CN105315641B - A kind of polycarbonate compositions and preparation method thereof - Google Patents
A kind of polycarbonate compositions and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of polycarbonate compositions, by weight, including consisting of：A, 30 parts 87 parts of makrolon；B, 8 parts 50 parts of graft copolymer；C, 5 parts 25 parts of fire retardant；D, 0 10 parts of other auxiliary agents；Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts.The present invention is by selecting when being no more than 80ppm during the content for adding phenol type substances during polycarbonate compositions are formulated is based on the total weight of polycarbonate compositions, the long-term thermo-oxidative ageing and weather resistance of polycarbonate compositions can be significantly improved, and relatively high occasion is required especially suitable for use environment, the wherein structural formula of phenol type substances such as formula（1）：Formula（1）Wherein R1And R5Represent the hydrogen-based other than the group that is obstructed, alkyl, alkoxy, hydroxyl, carboxyl or carbonyl, ester group, R2, R3, R4Represent the substituent group of hydrogen atoms, preferably hydrogen atom.
Description
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 performance and to notch shock
Sensitive disadvantage, it is polymer-modified to may be typically added rubber, such as ABS, MBS, ACR and silicon rubber etc., especially with PC
It is a kind of important engineering plastics with PC/ABS alloys that ABS is primary raw material, the excellent performance that both can be integrated accomplishes physics
Performance and processing performance are improved, but due to the addition of ABS, in system double bond can bring long-term thermal-oxidative aging property with
And the hidden danger of weather resistance, relatively high occasion is especially required use environment.
Patent US20130289177A1 discloses the PC/ABS compositions with good thermally and chemically stability, bisphenol-A
Use increase the colour stability of composition, but bisphenol-A is defective in terms of environmental protection, while bisphenol-A can be special to performance
It is not that impact property brings hidden danger.
Patent CN1218070, which is disclosed, selects the ABS of emulsion method synthesis that can improve heat resistance, but only limits emulsion method
The use of ABS is unpractiaca in many application scenarios, and rubber size distribution is different in emulsion method ABS, causes machinery
Strength stability is inadequate, can also be restricted in the application.
Up to the present, about the content of phenol type substances to the long-term thermo-oxidative ageing of the polycarbonate compositions and resistance to
The influence for waiting performance has not been reported.
The present inventor pass through many experiments surprisingly it has been found that, select polycarbonate compositions formula in add phenol object
When being no more than 80ppm in total weight of the content of matter based on polycarbonate compositions, after pretreatment and pass through modified trace
The phenol type substances that grade is retained can significantly improve the long-term thermo-oxidative ageing and weather resistance of polycarbonate compositions, and especially suitable
Relatively high occasion is required for use environment.
Invention content
In order to overcome the disadvantages and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of long-term thermo-oxidative ageing
And the polycarbonate compositions that weather resistance significantly improves.
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 consisting of：
A, 30 parts -87 parts of makrolon；
B, 8 parts -50 parts of graft copolymer；
C, 5 parts -25 parts of fire retardant；
D, 0-10 parts of other auxiliary agents；
Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts.
Preferably, a kind of polycarbonate compositions, by weight, including consisting of：
A, 50 parts -75 parts of makrolon；
B, 8 parts -35 parts of graft polymers；
C, 5 parts -25 parts of fire retardant；
D, 0-10 parts of other auxiliary agents；
Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts,
The content of phenol type substances is less than or equal to 80ppm and is more than or equal in total weight based on polycarbonate compositions
0.1ppm；
The wherein structural formula of phenol type substances such as formula（1）：
Formula（1）
Wherein R1And R5Represent the hydrogen-based other than the group that is obstructed, alkyl, alkoxy, hydroxyl, carboxyl or carbonyl, ester
Base, R2, R3, R4Represent the substituent group of hydrogen atoms, preferably hydrogen atom.
