CN107793725A - 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
CN107793725A
CN107793725A CN201611077223.3A CN201611077223A CN107793725A CN 107793725 A CN107793725 A CN 107793725A CN 201611077223 A CN201611077223 A CN 201611077223A CN 107793725 A CN107793725 A CN 107793725A
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Prior art keywords
polycarbonate compositions
parts
ester
polycarbonate
ficiency
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Inventor
岑茵
艾军伟
田征宇
李明昆
谢修好
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 CN201611077223.3A priority Critical patent/CN107793725A/en
Priority to PCT/CN2017/107748 priority patent/WO2018099217A1/en
Publication of CN107793725A publication Critical patent/CN107793725A/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
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • 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
    • C08K3/34—Silicon-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
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • 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
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • 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

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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)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses a kind of polycarbonate compositions and preparation method thereof, by weight, including following component：40 parts 75 parts of makrolon；0 part 35 parts of graft copolymer；5 parts 30 parts of fire retardant；8 parts 45 parts of mineral filler；Wherein, the gross weight based on polycarbonate compositions, the weight content of Zn-ef ficiency is 0.1ppm 20ppm.The present invention in polycarbonate compositions by adding zinc compound and reduction or the addition for avoiding other zinc compounds with relatively low soluble Zn content, the content of Zn-ef ficiency in polycarbonate compositions is controlled in the range of 0.1 20ppm, obtained polycarbonate compositions can be made to be less than 30% in 80 DEG C of aging 500h thermo-oxidative ageing MI growth rates, there is 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 have it is relatively low can The zinc compound of dissolubility Zn content and reduction or the addition for avoiding other zinc compounds, by polycarbonate compositions The content of Zn-ef ficiency is controlled in the range of 0.1-20ppm, can make obtained polycarbonate compositions in 80 DEG C of aging 500h heat Oxygen aging MI growth rates are less than 30%, have 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 be obviously improved The polycarbonate compositions of thermo-oxidative stability.
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：
40 parts -75 parts of makrolon；
0 part -35 parts of graft copolymer；
5 parts -30 parts of fire retardant；
8 parts -45 parts of mineral filler；
Wherein, the gross weight based on polycarbonate compositions, the weight content of Zn-ef ficiency is 0.1ppm-20ppm.
The weight content of the Zn-ef ficiency determines with the following method：It is (accurate to weigh 200mg polycarbonate compositions sample 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, opens bottle cap, is cooled to room temperature, adds 4mlHCL liquid, 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-MSs of the 1ml by Agilent Tcechnologies 700series Mixed mark method is tested, and finally measures the Zn-ef ficiency content in polycarbonate compositions, and detection is limited to 2ppm.
The present invention has found by research, by adding containing with relatively low soluble Zn content in polycarbonate compositions Zinc compound, and reduce or avoid the additions of other zinc compounds, and Zn-ef ficiency in polycarbonate compositions is contained Amount control can make obtained polycarbonate compositions in 80 DEG C of aging 500h thermo-oxidative ageings MI in the range of 0.1ppm-20ppm Growth rate is less than 30%, can obviously improve the thermo-oxidative stability of polycarbonate compositions.When the content of Zn-ef ficiency is higher than 20ppm When, the alkalescence increase of system, when the content of Zn-ef ficiency is less than 0.1ppm, it is not easy to be uniformly dispersed, cause thermo-oxidative stability to become Difference.
Preferably, the gross weight based on polycarbonate compositions, the weight content of Zn-ef ficiency is 1ppm-15ppm, more preferably For 3ppm-10ppm.
Wherein, the Zn-ef ficiency derives from zinc compound, and the zinc compound is selected from the oxidation of the oxide, zinc of zinc One or more in the complex compound of salt, the chelate of zinc or zinc, specific example are zinc nitrate, zinc sulfate, zinc chloride etc..Containing zinc The addition of compound is so that the content of Zn-ef ficiency is to be advisable in the range of 0.1ppm-20ppm in polycarbonate compositions.
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, preferably viscosity average molecular weigh 16000-28000 aromatic copolycarbonate.When viscosity average molecular weigh within the above range, mechanical strength is good and can keep excellent Different 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 to add polymerization regulator and freedom Base initiator, by monomer mixture in 80 DEG C of -120 DEG C of progress polymerisation in bulks, it is stirred continuously in polymerization process, and by deionized water It is added to suspending agent in mixture, is disperseed mixture, is then carried out suspension polymerisation using free radical catalyst, obtain By cohesion after certain 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 50 DEG C -80 DEG C, monomer mixture is added to elastomer latex and is grafted, is finally washed, be granulated and made after being dehydrated and drying 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, phosphorous acid three-(2,6- 3,5-dimethylphenyl) 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 ethylene bis stearamide EBS, erucyl amide, silicone oil, one or two kinds of in PETS and with On 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) zinc compound is made into the hydrosiloxane that mass fraction is 12.5ppm-2000ppm with hydrosiloxane to hang Turbid；
2) hydrosiloxane suspension is blended in high mixer with makrolon, the poly- carbonic acid pre-processed Ester；
3) makrolon of pretreatment, graft copolymer, fire retardant, mineral filler, other auxiliary agents are proportionally weighed Afterwards, blending is completed by high mixer or mixer, extrusion crosses water cooling, and granulation obtains the polycarbonate composition of cylindrical particle Thing.
The present invention compared with prior art, has the advantages that：
The present invention in polycarbonate compositions, by add with relatively low soluble Zn content zinc compound and The addition of other zinc compounds is reduced or avoided, the content of Zn-ef ficiency in polycarbonate compositions is controlled in 0.1- In the range of 20ppm, obtained polycarbonate compositions can be made to be less than 30% in 80 DEG C of aging 500h thermo-oxidative ageing MI growth rates, Significantly improve the thermo-oxidative stability of polycarbonate compositions.
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 (Mitsubishis)；
The graft copolymer used in the present invention：
ABS emulsion polymerizations, particle diameter 0.05um-0.2um, wherein weight of the butadiene rubber matter polymer in ABS points Number is 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) CR741 (big eight) of Japan；
Mineral filler：Talcum powder H30 (woods chemical conversion)；
The zinc compound used in the present invention such as zinc nitrate, zinc sulfate, zinc chloride derive from purchased in market；
The other auxiliary agents used in the present invention：
Stabilizer：PEP-36 (double (2,6- di-t-butyl -4- aminomethyl phenyls) pentaerythritol diphosphates)；
Lubricant：PETS, Long Sha；
Anti-dripping agent：PTFE (polytetrafluoroethylene (PTFE)) micro mist, great Jin
Colouring agent：Carbon black M717, Cabot.
The testing standard or method of each performance：
The method of testing of Zn-ef ficiency content：200mg polycarbonate compositions sample (being accurate to 0.1mg) is weighed to 50ml to hold In measuring bottle, add 5ml nitric acid, 0.1-1ml hydrogen peroxide, add water constant volume arrive assigned scale, cover bottle cap be put into micro-wave oven clear up, Open bottle cap, be 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, Filtering, take 1ml to mix mark method by Agilent Tcechnologies 700series ICP-MS digestion solution and tested, The Zn-ef ficiency content in composition is finally measured, detection is limited to 2ppm.
Thermo-oxidative stability：The particle of 200g extrusions will be taken to be placed under 270 DEG C of injection temperatures in 80 DEG C of constant temperature ovens After 500h, in 260 DEG C of loading 2.16kg of melting means instrument counterweights, MI tests are carried out according to ISO1133 standard, are tested 5 times altogether, The average value tried to achieve calculates MI growth rate compared with not being put into the value of constant temperature oven, and growth rate is bigger, and thermo-oxidative stability is got over Difference, conversely, growth rate is smaller, thermo-oxidative stability is better.
Tensile strength is carried out according to ASTM standard；
Impact strength is carried out according to ASTM standard.
Embodiment 1-16 and comparative example 1-2：The preparation of polycarbonate compositions
It is suspended that zinc compound and hydrosiloxane are made into the hydrosiloxane that mass fraction is 12.5ppm-2000ppm Liquid；Hydrosiloxane suspension is blended in high mixer with makrolon, the makrolon pre-processed；By table 1 Formula the makrolon of pretreatment, graft copolymer, fire retardant, mineral filler, other auxiliary agents are proportionally weighed after, lead to Cross high mixer or mixer completes blending, extrusion crosses water cooling, and granulation obtains the polycarbonate compositions of cylindrical particle；It is right Polycarbonate compositions carry out performance test, and 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
Continued 1：
It can be seen that from the comparison of the embodiment and comparative example of table 1：By in polycarbonate compositions add have compared with The zinc compound of low soluble Zn content, the content of Zn-ef ficiency in polycarbonate compositions is controlled in 0.1-20ppm scopes It is interior, obtained polycarbonate compositions can be made to be less than 30% in 80 DEG C of aging 500h thermo-oxidative ageing MI growth rates, hence it is evident that improve The thermo-oxidative stability of polycarbonate compositions, in comparative example 1-2, in polycarbonate compositions the content of Zn-ef ficiency is less than 0.1ppm or during higher than 20ppm, the thermo-oxidative stability of polycarbonate compositions is poor.

