CN105440624A - Polycarbonate composition and preparation method therefor - Google Patents
Polycarbonate composition and preparation method therefor Download PDFInfo
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- CN105440624A CN105440624A CN201510277668.5A CN201510277668A CN105440624A CN 105440624 A CN105440624 A CN 105440624A CN 201510277668 A CN201510277668 A CN 201510277668A CN 105440624 A CN105440624 A CN 105440624A
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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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- 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
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- 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
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- 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
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Abstract
The present invention discloses a polycarbonate composition. The polycarbonate composition comprises the following components in parts by weight: a, 30 parts to 80 parts of polycarbonate; b, 8 parts to 50 parts of a graft copolymer; c, 5 parts to 25 parts of a flame retardant; and d, 0-10 parts of other auxiliaries, wherein the sum of the weight parts of the components a, b, c, and d is 100 parts. According to the present invention, good flowability of the polycarbonate composition is obtained when the total mixing amount of the phenols and the manganese metal element which are added into the polycarbonate composition are not greater than 500 ppm based on the total weight of the polycarbonate composition, and the polycarbonate composition has color stability and high-gloss before and after long-term thermal oxidizing aging, so that the polycarbonate composition is particularly suitable for use in occasions with relatively high environment requirements. The phenols have a structural formula (1) as shown in the specification, wherein R1 and R5 denote H, alkyl, alkxoy, hydroxy, carboxyl or carbonyl, except a hindered group and an ester group, R2, R3 and R4 denote a substituent containing hydrogen atoms, preferably hydrogen atoms.
Description
Technical field
The present invention relates to engineering plastics technical field, particularly a kind of polycarbonate compositions and preparation method thereof.
Background technology
Polycarbonate has the comparatively characteristic such as high-impact and thermotolerance, for improving its processing characteristics and the shortcoming to notch shock sensitivity, usually rubber-like can be added polymer-modified, as ABS, MBS etc., the PC/ABS alloy being particularly main raw material with PC and ABS is a kind of important engineering plastics, can comprehensive both premium properties, accomplish that physicals and processing characteristics are improved, but due to adding of ABS, in system, double bond can bring the hidden danger of long-term thermal-oxidative aging property and weather resistance, particularly higher occasion is required to environment for use, its surface easily forms defect and its color easily changes.
Patent CN102292393 discloses and uses salt inclusion can improve surface quality after heat wets storage, is therefore suitable for preparing the moulded work with ageing-resistant zero defect A level surface;
Patent CN104271610 discloses and selects the preparation of sodium, magnesium, calcium impurities to have the polymkeric substance that damp and hot storage improves surface afterwards; But above light metal impurity easily forms alkalescence under hygrothermal environment, promote the degraded of polycarbonate, thus after causing it before use, performance degradation and color distortion are comparatively large, less stable in actual applications.
Up to the present, about the composite total amount of phenol type substances and manganese metal element to mobility, the high glossiness of described polycarbonate compositions, and the impact of colour stability has no report.
The present inventor surprisingly finds through great many of experiments, select the composite total amount of adding phenol type substances and manganese metal element in polycarbonate compositions formula based on when being no more than 500ppm in the gross weight of polycarbonate compositions, make the good fluidity of polycarbonate compositions, and there is colour stability and high glossiness before and after long term thermal oxygen aging, be specially adapted to environment for use and require higher occasion.
Summary of the invention
In order to overcome the shortcoming of prior art with not enough, primary and foremost purpose of the present invention is that providing a kind of has excellent mobility, and has the polycarbonate compositions of colour stability and high glossiness before and after long term thermal oxygen aging.
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, comprises following composition:
A, the polycarbonate of 30 parts-80 parts;
B, the graft copolymer of 8 parts-50 parts;
C, the fire retardant of 5 parts-25 parts;
Other auxiliary agent of d, 0-10 part;
Wherein, the weight part sum of a, b, c, d tetra-kinds of components is 100 parts.