It is highly preferred that a kind of polycarbonate compositions, by weight, including consisting of：
A, 50 parts -70 parts of makrolon；
B, 8 parts -30 parts of graft polymers；
C, 5 parts -18 parts of fire retardant；
D, 0-10 parts of other auxiliary agents；
Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts,
The content of phenol type substances is less than or equal to 80ppm and is more than or equal in total weight based on polycarbonate compositions
0.1ppm；The wherein structural formula of phenol type substances such as formula（1）：
Formula（1）
Wherein R1And R5Represent the hydrogen-based other than the group that is obstructed, alkyl, alkoxy, hydroxyl, carboxyl or carbonyl, ester
Base, R2, R3, R4Represent the substituent group of hydrogen atoms, preferably hydrogen atom.
Wherein, the test method of the content of phenol type substances：It, will after polycarbonate compositions with electronic balance weighing 2g
Sample is put into 120 DEG C of preset temperature and the constant temperature oven of temperature stable homogeneous after 2h, is put into soxhlet type apparatus and is carried out first
Alcohol extracts, and extraction temperature is 85 DEG C, time 48h, and after extract is placed into constant temperature, 20ul is extracted out by filter screen, with
The flow velocity of 10ml/min, by mobile phase（Methanol:Pure water=90:10）It will be divided in the adsorption column of extract sample introduction to C18
From and it is quantitative, after the standard solution by establishing 1ppm, 5ppm, 10ppm and 20ppm establishes standard curve, can pass through
The specific delivery time of standard specimen and calculation by extrapolation obtain the content of phenol type substances.
When the content of phenol type substances in the total weight based on polycarbonate compositions is more than 80ppm, obtained product
Colour stability is poor, and yellowness index is high, and in process since small-molecule substance will produce surface appearance defects.
The content for being preferably based on phenol type substances in the total weight of polycarbonate compositions is less than or equal to 70ppm and big
In equal to 10ppm；More preferably less than it is equal to 50ppm and is more than or equal to 25ppm.
Wherein, the makrolon is selected from aromatic copolycarbonate, fatty poly-ester carbonate, the poly- carbon of aromatic-aliphatic
One or more of acid esters, branching polycarbonate, siloxane copolycarbonate；Preferably aromatic copolycarbonate.
Preferably, the makrolon is the aromatic copolycarbonate of viscosity average molecular weigh 13000-40000, more preferably viscous
The aromatic copolycarbonate of average molecular weight 16000-28000.When viscosity average molecular weigh within the above range, mechanical strength it is good and
It can keep excellent mouldability.Wherein, viscosity average molecular weigh be by using dichloromethane as solvent test temperature be 25 DEG C
Solution viscosity calculate.
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 refers in the presence of rubber polymer by styrene monomer, acrylic compounds
Monomer and the polymer of silicon class monomer copolymerization and acquisition, selected from mass polymerization, emulsion polymerization, bulk-suspension polymerization method
The one or more of the graft copolymer of preparation.
Mass polymerization：Including colloidal sol, prepolymerization, polymerization, five steps of devolatilization and granulation：By rubber solution in ethylbenzene and
In styrene, monomer is added according to formula ratio and is made into material liquid, the material liquid prepared is inputted in pre-polymerization axe and carries out prepolymerization,
In polymerization process, grafting rubbers monomer, while monomer is copolymerized, and is 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
It forms discontinuous phase to be dispersed in continuous copolymer phase, completes phase transition, finally by further polymerization, vacuum outgas is squeezed
Go out, cooling and pelletizing obtains end article；
Bulk-suspension polymerization method：Rubber and monomer solution are adjusted according to formula, and polymerization regulator and freedom are added simultaneously
Base initiator is stirred continuously by monomer mixture in 80 DEG C of -120 DEG C of progress bulk polymerizations in polymerization process, and by deionized water
It is added in mixture with suspending agent, mixture is made to be disperseed, then carried out suspension polymerisation using free radical catalyst, obtain
It is washed by cohesion, filtering after certain degree of polymerization, is dehydrated and is granulated after dry acquisition product.
Emulsion polymerization：Rubber is by the way that in initiator, deionized water, emulsifier and crosslinking agent, polymerization temperature is controlled 50
DEG C -80 DEG C, monomer mixture is added to elastomer latex and is grafted, is finally washed, is granulated and made after being dehydrated and drying
Product.
