CN107793724A - 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
CN107793724A
CN107793724A CN201611070240.4A CN201611070240A CN107793724A CN 107793724 A CN107793724 A CN 107793724A CN 201611070240 A CN201611070240 A CN 201611070240A CN 107793724 A CN107793724 A CN 107793724A
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polycarbonate compositions
titanium
parts
ester
polycarbonate
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岑茵
田征宇
谢修好
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 CN201611070240.4A priority Critical patent/CN107793724A/en
Priority to PCT/CN2017/107756 priority patent/WO2018099218A1/en
Publication of CN107793724A publication Critical patent/CN107793724A/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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • 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
    • 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
    • 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：35 parts 75 parts of makrolon；0 part 30 parts of graft copolymer；5 parts 25 parts of fire retardant；10 parts 50 parts of mineral filler；Wherein, the gross weight based on polycarbonate compositions, the weight content of titanium elements is 1ppm 40ppm.The present invention in polycarbonate compositions by adding titanium-containing compound and reduction or the addition for avoiding other titanium-containing compounds with relatively low soluble titanium content, the content of titanium elements in polycarbonate compositions is controlled in the range of 1 40ppm, after obtained polycarbonate compositions can be made to toast 500h under 90 DEG C and 90% humidity, wet and heat ageing resistant property retention rate is more than 70%, with the wet and heat ageing resistant performance being obviously improved, there is more high surface quality simultaneously, keep excellent mechanical performance.

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 titanium-containing compound of dissolubility Ti content and reduction or the addition for avoiding other titanium-containing compounds, by polycarbonate compositions The content of titanium elements is controlled in the range of 1-40ppm, can make obtained polycarbonate compositions under 90 DEG C and 90% humidity After toasting 500h, wet and heat ageing resistant property retention rate is more than 70%, has the wet and heat ageing resistant performance being obviously improved, has simultaneously More high surface quality, keep excellent mechanical performance.
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 wet and heat ageing resistant performance.
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 -75 parts of makrolon；
0 part -30 parts of graft copolymer；
5 parts -25 parts of fire retardant；
10 parts -50 parts of mineral filler；
Wherein, the gross weight based on polycarbonate compositions, the weight content of titanium elements is 1ppm-40ppm.
The weight content of the titanium elements 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 titanium elements content in polycarbonate compositions, and detection is limited to 2ppm.
The present invention has found by research, by adding containing with relatively low soluble titanium content in polycarbonate compositions Titanium compound, and reduce or avoid the additions of other titanium-containing compounds, and titanium elements in polycarbonate compositions are contained Amount control can make obtained polycarbonate compositions toast 500h under 90 DEG C and 90% humidity in the range of 1ppm-40ppm Afterwards, wet and heat ageing resistant property retention rate is more than 70%, can obviously improve wet and heat ageing resistant performance, while have more high surface Quality, keep excellent mechanical performance.When the content of titanium elements is higher than 40ppm, the compound of titanium can cause matrix resin Degraded, when the content of titanium elements is less than 1ppm, stabilization can not play, while dispersity cannot guarantee that, therefore make Use unobvious.
Preferably, the gross weight based on polycarbonate compositions, the weight content of titanium elements is 5ppm-30ppm, more preferably For 8ppm-20ppm.
Wherein, the titanium elements derive from titanium-containing compound, and the titanium-containing compound is selected from the oxidation of titanyl compound, titanium Salt, the chelate of titanium, titanium complex compound in one or more, such as isopropyl titanate, titanium dioxide, tetrabutyl titanate.Contain The addition of titanium compound is so that the content of titanium elements is to be advisable in the range of 1ppm-40ppm 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) titanium-containing 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 titanium content titanium-containing compound and The addition of other titanium-containing compounds is reduced or avoided, the content of titanium elements in polycarbonate compositions is controlled in 1-40ppm In the range of, after obtained polycarbonate compositions can be made to toast 500h under 90 DEG C and 90% humidity, wet and heat ageing resistant performance Conservation rate is more than 70%, hence it is evident that improves the wet and heat ageing resistant performance of polycarbonate compositions, while has more high surface Quality, keep excellent mechanical performance.
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 titanium-containing compound used in the present invention such as isopropyl titanate, titanium dioxide, tetrabutyl titanate 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 titanium elements 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 titanium elements content in composition is finally measured, detection is limited to 2ppm.
Wet and heat ageing resistant performance：The particle of extrusion is shaped to the survey of ASTM standard stretching I types under 270 DEG C of injection temperatures Test plate (panel) material, it is placed on after injection under the constant-temperature constant-humidity environment of 25 DEG C of temperature and 25% humidity after 48h, test board is put in 90 DEG C Take out, be placed under the constant-temperature constant-humidity environment of 25 DEG C of temperature and 25% humidity with after the constant temperature oven baking 500h of 90% humidity After 48h, record places front and rear tensile strength (test speed 10mm/min), by the way that property retention rate is calculated；
Surface quality：The particle of extrusion is shaped to 100mm*100mm*2mm test board under 270 DEG C of injection temperatures Material, now cast gate size selection 0.5mm, is placed on 48h under the constant-temperature constant-humidity environment of 25 DEG C of temperature and 25% humidity after injection Afterwards, observe, in the hickie size that cast gate goes out, it is excellent not observe any hickie, observes hickie, and hickie diameter is less than 0.5cm evaluation and tests are good, observe hickie, it is general that hickie diameter, which is more than 0.5cm and is less than 1cm evaluation and tests, observes hickie, hickie It is poor that diameter, which is more than 1cm evaluation and tests,.
Tensile strength：ASTM standard.
Embodiment 1-16 and comparative example 1-2：The preparation of polycarbonate compositions
It is suspended that titanium-containing 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 titanium-containing compound of low soluble titanium content, the content of titanium elements in polycarbonate compositions is controlled in the range of 1-40ppm, After obtained polycarbonate compositions can be made to toast 500h under 90 DEG C and 90% humidity, wet and heat ageing resistant property retention rate is big In 70%, hence it is evident that improve the wet and heat ageing resistant performance of polycarbonate compositions, while there is more high surface quality, keep Excellent mechanical performance；In comparative example 1-2, when the content of titanium elements is less than 1ppm or higher than 40ppm in polycarbonate compositions, Wet and heat ageing resistant performance, the surface quality of polycarbonate compositions are poor.

Claims (12)

  1. A kind of 1. polycarbonate compositions, it is characterised in that by weight, including following component：
    35 parts -75 parts of makrolon；
    0 part -30 parts of graft copolymer；
    5 parts -25 parts of fire retardant；
    10 parts -50 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 titanium elements is 1ppm-40ppm.
  3. 3. polycarbonate compositions according to claim 2, it is characterised in that the weight content of the titanium elements 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 Titanium elements 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 titanium elements is 5ppm-30ppm, preferably 8ppm-20ppm.
  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 titanium elements derive from Titanium-containing compound, the titanium-containing compound selected from titanyl compound, the saline oxide of titanium, the chelate of titanium, titanium 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 titanium-containing 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.
CN201611070240.4A 2016-11-29 2016-11-29 A kind of polycarbonate compositions and preparation method thereof Pending CN107793724A (en)

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CN201611070240.4A CN107793724A (en) 2016-11-29 2016-11-29 A kind of polycarbonate compositions and preparation method thereof
PCT/CN2017/107756 WO2018099218A1 (en) 2016-11-29 2017-10-26 Polycarbonate composition and preparation method therefor

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