CN105440624B - 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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- 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
- C08K3/08—Metals
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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
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
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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
- 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
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- 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
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- 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
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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Abstract
The invention discloses a kind of polycarbonate compositions, by weight, including consisting of: a, 30 parts -80 parts of polycarbonate；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.When the present invention is added in total weight of the compounding total amount based on polycarbonate compositions of phenol type substances and metal manganese element by selecting in polycarbonate compositions formula no more than 500ppm, so that the good fluidity of polycarbonate compositions, and there is colour stability and high gloss before and after long-term thermo-oxidative ageing, 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, in particular to a kind of polycarbonate compositions and preparation method thereof.
Background technique
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, especially using PC and ABS as primary raw material
PC/ABS alloy is a kind of important engineering plastics, can integrate the excellent performance of the two, accomplish physical property and processing performance
It is improved, but due to the addition of ABS, double bond can bring the hidden of long-term thermal-oxidative aging property and weather resistance in system
Suffer from, especially requires use environment relatively high occasion, surface defect easy to form and its color are easy to happen variation.
Patent CN102292393, which is disclosed, can improve surface quality after the wet storage of heat using salt field trash, therefore
It is suitable for the moulded work that preparation has ageing-resistant zero defect class-A surfaces；
Patent CN104271610, which is disclosed, selects sodium, magnesium, calcium impurities preparation with the polymerization for improving surface after damp and hot storage
Object；But the above light metal impurity be easy under hygrothermal environment formed alkalinity, promote the degradation of polycarbonate, so as to cause its
Performance degradation and color difference are larger before and after use, and stability is poor in practical applications.
Up to the present, about the compounding total amount of phenol type substances and metal manganese element to the polycarbonate compositions
The influence of mobility, high gloss and colour stability 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
Matter and the compounding total amount of metal manganese element are based on 500ppm is no more than in the total weight of polycarbonate compositions when, so that poly- carbonic acid
The good fluidity of ester composition, and there is colour stability and high gloss before and after long-term thermo-oxidative ageing, especially suitable for using
The relatively high occasion of environmental requirement.
Summary of the invention
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 with excellent stream
Dynamic property, and the polycarbonate compositions with colour stability and high gloss before and after long-term thermo-oxidative ageing.
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 -80 parts of polycarbonate；
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, 30 parts -75 parts of polycarbonate；
B, 8 parts -35 parts of graft copolymer；
C, 5 parts -23 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 compounding total amount of phenol type substances and metal manganese element is more than or equal in total weight based on polycarbonate compositions
10ppm and be less than or equal to 500ppm；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, 30 parts -70 parts of polycarbonate；
B, 8 parts -30 parts of graft copolymer；
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 compounding total amount of phenol type substances and metal manganese element is more than or equal in total weight based on polycarbonate compositions
10ppm and be less than or equal to 500ppm；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:, will after the 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 extracting, extraction temperature are 85 DEG C, time 48h, after extract is placed into constant temperature, extract 20ul out by filter screen, with
The flow velocity of 10ml/min will be divided by mobile phase (methanol: pure water=90:10) 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.
The test method of the content of metal manganese element: ICP-MS mixes mark method.
When the compounding total amount of phenol type substances in the total weight based on polycarbonate compositions and metal manganese element is more than
500ppm will lead to flowing instability and apparent surface point spray due to the small molecule of interference in system, thus in the presence of
The hidden danger of processing stability and surface defect.
Preferably, the compounding total amount of the phenol type substances and metal manganese element is more than or equal to 20ppm and to be less than or equal to
400ppm；Preferably greater than it is equal to 30ppm and is less than or equal to 300ppm；More preferably higher than it is equal to 50ppm and is less than or equal to
200ppm。
Wherein, the compounding weight ratio of the phenol type substances and metal manganese element is 2:3-4:3.
Wherein, the polycarbonate 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.
The polycarbonate is the aromatic copolycarbonate of viscosity average molecular weigh 13000-40000, more preferably glues equal molecule
Measure the aromatic copolycarbonate of 16000-28000.When viscosity average molecular weigh within the above range, mechanical strength is good and is able to maintain
Excellent mouldability.Wherein, viscosity average molecular weigh is the solution for being 25 DEG C in test temperature as solvent by using methylene chloride
What viscosity calculations came out.