Preferably, a kind of polycarbonate compositions, by weight, comprises following composition:
A, the polycarbonate of 30 parts-75 parts;
B, the graft copolymer of 8 parts-35 parts;
C, the fire retardant of 5 parts-23 parts;
Other auxiliary agent of d, 0-10 part;
Wherein, the weight part sum of a, b, c, d tetra-kinds of components is 100 parts;
Composite total amount based on phenol type substances in the gross weight of polycarbonate compositions and manganese metal element is more than or equal to 10ppm and is less than or equal to 500ppm; Wherein the structural formula of phenol type substances is such as formula (1):
formula (1)
Wherein R
1and R
5the hydrogen base of representative except the group that is obstructed, alkyl, alkoxyl group, hydroxyl, carboxyl or carbonyl, ester group, R
2, R
3, R
4represent the substituting group of hydrogen atoms, preferred hydrogen atom.
More preferably, a kind of polycarbonate compositions, by weight, comprises following composition:
A, the polycarbonate of 30 parts-70 parts;
B, the graft copolymer of 8 parts-30 parts;
C, the fire retardant of 5 parts-18 parts;
Other auxiliary agent of d, 0-10 part;
Wherein, the weight part sum of a, b, c, d tetra-kinds of components is 100 parts;
Composite total amount based on phenol type substances in the gross weight of polycarbonate compositions and manganese metal element is more than or equal to 10ppm and is less than or equal to 500ppm; Wherein the structural formula of phenol type substances is such as formula (1):
formula (1)
Wherein R
1and R
5the hydrogen base of representative except the group that is obstructed, alkyl, alkoxyl group, hydroxyl, carboxyl or carbonyl, ester group, R
2, R
3, R
4represent the substituting group of hydrogen atoms, preferred hydrogen atom.
Wherein, the testing method of the content of phenol type substances: after the polycarbonate compositions with electronic balance weighing 2g, sample is put into preset temp 120 DEG C and after the constant temperature oven 2h of temperature stable homogeneous, put into soxhlet type apparatus and carry out methyl alcohol extracting, extraction temperature is 85 DEG C, time is 48h, after extract is placed into constant temperature, 20ul is extracted out by filtering net, with the flow velocity of 10ml/min, to be separated carrying out in extract sample introduction to the adsorption column of C18 by moving phase (methyl alcohol: pure water=90:10) and quantitatively, by setting up 1ppm, 5ppm, after the standardized solution Criterion curve of 10ppm and 20ppm, the content of phenol type substances can be drawn by the specific elution time of standard specimen and calculation by extrapolation.
The testing method of the content of manganese metal element: ICP-MS mixes mark method.
The composite total amount of phenol type substances and manganese metal element is more than 500ppm in based on the gross weight of polycarbonate compositions, due to the small molecules of interference in system, flowing instability and obvious surperficial pit spray can be caused, thus there is the hidden danger of processing stability and surface imperfection.
Preferably, the composite total amount of described phenol type substances and manganese metal element is for being more than or equal to 20ppm and being less than or equal to 400ppm; Be preferably greater than and equal 30ppm and be less than or equal to 300ppm; Be more preferably and be more than or equal to 50ppm and be less than or equal to 200ppm.
Wherein, the composite weight ratio of described phenol type substances and manganese metal element is 2:3-4:3.
Wherein, described polycarbonate is selected from one or more in aromatic copolycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branching polycarbonate, siloxane copolycarbonate; Be preferably aromatic copolycarbonate.
Described polycarbonate is the aromatic copolycarbonate of viscosity-average molecular weight 13000-40000, is more preferably the aromatic copolycarbonate of viscosity-average molecular weight 16000-28000.When viscosity-average molecular weight is in above-mentioned scope, physical strength is good and can keep the formability of excellence.Wherein, viscosity-average molecular weight is by using methylene dichloride to calculate at the soltion viscosity that probe temperature is 25 DEG C as solvent.