Claims (12)

  1. A kind of 1. polycarbonate compositions, it is characterised in that by weight, including following component：
    40 parts -75 parts of makrolon；
    0 part -35 parts of graft copolymer；
    5 parts -30 parts of fire retardant；
    8 parts -45 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 Zn-ef ficiency is 0.1ppm-20ppm.
  3. 3. polycarbonate compositions according to claim 2, it is characterised in that the weight content of the Zn-ef ficiency 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, open bottle cap, be 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 Zn-ef ficiency 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 compositions Amount, the weight content of Zn-ef ficiency is 1ppm-15ppm, preferably 3ppm-10ppm.
  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 Zn-ef ficiency derives from Zinc compound, oxide of the zinc compound selected from zinc, the saline oxide of zinc, the chelate of zinc or zinc complex compound in It is one or more of.
  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）It is suspended that zinc compound and hydrosiloxane are made into the hydrosiloxane that mass fraction is 12.5ppm-2000ppm Liquid；
    2）Hydrosiloxane suspension is blended in high mixer with makrolon, the makrolon pre-processed；
    3）After the makrolon of pretreatment, graft copolymer, fire retardant, mineral filler, other auxiliary agents are proportionally weighed, lead to Cross high mixer or mixer completes blending, extrusion crosses water cooling, and granulation obtains the polycarbonate compositions of cylindrical particle.
CN201611077223.3A 2016-11-30 2016-11-30 A kind of polycarbonate compositions and preparation method thereof Pending CN107793725A (en)

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CN105315641A (en) * 2015-05-27 2016-02-10 金发科技股份有限公司 Polycarbonate composition and preparation method thereof
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