The preparation method of above-mentioned polycarbonate 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 and is granulated five steps at devolatilization: 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 prepolymerization kettle 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
Out, cooling and pelletizing obtains final product；
Bulk-suspension polymerization method: adjusting rubber and monomer solution according to formula, and notifies that polymerization regulator and freedom is added
Monomer mixture is stirred continuously by base initiator in 80 DEG C of -120 DEG C of progress bulk polymerizations, polymerization process, and by deionized water
It is added in mixture with suspending agent, disperses mixture, then carried out suspension polymerisation using free radical catalyst, obtain
By cohesion after certain degree of polymerization, filtering is washed, and 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 copolymer 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- Arrcostab, acrylic acid C1-C8- Arrcostab, dimethyl siloxane, phenyl silicon oxygen
The one or more of alkane, more alkylsiloxanes；
B.1.2,5 parts -50 parts of acrylonitrile, methacrylonitrile, methacrylic acid C1-C8- Arrcostab, acrylic acid C1-C8-
The one or more of Arrcostab；
B.2,5 parts -95 parts of grafting rubbers basis such as polybutadiene, polyisoprene, styrene-butadiene random copolymerization
Object and block copolymer, acrylonitrile-butadiene random copolymer and block copolymer, polybutadiene and polyisoprene copolymer
Object, ethylene and a- olefin copolymer, ethylene and a- unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene ternary polymerization
The one or more of object, acryloyl rubber, 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；
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 or tools or with upward peak
More distributions.
Preferably, the graft copolymer, by weight, selected from including the b.1 graft polymers on b.2 as follows:
B.1,30 parts -80 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- Arrcostab, acrylic acid C1-C8- Arrcostab, dimethyl siloxane, phenyl silicon oxygen
The one or more of alkane, more alkylsiloxanes；
B.1.2,5 parts -50 parts of acrylonitrile, methacrylonitrile, methacrylic acid C1-C8- Arrcostab, acrylic acid C1-C8-
The one or more of Arrcostab；
B.2,20 parts -70 parts of basis containing grafting rubbers such as polybutadiene, polyisoprene, styrene-butadiene random
Copolymer and block copolymer, acrylonitrile-butadiene random copolymer and block copolymer, polybutadiene and polyisoprene are total
Polymers, ethylene and a- olefin copolymer, ethylene and a- unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene ternary are total
The one or more of polymers, acryloyl rubber, 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 the partial size of MBS, the preferred 0.1um-2um of mass polymerization ABS partial size, emulsion polymerization ABS partial size 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 or 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- trimethylphenyl) ester, tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester, phosphorus
It is sour three (2,6- di-tert-butyl-phenyl) esters, resorcinol bis- (diphenyl phoshates), hydroquinone bis- (diphenyl phoshates), double
Phenol A- bis- (diphenyl phoshates), resorcinol bis- (2,6- di-tert-butyl-phenyl phosphates), bis- (the 2,6- dimethyl of hydroquinone
Phenyl phosphate ester) one or more.
It can also include other auxiliary agents in the polymer blend, such as be selected from stabilizer, retardant synergist, anti-dripping agent, profit
The one or more of lubrication prescription, release agent, plasticizer, filler, colorant.
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., organic phosphite, alkylated unitary
The butylation of the alkylation reaction product of phenol or polyphenol, polyphenol and diene, paracresol or bicyclopentadiene, which reacts, to be produced
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 release 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) by phenol type substances and standard manganese solution and phenyl siloxane, mass fraction is 12.5ppm- according to the proportion
The phenyl siloxane solution of 2000ppm；
2) phenyl siloxane solution is blended in high mixer with polycarbonate, obtains pretreated polycarbonate；
3) after proportionally weighing pretreated polycarbonate, graft copolymer, fire retardant, other auxiliary agents, pass through height
The machine of mixing or mixing machine are completed to be blended, and squeeze out, and cross water cooling, and granulation obtains the polycarbonate compositions of cylindrical particle.
Polycarbonate compositions of the 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 shell, display casing etc., or the automobile component used outdoors, building neck
The shell or lid and electrical appliance shell and frame in domain.