The preparation method of above-mentioned polycarbonate can be obtained by interfacial polymerization and ester-interchange method, and can the content of control end hydroxyl during the course.
Wherein, described graft copolymer is selected from one or more of the standby graft copolymer of mass polymerization, emulsion polymerization, bulk-suspension polymerization legal system.
Mass polymerization: comprise colloidal sol, prepolymerization, polymerization, devolatilization and granulation five steps: by rubber solution in ethylbenzene and vinylbenzene, add monomer according to formula ratio and be made into stock liquid, prepolymerization is carried out by the stock liquid prepared input prepolymerization kettle, in the course of the polymerization process, grafting rubbers monomer, monomer copolymerization simultaneously, separate from solution, form the discontinuous phase be dispersed in stock liquid in external phase, after there is abundant monomer polymerization, the multipolymer of discontinuous phase becomes external phase, the rubber of grafting formed discontinuous phase be dispersed in continuous print multipolymer mutually in, complete phase in version, eventually pass further polymerization, vacuum outgas, extrude, cooling and pelletizing obtain end article,
Bulk-suspension polymerization method: regulate rubber and monomer solution according to formula, and notice adds polymerization regulator and radical initiator, monomer mixture is carried out mass polymerization at 80 DEG C-120 DEG C, constantly stirs in polymerization process, and deionized water and suspension agent are joined in mixture, mixture is disperseed, then utilizing free radical catalyst to carry out suspension polymerization, through condensing after obtaining certain polymerization degree, filtering, washing, dewaters and after drying, granulation obtains goods;
Emulsion polymerization: rubber passes through at initiator, deionized water, emulsifying agent and linking agent, and polymerization temperature controls at 50 DEG C-80 DEG C, monomer mixture is added to elastomer latex and carries out grafting, finally wash, dewaters and after drying, granulation obtains goods.
Wherein, described graft copolymer, by weight, is selected from the graft copolymer comprising and b.1 b.2 going up as follows:
B.1, the mixture b.1.1 and b.1.2 of 5 parts-95 parts:
B.1.1,50 parts-95 parts vinylbenzene, styrene derivatives is as alpha-methyl styrene, to phenmethyl vinylbenzene, divinylstyrene, one or more of methacrylic acid C1-C8-alkyl ester, vinylformic acid C1-C8-alkyl ester, dimethyl siloxane, phenyl siloxane, many alkylsiloxanes;
B.1.2,5 parts-50 parts vinyl cyanide, methacrylonitrile, methacrylic acid C1-C8-alkyl ester, vinylformic acid C1-C8-alkyl ester one or more;
B.2,5 parts-95 parts grafting rubbers basis as polyhutadiene, polyisoprene, styrene butadiene random copolymer and segmented copolymer, acrylonitrile-butadiene random copolymers and segmented copolymer, polyhutadiene and polyisoprene copolymers, ethene and a-olefin copolymer, ethene and a-unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene terpolymer, acryloyl rubber, organopolysiloxane elastomer one or more.
More preferably, described graft copolymer is selected from one or more in acrylonitritrile-styrene resin AS, acrylonitrile-butadiene-phenylethene grafted copolymer ABS, methyl methacrylate-nitrile-butadiene-styrene multipolymer MABS, acrylonitrile-styrene-acrylic terpolymer ASA, MBS graft copolymer MBS;
More preferably acrylonitrile-butadiene-phenylethene grafted copolymer ABS, wherein the weight fraction of divinyl rubber matter polymkeric substance in ABS is 5wt%-50wt%, and size distribution can be uniform or have two or with many distributions of upward peak.