Wherein, the graft copolymer, by weight, selected from including the b.1 graft polymers on b.2 as follows：
B.1,5 parts -95 parts of mixture b.1.1 and b.1.2：
B.1.1,50 parts -95 parts of styrene, styrene derivative such as α-methylstyrene, to benzyl styrene, two
Vinylstyrene, methacrylic acid C1-C8- Arrcostabs, acrylic acid C1-C8- Arrcostabs, dimethyl siloxane, phenyl silica
The one or more of alkane, more alkylsiloxanes；
B.1.2,5 parts -50 parts of acrylonitrile, methacrylonitrile, methacrylic acid C1-C8- Arrcostabs, acrylic acid C1-C8-
The one or more of Arrcostab；
B.2,5 parts -95 parts of polybutadiene, polyisoprene, styrene butadiene random copolymer and block copolymerization
Object, acrylonitrile-butadiene random copolymer and block copolymer, polybutadiene and polyisoprene copolymers, ethylene and a- alkene
Hydrocarbon copolymer, ethylene and a- unsaturated carboxylic acids ester copolymer, ethylene-propylene-non-conjugated diene terpolymer, acryloyl rubber
The one or more of glue, organopolysiloxane elastomer.
It is highly preferred that the graft copolymer is selected from acrylonitritrile-styrene resin AS, acrylonitrile-butadiene-styrene (ABS)
Graft copolymer ABS, methyl methacrylate-nitrile-butadiene-styrene copolymer MABS, acrylonitrile-styrene-propylene
One or more of acid ter-polymer ASA, methyl methacrylate-butadiene-styrene graft copolymer MBS；Wherein,
The preferred 0.1um-0.5um of grain size of MBS, the preferred 0.1um-2um of mass polymerization ABS grain sizes, emulsion polymerization ABS grain sizes are preferred
0.05um-0.2um。
Further 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 there are two uniform either tools 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, three cyclopentadecane of perbromo-
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 of 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 bis- (diphenyl phoshates), hydroquinone bis- (diphenyl phoshates), double
Phenol A- bis- (diphenyl phoshates), resorcinol bis- (2,6- di-tert-butyl-phenyls phosphates), bis- (the 2,6- dimethyl of hydroquinone
Phenyl phosphate ester) one or more.
Can also include other auxiliary agents in the polymer blend, such as selected from stabilizer, retardant synergist, anti-dripping agent, profit
The one or more of lubrication prescription, releasing agent, plasticizer, filler, colorant.
Suitable stabilizer includes organic phosphite, such as triphenyl phosphite, phosphorous acid three-（2,6- 3,5-dimethylphenyls）
Ester, phosphorous acid three-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphate etc., organic phosphite, alkylated unitary
The butylation reaction production of the alkylation reaction product of phenol or polyphenol, polyphenol and diene, paracresol or bicyclopentadiene
Object, alkylated hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene-bis-phenol, benzyl compounds, polyalcohol esters, benzene
And triazole type, one or more kinds of combinations of benzophenone.
Suitable plasticizer is phthalic acid ester.
Suitable releasing agent includes metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, stone
Wax, lignite wax etc..
Suitable colorant includes various pigment, dyestuff.
The preparation method of above-mentioned polycarbonate compositions, includes the following steps：
1）Phenol type substances and methylsiloxane are made into the phenol type substances first that mass fraction is 0.15ppm-300ppm
Radical siloxane solution；
2）Phenol type substances methylsiloxane solution is blended with makrolon in high mixer, is obtained pretreated
Makrolon；
3）After pretreated makrolon, graft copolymer, fire retardant, other auxiliary agents are proportionally weighed, pass through height
Mixed machine or mixing machine are completed to be blended, and squeeze out, and cross water cooling, and granulation obtains the polycarbonate compositions of cylindrical particle.