Compared with prior art, the present invention having the following beneficial effects:
1) present invention is by pre-processing polycarbonate with phenol type substances and metal manganese element, metal manganese element
Reduction is played in system, can balance iron atom or its compound to the degradation of polymer, while in trace
The phenol type substances that grade is retained can capture the association that polycarbonate hot oxygen in post-processing and molding shears the active site to be formed
Under same-action, can the phenolic hydroxyl group preferably in stabilising system avoid existing skill so that polycarbonate keeps excellent mobility
In art generally using phenol type substances be used as in the synthesis process end-capping reagent formed phenolic hydroxyl group and can not residual traces phenol
The defect of substance.
2) present invention adds answering for phenol type substances and metal manganese element by selecting in polycarbonate compositions formula
When with total amount based on 500ppm is no more than in the total weight of polycarbonate compositions, so that the mobility of polycarbonate compositions
It is good, and there is colour stability and high gloss before and after long-term thermo-oxidative ageing, it is required especially suitable for use environment relatively high
Occasion.
Specific embodiment
Further illustrate that the present invention, following embodiment are the preferable embodiment party of the present invention below by specific embodiment
Formula, but embodiments of the present invention are not limited by following embodiments.
The testing standard or method of each performance:
The measuring method of content of phenol type substances: after the 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 will be separated and be determined in the adsorption column of extract sample introduction to C18 by mobile phase (methanol: pure water=90:10)
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 test method of manganese metal constituent content: ICP-MS mixes mark method；
The measuring method of newton index: die orifice draw ratio is 20, and shearing steady temperature is 260 DEG C, shear rate 100s-1-
10000s-1, preheating time 300s, after obtain the curve of shear rate and shear stress after exponentiation n obtain newton index.Its
In, the calculation method of newton index: doing power fitting by shear rate and shear stress, obtains fitting formula y=a xn, intend
Close the variance R of formula2It is greater than 0.99；Wherein, n is newton index, and newton index is smaller, and processing performance is better, also, ox
The index that pauses reduces by 0.01, and processing performance has clear improvement.
The measuring method of long-term thermo-oxidative ageing colour stability: the hot oxygen colour table color change grade of 80 DEG C of baking ovens, 1 grade is most
Good, 5 grades are worst；
The measuring method of glossiness: the glossiness at 60 ° of angles, table are measured after colour table constant temperature and humidity placement 48h with vancometer
Face glossiness grade, 1 grade to be best, without any defect, 2 grades have slight spray point, and 3 grades are poor for surface gloss, hence it is evident that
Spray and point；
Polycarbonate used in the present invention:
Component a-1:PC 1300-10(South Korea LG)；
Component a-2:PC 1225 (Japanese Supreme Being people)；
Phenol type substances used in the present invention:
Phenol type substances used in the present invention:
P-methyl phenol substance: (Aladdin)；
Dimethyl benzene phenolic substances: (Aladdin)；
Standard manganese solution: (national iron and steel research institute)
Graft copolymer used in the present invention:
The odd beauty in the Taiwan component b-1:ABS1 emulsion method 757()；
Component b-2:ABS2 substance law 8391(Shanghai Gaoqiao)；
Component b-3:MBS EM500(South Korea LG)；
Fire retardant used in the present invention:
Component c:BDP, bisphenol-A-bis- (diphenyl phoshates) (Ai Dike)；
Other auxiliary agents used in the present invention:
Bis- (2,6- di-t-butyl -4- aminomethyl phenyl) pentaerythritol diphosphates of component d-1:PEP-36() as stabilization
Agent；
Component d-2:C wax is as lubricant；
Component d-3:PTFE(polytetrafluoroethylene (PTFE)) it is used as anti-dripping agent；
Component d-4: colorant carbon black M717.
Embodiment 1-12 and comparative example 1-8: the preparation of polycarbonate compositions
It is 12.5ppm-2000ppm's that phenol type substances and standard manganese solution and phenyl siloxane, which are made into mass fraction,
Phenyl siloxane solution；Phenyl siloxane solution is blended in high mixer with polycarbonate, obtains pretreated poly- carbon
Acid esters；After pretreated polycarbonate, graft copolymer, fire retardant, other auxiliary agents are proportionally weighed by the formula of table 1,
It completes to be blended by high mixer or mixing machine, squeeze out, cross water cooling, granulation obtains the polycarbonate compositions of cylindrical particle；
Mobility (newton index), long-term thermo-oxidative ageing colour stability (color difference) and the glossiness of polycarbonate compositions are surveyed
Examination, data are shown in Table 1.