Preferably, described graft copolymer, by weight, is selected from the graftomer comprising and b.1 b.2 going up as follows:
B.1, the mixture b.1.1 and b.1.2 of 30 parts-80 parts:
B.1.1,50 parts-95 parts vinylbenzene, styrene derivatives is as alpha-methyl styrene, to phenmethyl vinylbenzene, divinylstyrene, one or more of methacrylic acid C1-C8-alkyl ester, vinylformic acid C1-C8-alkyl ester, dimethyl siloxane, phenyl siloxane, many alkylsiloxanes;
B.1.2,5 parts-50 parts vinyl cyanide, methacrylonitrile, methacrylic acid C1-C8-alkyl ester, vinylformic acid C1-C8-alkyl ester one or more;
B.2,20 parts-70 parts containing grafting rubbers basis as polyhutadiene, polyisoprene, styrene butadiene random copolymer and segmented copolymer, acrylonitrile-butadiene random copolymers and segmented copolymer, polyhutadiene and polyisoprene copolymers, ethene and a-olefin copolymer, ethene and a-unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene terpolymer, acryloyl rubber, organopolysiloxane elastomer one or more.
More preferably, described graft copolymer is selected from one or more in acrylonitritrile-styrene resin AS, acrylonitrile-butadiene-phenylethene grafted copolymer ABS, methyl methacrylate-nitrile-butadiene-styrene multipolymer MABS, acrylonitrile-styrene-acrylic terpolymer ASA, MBS graft copolymer MBS; The wherein preferred 0.1um-0.5um of the particle diameter of MBS, the preferred 0.1um-2um of mass polymerization ABS particle diameter, the preferred 0.05um-0.2um of emulsion polymerization ABS particle diameter.
More preferably acrylonitrile-butadiene-phenylethene grafted copolymer ABS, wherein the weight fraction of divinyl rubber matter polymkeric substance in ABS is 5wt%-50wt%, and size distribution can be uniform or have two or with many distributions of upward peak.
Wherein, described fire retardant is selected from halogenated flame retardant or halogen-free flame retardants, preferred halogen-free flame retardants; Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymer, is preferably brominated Polystyrene; Described halogen-free flame retardants is selected from one or more in the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant or nitrogenous and phosphorus, is preferably phosphonium flame retardant.
Preferably, described phosphonium flame retardant is selected from Triphenyl phosphate, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate xylyl ester, tricresyl phosphate (2, 4, 6-trimethylphenyl) ester, tricresyl phosphate (2, 4-di-tert-butyl-phenyl) ester, tricresyl phosphate (2, 6-di-tert-butyl-phenyl) ester, Resorcinol two (diphenyl phoshate), Resorcinol two (diphenyl phoshate), dihydroxyphenyl propane-bis-(diphenyl phoshate), Resorcinol two (2, 6-di-tert-butyl-phenyl phosphoric acid ester), Resorcinol two (2, 6-dimethylphenylphosphate) one or more.
Other auxiliary agent can also be comprised in this polymer blend, as be selected from stablizer, retardant synergist, anti-dripping agent, lubricant, releasing agent, softening agent, filler, tinting material one or more.
Suitable stablizer comprises organophosphite, as triphenyl phosphite, tricresyl phosphite-(2, 6-3,5-dimethylphenyl) ester, tricresyl phosphite-nonyl phenylester, dimethylbenene phosphonate, trimethyl phosphite 99 etc., organophosphite, alkylating monohydric phenol or polyphenol, the alkylation reaction product of polyphenol and diene, the butylation reaction product of p-cresol or Dicyclopentadiene (DCPD), alkylating hydroquinones, hydroxylated thiodiphenvl ethers, alkylidene group-bis-phenol, benzyl compounds, polyol ester class, benzotriazole category, one or more combinations of benzophenone.
Suitable softening agent is phthalic ester.
Suitable releasing agent comprises metallic stearic salt, allcyl stearate class, stearic acid pentaerythritol esters, paraffin, montanin wax etc.
Suitable tinting material comprises various pigment, dyestuff.