The polycarbonate compositions of the present invention due to excellent long-term thermal stability and weatherability, appearance zero defect with
And excellent mechanical property, it can be used for outdoor and indoor application field, such as the case member of various types and size, family
Electrical appliance such as television set, printer, modem shells, display casing etc., or the automobile component that uses outdoors, building neck
The shell or lid and electrical appliance shell and frame in domain.
Compared with prior art, the present invention having the advantages that：
1）The present invention is by pre-processing polycarbonate resin with phenol type substances, by modified trace after pretreatment
The phenol type substances that grade is retained can capture makrolon hot oxygen in post-processing and molding and shear the active site to be formed, and stablize
Phenolic hydroxyl group, while makrolon being made to keep excellent mobility, it avoids generally closing using phenol type substances in the prior art
At in the process as end-capping reagent formed phenolic hydroxyl group and can not residual traces phenol type substances defect.
2）The present invention is by selecting the content of the addition phenol type substances in polycarbonate compositions formula to be based on poly- carbonic acid
When being no more than 80ppm in the total weight of ester composition, the phenol type substances retained by modified trace level after pretreatment can be bright
The aobvious long-term thermo-oxidative ageing and weather resistance for improving polycarbonate compositions, relatively high field is required especially suitable for use environment
It closes.
Specific implementation mode
It is further illustrated the present invention below by specific implementation mode, following embodiment is the preferable embodiment party of the present invention
Formula, but embodiments of the present invention are not limited by following embodiments.
The testing standard or method of each performance：
The assay method of content of phenol type substances：After polycarbonate compositions with electronic balance weighing 2g, sample is put
Enter in 120 DEG C of preset temperature and the constant temperature oven of temperature stable homogeneous after 2h, be put into soxhlet type apparatus and carry out methanol extracting,
Extraction temperature is 85 DEG C, time 48h, after extract is placed into constant temperature, 20ul is extracted out by filter screen, with 10ml/min's
Flow velocity, by mobile phase（Methanol:Pure water=90:10）It will be detached and determined in the adsorption column of extract sample introduction to C18
Amount, after the standard solution by establishing 1ppm, 5ppm, 10ppm and 20ppm establishes standard curve, can pass through the spy of standard specimen
Determine the delivery time and calculation by extrapolation obtains the content of phenol type substances；
The assay method of UV ageing properties chromatic aberrations：Under the processing temperature of polycarbonate compositions, to the combination room
Be molded, prepare thickness be 2mm, the plate that width is 40nn and length is 100mm, and mold temperature set be 100
DEG C, plank puts ageing oven standard into according to ISO4892 to be tested, and ageing time is defined as 150h, and " SM coloured silks are used after aging
Color computer " (manufacture of SUGA test equipments company), by the method proposed in JIS Z 8730, determines the brightness (value of plate：
L), red (value：A), yellow (value：b).Chromatic aberration is calculated by following the equation：
Chromatic aberration=100- [(100-L) 2+a2+b2] 1/2 aberration is bigger, and colour stability is poorer.；
The assay method of 150 DEG C of impact property conservation rate 500h：Test bars pass through Nissei Plastic Industrial Co., Ltd's system
The 80 tons of injection (mo(u)lding) machines made, after being obtained under conditions of 100 DEG C of 280 DEG C of barrel temperature and mold temperature, according to ASTM
D265 measures notched Ai Zuode impacts using lzod impact tester (manufactured by Toyo Co., Ltd.'s essence mechanism work)
Value measures aging after being put into the constant temperature oven aging 500h that preset temperature is 150 DEG C by batten according to test method above-mentioned
Ai Zuode impact values afterwards obtain 150 DEG C of impact property conservation rates according to the calculation formula of conservation rate, and numerical value is bigger, and performance is protected
It is better to hold.