Specific proportion (parts by weight) and its test performance result of table 1 embodiment 1-12 and comparative example 1-8
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 | Embodiment 12 | |
| Component a-1 | 30 | 51 | 64 | 69 | 70 | 80 | ||||||
| Component a-2 | 30 | 51 | 64 | 69 | 70 | 80 | ||||||
| Component b-1 | 50 | 15 | 8 | 50 | 15 | 8 | ||||||
| Component b-2 | 30 | 15 | 30 | 15 | ||||||||
| Component b-3 | 20 | 20 | ||||||||||
| Component c | 19 | 18 | 15 | 15 | 14 | 11 | 19 | 18 | 15 | 15 | 14 | 11 |
| Component d-1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Component d-2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Component d-3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Component d-4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Content of phenol type substances (ppm) | 4 | 8 | 12 | 18 | 50 | 250 | 11 | 140 | 20 | 70 | 160 | 40 |
| Manganese element content (ppm) | 6 | 10 | 14 | 16 | 50 | 250 | 11 | 150 | 20 | 60 | 200 | 30 |
| Bisphenol-A (ppm) | ||||||||||||
| Phenol content of being obstructed (ppm) | ||||||||||||
| Newton index (n) | 0.4580 | 0.4364 | 0.4213 | 0.4159 | 0.4003 | 0.4437 | 0.4214 | 0.4113 | 0.4103 | 0.4005 | 0.4215 | 0.4027 |
| Long-term thermo-oxidative ageing colour stable grade | 2 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 2 | 1 |
| Lustrous surface grade | 2 | 1 | 2 | 2 | 1 | 2 | 2 | 1 | 1 | 1 | 1 | 1 |
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 | |
| Component a-1 | 30 | 51 | 64 | 69 | 70 | 80 | 69 | 69 |
| Component a-2 | ||||||||
| Component b-1 | 50 | 15 | 8 | |||||
| Component b-2 | 30 | 15 | 15 | 15 | ||||
| Component b-3 | 20 | |||||||
| Component c | 19 | 18 | 15 | 15 | 14 | 11 | 15 | 15 |
| Component d-1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 | 0.1 |
| Component d-2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Component d-3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Component d-4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 | 0.4 |
| Phenol type substances (ppm) | 2 | 18 | 0 | 180 | 400 | 280 | ||
| Manganese element content (ppm) | 3 | 0 | 26 | 540 | 200 | 280 | 16 | 16 |
| Bisphenol-A (ppm) | 18 | |||||||
| Phenol content of being obstructed (ppm) | 18 | |||||||
| Newton index | 0.5938 | 0.5383 | 0.5402 | 0.5903 | 0.5672 | 0.5231 | 0.5432 | 0.6063 |
| Long-term thermo-oxidative ageing colour stable grade | 5 | 4 | 4 | 5 | 3 | 5 | 5 | 5 |
| Lustrous surface grade | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
Benzene is added in polycarbonate compositions formula from the comparison of the embodiment and comparative example of table 1 it can be seen that selecting
Phenolic substances and the compounding total amount of metal manganese element are based on 500ppm is no more than in the total weight of polycarbonate compositions when, poly- carbon
The good fluidity of acid ester composite, and there is colour stability and high gloss before and after long-term thermo-oxidative ageing, especially suitable for making
With the relatively high occasion of environmental requirement.
Claims (25)
1. a kind of polycarbonate compositions, by weight, including consisting of:
A, 30 parts -80 parts of polycarbonate；
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 compounding total amount of phenol type substances and metal manganese element is more than or equal to 10ppm in total weight based on polycarbonate compositions
Be less than or equal to 500ppm；The wherein structural formula of phenol type substances such as formula (1):
Formula (1)
Wherein R1And R5Hydrogen-based of the representative other than the group that is obstructed, alkyl, alkoxy, hydroxyl, carboxyl or carbonyl, ester group,
R2, R3, R4Represent the substituent group of hydrogen atoms；
The compounding weight ratio of the phenol type substances and metal manganese element is 2:3-4:3；
And the content of phenol type substances and metal manganese element is respectively greater than zero.
