4. 4. polycarbonate compositions according to claim 2, it is characterised in that the gross weight based on polycarbonate composite material Amount, the weight content of chromium is 30ppm-150ppm, preferably 60ppm-120ppm.
  5. 5. according to the polycarbonate compositions described in claim any one of 1-4, it is characterised in that the makrolon is selected from virtue Fragrant adoption carbonic ester, fatty poly-ester carbonate, aromatic-aliphatic makrolon, branching polycarbonate, copolymeric siloxane carbonic acid One or more in ester；Preferably aromatic copolycarbonate.
  6. 6. polycarbonate compositions according to claim 5, it is characterised in that the aromatic copolycarbonate is selected from viscous equal Molecular weight 13000-40000 aromatic copolycarbonate, viscosity average molecular weigh are tested by viscosimetry：Using dichloromethane as molten Agent, test temperature are 25 DEG C, preferably viscosity average molecular weigh 16000-28000 aromatic copolycarbonate.
  7. 7. according to the polycarbonate compositions described in claim any one of 1-4, it is characterised in that the graft copolymer is selected from Acrylonitritrile-styrene resin AS, acrylonitrile-butadiene-phenylethene grafted copolymer ABS, methyl methacrylate-propylene Nitrile-butadienestyrene copolymer MABS, acrylonitrile-styrene-acrylic ternary copolymer ASA, methyl methacrylate-fourth One or more in styrene graft copolymer MBS；Preferably acrylonitrile-butadiene-phenylethene grafted copolymer ABS。
  8. 8. according to the polycarbonate compositions described in claim any one of 1-4, it is characterised in that the fire retardant is selected from halogen system Fire retardant or halogen-free flame retardants, preferably halogen-free flame retardants；The halogenated flame retardant be selected from brominated Polystyrene, brominated polyphenylether, Brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, ten Dibromodiphenyl ether, decabromodiphenyl, brominated polycarbonate, the cyclopentadecane of perbromo- three or brominated aromatic cross-linked polymer one kind or It is several, preferably brominated Polystyrene；The halogen-free flame retardants is selected from nitrogenous flame ratardant, phosphonium flame retardant, nitrogenous and phosphorus resistance Fire the one or more in agent, preferably phosphonium flame retardant.
  9. 9. polycarbonate compositions according to claim 8, it is characterised in that the phosphonium flame retardant is selected from phosphoric acid triphen Base ester, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate dimethylbenzene base ester, tricresyl phosphate (2,4,6- trimethylbenzenes Base) ester, tricresyl phosphate (2,4- di-tert-butyl-phenyls) ester, tricresyl phosphate (2,6- di-tert-butyl-phenyls) ester, the double (di(2-ethylhexyl)phosphates of resorcinol Phenylester), hydroquinones double (diphenyl phoshate), bisphenol-A-bis- (diphenyl phoshate), double (the bis- tertiary fourths of 2,6- of resorcinol Base phenyl phosphate ester), the one or more of hydroquinones double (2,6- dimethylphenylphosphates).
  10. 10. according to the polycarbonate compositions described in claim any one of 1-4, it is characterised in that the chromium derives from Containing chromium compound, change containing chromium of the pH value containing chromium compound in 60 DEG C of pure water not less than 5.5 and no more than 8.5 One or more in the organic complex of the halide of compound, preferably chromium, the sulfonated bodies of chromium or chromium.
  11. 11. according to the polycarbonate compositions described in claim any one of 1-4, it is characterised in that the polycarbonate composition Thing also includes the other auxiliary agents of 0-20 parts by weight, and other auxiliary agents are selected from stabilizer, anti-dripping agent, lubricant, releasing agent, plasticising Agent, the one or more of colouring agent.
  12. 12. the preparation method of the polycarbonate compositions according to claim any one of 1-11, it is characterised in that including such as Lower step：
    1）The alcohol suspending liquid that mass fraction is 12.5ppm-2000ppm will be made into containing chromium compound and ethanol；
    2）By 1）Alcohol suspending liquid is at the uniform velocity sprayed to enter in the high mixer containing quantitative makrolon and mineral filler with liquid pump Row blending, the polycarbonate blend pre-processed；
    3）After the polycarbonate blend of pretreatment, graft copolymer, fire retardant, other auxiliary agents are proportionally weighed, pass through High mixer or mixer complete blending, and extrusion crosses water cooling, and granulation obtains the polycarbonate compositions of cylindrical particle.
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