The makrolon used in the present invention：
Component a-1：PC 1300-10（South Korea LG）；
Component a-2：PC 1225 （Japanese Supreme Being people）；
The phenol type substances used in the present invention：Phenol：（Shanghai TCI）；
P-methyl phenol substance：（Aladdin）；
Dimethyl benzene aldehydes matter：（Aladdin）；The graft copolymer used in the present invention：
Component b-1：ABS1 emulsion methods 757（Taiwan is very beautiful）；
Component b-2：ABS2 substance laws 8391（Shanghai Gaoqiao）；
Component b-3：MBS EM500（South Korea LG）；
The fire retardant used in the present invention：
Component c：BDP, bisphenol-A-are bis- (diphenyl phoshate)（Ai Dike）；
The other auxiliary agents used in the present invention：
Component d-1：PTFE（Polytetrafluoroethylene (PTFE)）As anti-dripping agent；
Component d-2：PETS（Pentaerythritol stearate）As releasing agent.Wherein d1+d2 constant additions in formula
For 1% weight fraction.
Embodiment 1-10 and comparative example 1-11：The preparation of polycarbonate compositions
Phenol type substances and methylsiloxane are made into the phenol type substances methyl that mass fraction is 0.15ppm-300ppm
Siloxane solution；Phenol type substances methylsiloxane solution is blended with makrolon in high mixer, is pre-processed
Makrolon；Pretreated makrolon, graft copolymer, fire retardant, other auxiliary agents are proportionally claimed by the formula of table 1
It after amount, completes to be blended by high mixer or mixing machine, squeeze out, cross water cooling, granulation obtains the makrolon group of cylindrical particle
Close object；To 150 DEG C of impact property conservation rates of polycarbonate compositions（0h、150h）With UV ageing properties chromatic aberrations（150h）
It is tested, data are shown in Table 1.
The specific proportioning of table 1 embodiment 1-10 and comparative example 1-11（Parts by weight）And its test performance result
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | |
| Component a-1 | 30 | 51 | 64 | 69 | 70 | 87 | ||||
| Component a-2 | 51 | 64 | 69 | 70 | ||||||
| Component b-1 | 50 | 15 | 11 | |||||||
| Component b-2 | 30 | 15 | 30 | 15 | ||||||
| Component b-3 | 20 | 20 | 15 | |||||||
| Component c | 19 | 18 | 15 | 15 | 14 | 1 | 18 | 15 | 15 | 14 |
| Component d-1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Component d-2 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Content of phenol type substances（ppm） | 0.1 | 20 | 0.5 | 10 | 40 | 60 | 80 | 30 | 5 | 60 |
| Content of bisphenol A（ppm） | - | - | - | - | - | - | - | - | - | - |
| Hindered phenol content（ppm） | ||||||||||
| 150 DEG C of impact property conservation rates（0h） | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% |
| 150 DEG C of impact property conservation rates（500h） | 62% | 80% | 60% | 72% | 73% | 60% | 65% | 83% | 65% | 63% |
| UV ageing properties chromatic aberrations（500h） | 4 | 1 | 1 | 1 | 2 | 5 | 4 | 1 | 2 | 2 |
Continued 1
| Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | Comparative example 6 | Comparative example 7 | Comparative example 8 | Comparative example 9 | Comparative example 10 | Comparative example 11 | |
| Component a-1 | 24 | 90 | 69 | 30 | 70 | 70 | 51 | 64 | 69 | 70 | 70 |
| Component a-2 | |||||||||||
| Component b-1 | 50 | 8 | 15 | 15 | 15 | 15 | |||||
| Component b-2 | 60 | 30 | 15 | ||||||||
| Component b-3 | 5 | 20 | |||||||||
| Component c | 25 | 1 | 25 | 9 | 14 | 14 | 18 | 15 | 15 | 14 | 14 |
| Component d-1 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Component d-2 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Content of phenol type substances（ppm） | 0.1 | 60 | 10 | 0.1 | 0 | 100 | 95 | 0.05 | 120 | ||
| Content of bisphenol A（ppm） | 17 | ||||||||||
| Hindered phenol content（ppm） | 17 | ||||||||||
| 150 DEG C of impact property conservation rates（0h） | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% | 100% |
| 150 DEG C of impact property conservation rates（500h） | 30% | 44% | 12% | 23% | 15% | 33% | 42% | 45% | 50% | 55% | 50% |
| UV ageing properties chromatic aberrations（500h） | 50 | 32 | 27 | 14 | 33 | 20 | 30 | 42 | 33 | 53 | 62 |
From table 1 it follows that it is poly- to select the content of the addition phenol type substances in polycarbonate compositions formula to be based on
When being no more than 80ppm in the total weight of carbonate composition, by the phenol type substances energy of modified trace level retention after pretreatment
Enough significantly improve the long-term thermo-oxidative ageing and weather resistance of polycarbonate compositions.