2. polycarbonate compositions according to claim 1, the R2, R3, R4Represent hydrogen atom.
3. a kind of polycarbonate compositions as described in claim 1, by weight, including consisting of:
A, 30 parts -75 parts of polycarbonate；
B, 8 parts -35 parts of graft copolymer；
C, 5 parts -23 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, 30 parts -70 parts of polycarbonate；
B, 8 parts -30 parts of graft copolymer；
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 phenol type substances and metal manganese element
Compounding total amount be more than or equal to 20ppm and be less than or equal to 400ppm.
6. polycarbonate compositions according to claim 5, which is characterized in that the phenol type substances and metal manganese element
Compounding total amount be more than or equal to 30ppm and be less than or equal to 300ppm.
7. polycarbonate compositions according to claim 6, which is characterized in that the phenol type substances and metal manganese element
Compounding total amount be more than or equal to 50ppm and be less than or equal to 200ppm.
8. according to claim 1,3,4 described in any item polycarbonate compositions, which is characterized in that the polycarbonate is selected from
One of aromatic copolycarbonate, fatty poly-ester carbonate, aromatic-aliphatic polycarbonate, siloxane copolycarbonate
Or it is several.
9. polycarbonate compositions according to claim 8, which is characterized in that the polycarbonate is aromatic polycarbonate
Ester.
10. polycarbonate compositions according to claim 9, which is characterized in that the aromatic copolycarbonate is selected from viscous
The aromatic copolycarbonate of average molecular weight 13000-40000.
11. polycarbonate compositions according to claim 10, which is characterized in that the aromatic copolycarbonate is selected from viscous
The aromatic copolycarbonate of average molecular weight 16000-28000.
12. according to claim 1,3,4 described in any item polycarbonate compositions, which is characterized in that the graft copolymer
The one or more of the graft copolymer prepared selected from mass polymerization, emulsion polymerization, bulk-suspension polymerization method.
13. according to claim 1,3,4 described in any item polycarbonate compositions, which is characterized in that the graft copolymer,
By weight, selected from including the b.1 graft copolymer 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, α-methylstyrene, to benzyl styrene, divinylstyrene, methyl-prop
Olefin(e) acid C1-C8- Arrcostab, acrylic acid C1-C8- Arrcostab, dimethyl siloxane, phenyl siloxane, more alkylsiloxanes one
Kind is several；
B.1.2,5 parts -50 parts of acrylonitrile, methacrylonitrile, methacrylic acid C1-C8- Arrcostab, 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-copolymerization
It is object, ethylene and a- unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene terpolymer, acryloyl rubber, organic
The one or more of silicone rubber.
14. polycarbonate compositions according to claim 13, the graft copolymer is selected from acrylonitrile-styrene copolymerized
Object AS, acrylonitrile-butadiene-phenylethene grafted copolymer ABS, methyl methacrylate-nitrile-butadiene-styrene copolymerization
Object MABS, acrylonitrile-styrene-acrylic ternary copolymer ASA, methyl methacrylate-butadiene-styrene graft copolymerization
One or more of object MBS.
15. polycarbonate compositions according to claim 14, the graft copolymer is acrylonitrile-butadiene-benzene second
Alkene graft copolymer ABS.
16. polycarbonate compositions according to claim 14, the partial size of the MBS is 0.1um-0.5um.
17. polycarbonate compositions according to claim 14, the mass polymerization ABS partial size is 0.1um-2um.
18. polycarbonate compositions according to claim 14, the emulsion polymerization ABS partial size is 0.05um-
0.2um。
19. according to claim 1,3,4 described in any item polycarbonate compositions, which is characterized in that the fire retardant is selected from
Halogenated flame retardant or halogen-free flame retardants；The halogenated flame retardant is selected from brominated Polystyrene, brominated polyphenylether, bmminated bisphenol-A type
Epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, deca-BDE, ten
The one or more of bromobiphenyl, brominated polycarbonate, three cyclopentadecane of perbromo- or brominated aromatic cross-linked polymer；The nothing
Halogen fire retardant is selected from one or more of nitrogenous flame ratardant, phosphonium flame retardant, nitrogenous and phosphorus fire retardant.