The preparation method of above-mentioned polycarbonate compositions, comprises the steps:
1) be the phenyl siloxane solution of 12.5ppm-2000ppm by phenol type substances and standard manganese solution and phenyl siloxane according to proportioning massfraction;
2) phenyl siloxane solution and polycarbonate are carried out blended in high mixer, obtain pretreated polycarbonate;
3) after pretreated polycarbonate, graft copolymer, fire retardant, other auxiliary agent proportionally being weighed, complete blended, extrude by high mixer or mixing machine, cross water cooling, granulation obtains the polycarbonate compositions of cylindrical particle.
Polycarbonate compositions of the present invention is owing to having excellent long-term thermal stability and weathering resistance, the mechanical property of outward appearance zero defect and excellence, can be used for the Application Areas of open air and indoor, the case member of such as all kinds and size, household electrical appliance are as televisor, printer, modem shell, display casing etc., or the trolley part used out of doors, the shell of building field or lid, and electrical appliance shell and frame.
The present invention compared with prior art, has following beneficial effect:
1) the present invention is by carrying out pre-treatment with phenol type substances and manganese metal element to polycarbonate, manganese metal element plays reductive action in system, can Balance Iron atom or its compound to the Degradation of polymkeric substance, the phenol type substances simultaneously retained in trace level can catch polycarbonate under post-treatment and shaping middle hot oxygen shear the synergy of the active site formed, can phenolic hydroxyl group better in stabilising system, make the mobility that polycarbonate keeps excellent, the general phenol type substances that adopts is avoided in prior art to form phenolic hydroxyl group and cannot the defect of phenol type substances of residual traces as end-capping reagent in building-up process.
2) the present invention is by selecting the composite total amount of adding phenol type substances and manganese metal element in polycarbonate compositions formula based on when being no more than 500ppm in the gross weight of polycarbonate compositions, make the good fluidity of polycarbonate compositions, and there is colour stability and high glossiness before and after long term thermal oxygen aging, be specially adapted to environment for use and require higher occasion.
Embodiment
Further illustrate the present invention below by embodiment, following examples are the present invention's preferably embodiment, but embodiments of the present invention are not by the restriction of following embodiment.
The testing standard of each performance or method:
The measuring method of content of phenol type substances: after the polycarbonate compositions with electronic balance weighing 2g, sample is put into preset temp 120 DEG C and after the constant temperature oven 2h of temperature stable homogeneous, put into soxhlet type apparatus and carry out methyl alcohol extracting, extraction temperature is 85 DEG C, time is 48h, after extract is placed into constant temperature, 20ul is extracted out by filtering net, with the flow velocity of 10ml/min, to be separated carrying out in extract sample introduction to the adsorption column of C18 by moving phase (methyl alcohol: pure water=90:10) and quantitatively, by setting up 1ppm, 5ppm, after the standardized solution Criterion curve of 10ppm and 20ppm, the content of phenol type substances can be drawn by the specific elution time of standard specimen and calculation by extrapolation,
The testing method of manganese metal constituent content: ICP-MS mixes mark method;
The measuring method of newton's index: die orifice length-to-diameter ratio is 20, shearing steady temperature is 260 DEG C, and shearing rate is 100s
-1-10000s
-1, warm up time 300s, after obtain the curve of shearing rate and shear-stress after exponentiation n obtain newton's index.Wherein, the method for calculation of newton's index: do power matching by shearing rate and shear-stress, obtain fitting formula
y=ax n ,the variance R of fitting formula
2be greater than 0.99; Wherein, n is newton's index, and newton's index is less, and its processing characteristics is better, and newton's index reduces by 0.01, and its processing characteristics has clear improvement.