Claims (23)
1. a kind of polycarbonate compositions, by weight, including consisting of：
A, 30 parts -87 parts of makrolon；
B, 8 parts -50 parts of graft copolymer；
C, 5 parts -25 parts of fire retardant；
D, 0-10 parts of other auxiliary agents；
Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts；
The content of phenol type substances is less than or equal to 80ppm and is more than or equal in total weight based on polycarbonate compositions
0.1ppm；
The wherein structural formula of phenol type substances such as formula（1）：
Formula（1）
Wherein R1And R5The hydrogen-based other than the group that is obstructed, alkyl, alkoxy, hydroxyl, carboxyl, carbonyl or ester group are represented,
R2, R3, R4Represent the substituent group of hydrogen atoms.
2. polycarbonate compositions according to claim 1, which is characterized in that the R2, R3, R4For hydrogen atom.
3. a kind of polycarbonate compositions as described in claim 1, by weight, including consisting of：
A, 50 parts -75 parts of makrolon；
B, 8 parts -35 parts of graft polymers；
C, 5 parts -25 parts of fire retardant；
D, 0-10 parts of other auxiliary agents；
Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts.
4. a kind of polycarbonate compositions as described in claim 1, by weight, including consisting of：
A, 50 parts -70 parts of makrolon；
B, 8 parts -30 parts of graft polymers；
C, 5 parts -18 parts of fire retardant；
D, 0-10 parts of other auxiliary agents；
Wherein, the sum of parts by weight of tetra- kinds of components of a, b, c, d are 100 parts.
5. polycarbonate compositions according to claim 1, which is characterized in that the total weight based on polycarbonate compositions
The content of middle phenol type substances is less than or equal to 70ppm and is more than or equal to 10ppm.
6. polycarbonate compositions according to claim 5, which is characterized in that the total weight based on polycarbonate compositions
The content of middle phenol type substances is less than or equal to 50ppm and is more than or equal to 25ppm.
7. according to claim 1-4 any one of them polycarbonate compositions, which is characterized 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 of ester.
8. polycarbonate compositions according to claim 7, which is characterized in that the makrolon is aromatic polycarbonate
Ester.
9. according to claim 1-3 any one of them polycarbonate compositions, which is characterized in that the makrolon is viscous equal
The aromatic copolycarbonate of molecular weight 13000-40000.
10. polycarbonate compositions according to claim 9, which is characterized in that the makrolon is viscosity average molecular weigh
The aromatic copolycarbonate of 16000-28000.
11. according to claim 1-4 any one of them polycarbonate compositions, which is characterized in that the graft copolymer choosing
The one or more of the graft copolymer prepared from mass polymerization, emulsion polymerization, bulk-suspension polymerization method.
12. according to claim 1-4 any one of them polycarbonate compositions, which is characterized in that the graft copolymer is pressed
Parts by weight meter, selected from including the b.1 graft polymers on b.2 as follows：
B.1,5 parts -95 parts of mixture b.1.1 and b.1.2：
B.1.1,50 parts -95 parts of styrene, styrene derivative, methacrylic acid C1-C8- Arrcostabs, acrylic acid C1-C8-
The one or more of Arrcostab, dimethyl siloxane, phenyl siloxane, more alkylsiloxanes；
B.1.2,5 parts -50 parts of acrylonitrile, methacrylonitrile, methacrylic acid C1-C8- Arrcostabs, acrylic acid C1-C8- alkyl
The one or more of ester；
B.2,5 parts -95 parts of polybutadiene, polyisoprene, styrene butadiene random copolymer and block copolymer, third
Alkene nitrile-butadiene random copolymer and block copolymer, polybutadiene and polyisoprene copolymers, ethylene and a- olefin-copolymerizations
It is object, ethylene and a- unsaturated carboxylic acids ester copolymer, ethylene-propylene-non-conjugated diene terpolymer, acryloyl rubber, organic
The one or more of silicone rubber.