20. polycarbonate compositions according to claim 19, which is characterized in that the fire retardant is selected from halogen-free flameproof
Agent.
21. polycarbonate compositions according to claim 19, which is characterized in that the halogenated flame retardant is brominated polyphenylene
Ethylene.
22. polycarbonate compositions according to claim 20, which is characterized in that the halogen-free flame retardants is phosphor-containing flame-proof
Agent.
23. polycarbonate compositions according to claim 22, 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- trimethyl
Phenyl) ester, tricresyl phosphate (2,4- di-tert-butyl-phenyl) ester, tricresyl phosphate (2,6- di-tert-butyl-phenyl) 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).
24. according to claim 1,3,4 described in any item polycarbonate compositions, which is characterized in that the component d's is other
Auxiliary agent is selected from one kind or several of stabilizer, retardant synergist, anti-dripping agent, lubricant, release agent, plasticizer, filler, colorant
Kind.
25. a kind of preparation method of such as described in any item polycarbonate compositions of claim 1-24, which is characterized in that including
Following steps:
1) phenol type substances and standard manganese solution and phenyl siloxane are made into the benzene that mass fraction is 12.5ppm-2000ppm
Radical siloxane solution；
2) phenyl siloxane solution is blended in high mixer with polycarbonate, obtains pretreated polycarbonate；
3) after proportionally weighing pretreated polycarbonate, graft copolymer, fire retardant, other auxiliary agents, pass through high mixer
Or mixing machine is completed to be blended, and squeezes out, and crosses water cooling, granulation obtains the polycarbonate compositions of cylindrical particle.
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| WO2019060146A1 (en) * | 2017-09-22 | 2019-03-28 | Sabic Global Technologies B.V. | Process for the manufacture of flame retardant polycarbonate particles and flame retardant polycarbonate particles prepared thereby |
| CN111349304B (en) * | 2020-04-30 | 2023-08-22 | 上海锦湖日丽塑料有限公司 | Polycarbonate styrene resin alloy and preparation method thereof |
| CN111995855B (en) * | 2020-07-16 | 2022-10-14 | 天津金发新材料有限公司 | Flame-retardant PC/ABS composition and preparation method thereof |
| CN115386214B (en) * | 2022-10-09 | 2023-10-17 | 万华化学（宁波）有限公司 | Weather-resistant halogen-free flame-retardant polycarbonate alloy material and preparation method thereof |
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| CN1395592A (en) * | 2000-11-14 | 2003-02-05 | 帝人株式会社 | Aromatic polycarbonate, process for producing the same, and composition containing the same |
| CN101993586A (en) * | 2010-11-30 | 2011-03-30 | 金发科技股份有限公司 | Flame-resistant polycarbonate/ABS (Acrylonitrile Butadiene Styrene) material |
| CN103351463A (en) * | 2008-11-28 | 2013-10-16 | 三菱化学株式会社 | Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article |
| CN103380176A (en) * | 2011-02-16 | 2013-10-30 | 三菱化学株式会社 | Polycarbonate resin composition and molded article |
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| KR102015492B1 (en) * | 2011-05-12 | 2019-08-28 | 사빅 글로벌 테크놀러지스 비.브이. | Amorphous polycarbonate films for capacitors, methods of manufacture, and articles manufactured therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1395592A (en) * | 2000-11-14 | 2003-02-05 | 帝人株式会社 | Aromatic polycarbonate, process for producing the same, and composition containing the same |
| CN103351463A (en) * | 2008-11-28 | 2013-10-16 | 三菱化学株式会社 | Polycarbonate resin, polycarbonate resin composition, optical film, and polycarbonate resin molded article |
| CN101993586A (en) * | 2010-11-30 | 2011-03-30 | 金发科技股份有限公司 | Flame-resistant polycarbonate/ABS (Acrylonitrile Butadiene Styrene) material |
| CN103380176A (en) * | 2011-02-16 | 2013-10-30 | 三菱化学株式会社 | Polycarbonate resin composition and molded article |
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