The measuring method of long term thermal oxygen aging colour stability: 80 DEG C of baking oven hot oxygen colour table colour-change grades, 1 grade is best, and 5 grades is the poorest;
The measuring method of glossiness: the glossiness measuring 60 ° of angles after colour table fixed temperature and humidity places 48h with vancometer, surface gloss grade, 1 grade is best, and without any defect, 2 grades have slight spray pit, and 3 grades is that surface gloss is poor, obvious spray and pit;
The polycarbonate used in the present invention:
Component a-1:PC1300-10(Korea S LG);
Component a-2:PC1225(Japan Supreme Being people);
The phenol type substances used in the present invention:
The phenol type substances used in the present invention:
P-methyl phenol class material: (Aladdin);
Dimethyl benzene phenols material: (Aladdin);
Standard manganese solution: (national iron and steel research institute)
The graft copolymer used in the present invention:
Components b-1:ABS1 emulsion method 757(Taiwan is very beautiful);
Components b-2:ABS2 substance law 8391(Shanghai Gaoqiao);
Components b-3:MBSEM500(Korea S LG);
The fire retardant used in the present invention:
Amount of component b: BDP, dihydroxyphenyl propane-bis-(diphenyl phoshate) (Ai Dike);
Other auxiliary agent used in the present invention:
Two (2, the 6-di-t-butyl-4-aminomethyl phenyl) pentaerythritol diphosphate of component d-1:PEP-36() as stablizer;
Component d-2:C wax is as lubricant;
Component d-3:PTFE(tetrafluoroethylene) as anti-dripping agent;
Component d-4: tinting material carbon black M717.
embodiment 1-12 and comparative example 1-8: the preparation of polycarbonate compositions
Phenol type substances and standard manganese solution and phenyl siloxane are made into the phenyl siloxane solution that massfraction is 12.5ppm-2000ppm; Phenyl siloxane solution and polycarbonate are carried out blended in high mixer, obtains pretreated polycarbonate; After pretreated polycarbonate, graft copolymer, fire retardant, other auxiliary agent proportionally being weighed by the formula of table 1, complete blended, extrude by high mixer or mixing machine, cross water cooling, granulation obtains the polycarbonate compositions of cylindrical particle; Test the mobility (newton's index) of polycarbonate compositions, long term thermal oxygen aging colour stability (aberration) and glossiness, data are in table 1.
The concrete proportioning (weight part) of table 1 embodiment 1-12 and comparative example 1-8 and test performance result thereof
| 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 | ||||||
| Components b-1 | 50 | 15 | 8 | 50 | 15 | 8 | ||||||
| Components b-2 | 30 | 15 | 30 | 15 | ||||||||
| Components b-3 | 20 | 20 | ||||||||||
| Amount of component b | 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 |
| Dihydroxyphenyl propane (ppm) | ||||||||||||
| Hindered phenol content (ppm) | ||||||||||||
| Newton's 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 thermal oxygen aging colour stable grade | 2 | 2 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 1 | 2 | 1 |
| Surface luster 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 | ||||||||
| Components b-1 | 50 | 15 | 8 | |||||
| Components b-2 | 30 | 15 | 15 | 15 | ||||
| Components b-3 | 20 | |||||||
| Amount of component b | 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 |
| Dihydroxyphenyl propane (ppm) | 18 | |||||||
| Hindered phenol content (ppm) | 18 | |||||||
| Newton's index | 0.5938 | 0.5383 | 0.5402 | 0.5903 | 0.5672 | 0.5231 | 0.5432 | 0.6063 |
| Long term thermal oxygen aging colour stable grade | 5 | 4 | 4 | 5 | 3 | 5 | 5 | 5 |
| Surface luster grade | 3 | 3 | 3 | 3 | 3 | 3 | 3 | 3 |
As can be seen from the embodiment of table 1 and comparative example relatively: select the composite total amount of adding phenol type substances and manganese metal element in polycarbonate compositions formula based on when being no more than 500ppm in the gross weight of polycarbonate compositions, the good fluidity of polycarbonate compositions, and there is colour stability and high glossiness before and after long term thermal oxygen aging, be specially adapted to environment for use and require higher occasion.
Claims (14)
1. a polycarbonate compositions, by weight, comprises following composition:
A, the polycarbonate of 30 parts-80 parts;
B, the graft copolymer of 8 parts-50 parts;
C, the fire retardant of 5 parts-25 parts;
Other auxiliary agent of d, 0-10 part;
Wherein, the weight part sum of a, b, c, d tetra-kinds of components is 100 parts.