13. polycarbonate compositions according to claim 12, which is characterized in that the styrene derivative is Alpha-Methyl
Styrene, to the one or more of benzyl styrene, divinylstyrene.
14. polycarbonate compositions according to claim 12, which is characterized in that the graft copolymer is selected from propylene
Nitrile-butadiene-styrene graft copolymer ABS, methyl methacrylate-nitrile-butadiene-styrene copolymer MABS, first
One or more of base methylacrylate-butadiene-phenylethene grafted copolymer MBS；Wherein, the grain size of MBS is in 0.1um-
0.5um, mass polymerization ABS grain size 0.1um-2um, emulsion polymerization ABS grain sizes 0.05um-0.2um.
15. polycarbonate compositions according to claim 14, which is characterized in that the graft copolymer is acrylonitrile-
Butadiene-styrene graft copolymer ABS.
16. according to claim 1-4 any one of them polycarbonate compositions, which is characterized in that the fire retardant is selected from halogen
Flame retardant or halogen-free flame retardants；The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, brominated styrene-horse
Come acid anhydride copolymer, brominated epoxy resin, bromination phenoxy resin, deca-BDE, decabromodiphenyl, brominated polycarbonate,
The one or more of three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer；The halogen-free flame retardants is selected from nitrogenous fire-retardant
One or more of agent, phosphonium flame retardant or nitrogenous and phosphorus fire retardant.
17. polycarbonate compositions according to claim 16, which is characterized in that the brominated epoxy resin is that bromination is double
Phenol A type epoxy resin.
18. polycarbonate compositions according to claim 16, which is characterized in that the fire retardant is halogen-free flame retardants.
19. polycarbonate compositions according to claim 16, which is characterized in that the halogenated flame retardant is brominated polyphenylene
Ethylene.
20. polycarbonate compositions according to claim 18, which is characterized in that the halogen-free flame retardants is phosphor-containing flame-proof
Agent.
21. polycarbonate compositions according to claim 20, which is characterized in that the phosphonium flame retardant is selected from tricresyl phosphate
Phenylester, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate dimethylbenzene base ester, tricresyl phosphate (2,4,6- trimethyls
Phenyl) ester, tricresyl phosphate (2,4- di-tert-butyl-phenyls) ester, tricresyl phosphate (2,6- di-tert-butyl-phenyls) ester, the bis- (phosphoric acid of resorcinol
Diphenyl), hydroquinone bis- (diphenyl phoshates), bisphenol-A-bis- (diphenyl phoshates), bis- (bis- uncles of 2,6- of resorcinol
Butyl phenyl phosphate), the one or more of hydroquinone bis- (2,6- dimethylphenylphosphates).
22. according to claim 1-4 any one of them polycarbonate compositions, which is characterized in that the other of component d help
Agent is selected from one kind or several of stabilizer, retardant synergist, anti-dripping agent, lubricant, releasing agent, plasticizer, filler, colorant
Kind.
23. a kind of preparation method of such as claim 1-22 any one of them polycarbonate compositions, which is characterized in that including
Following steps：
1）Phenol type substances and methylsiloxane are made into the phenol type substances methyl silicon that mass fraction is 0.15ppm-300ppm
Oxygen alkane solution；
2）Phenol type substances methylsiloxane solution is blended with makrolon in high mixer, pretreated poly- carbon is obtained
Acid esters；
3）After pretreated makrolon, graft copolymer, fire retardant, other auxiliary agents are proportionally weighed, pass through mixing machine
It completes to be blended, squeeze out, cross water cooling, granulation obtains the polycarbonate compositions of cylindrical particle.
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