2. a polycarbonate compositions as claimed in claim 1, by weight, comprises following composition:
A, the polycarbonate of 30 parts-75 parts;
B, the graft copolymer of 8 parts-35 parts;
C, the fire retardant of 5 parts-23 parts;
Other auxiliary agent of d, 0-10 part;
Wherein, the weight part sum of a, b, c, d tetra-kinds of components is 100 parts;
Composite total amount based on phenol type substances in the gross weight of polycarbonate compositions and manganese metal element is more than or equal to 10ppm and is less than or equal to 500ppm; Wherein the structural formula of phenol type substances is such as formula (1):
formula (1)
Wherein R
1and R
5the hydrogen base of representative except the group that is obstructed, alkyl, alkoxyl group, hydroxyl, carboxyl or carbonyl, ester group, R
2, R
3, R
4represent the substituting group of hydrogen atoms, preferred hydrogen atom.
3. a polycarbonate compositions as claimed in claim 1, by weight, comprises following composition:
A, the polycarbonate of 30 parts-70 parts;
B, the graft copolymer of 8 parts-30 parts;
C, the fire retardant of 5 parts-18 parts;
Other auxiliary agent of d, 0-10 part;
Wherein, the weight part sum of a, b, c, d tetra-kinds of components is 100 parts;
Composite total amount based on phenol type substances in the gross weight of polycarbonate compositions and manganese metal element is more than or equal to 10ppm and is less than or equal to 500ppm; Wherein the structural formula of phenol type substances is such as formula (1):
formula (1)
Wherein R
1and R
5the hydrogen base of representative except the group that is obstructed, alkyl, alkoxyl group, hydroxyl, carboxyl or carbonyl, ester group, R
2, R
3, R
4represent the substituting group of hydrogen atoms, preferred hydrogen atom.
4. the polycarbonate compositions according to Claims 2 or 3, is characterized in that, the composite total amount of described phenol type substances and manganese metal element is for being more than or equal to 20ppm and being less than or equal to 400ppm; Be preferably greater than and equal 30ppm and be less than or equal to 300ppm; Be more preferably and be more than or equal to 50ppm and be less than or equal to 200ppm.
5. the polycarbonate compositions according to Claims 2 or 3, is characterized in that, the composite weight ratio of described phenol type substances and manganese metal element is 2:3-4:3.
6. the polycarbonate compositions according to any one of claim 1-3, it is characterized in that, described polycarbonate is selected from one in aromatic copolycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branching polycarbonate, siloxane copolycarbonate or one; Be preferably aromatic copolycarbonate.
7. polycarbonate compositions according to claim 6, is characterized in that, described aromatic copolycarbonate is selected from the aromatic copolycarbonate of viscosity-average molecular weight 13000-40000, is preferably the aromatic copolycarbonate of viscosity-average molecular weight 16000-28000.
8. the polycarbonate compositions according to any one of claim 1-3, is characterized in that, described graft copolymer is selected from one or more of the standby graft copolymer of mass polymerization, emulsion polymerization, bulk-suspension polymerization legal system.
9. the polycarbonate compositions according to any one of claim 1-3, is characterized in that, described graft copolymer, by weight, is selected from the graft copolymer comprising and b.1 b.2 going up as follows
B.1, the mixture b.1.1 and b.1.2 of 5 parts-95 parts:
B.1.1,50 parts-95 parts vinylbenzene, styrene derivatives is as alpha-methyl styrene, to phenmethyl vinylbenzene, divinylstyrene, one or more of methacrylic acid C1-C8-alkyl ester, vinylformic acid C1-C8-alkyl ester, dimethyl siloxane, phenyl siloxane, many alkylsiloxanes;
B.1.2,5 parts-50 parts vinyl cyanide, methacrylonitrile, methacrylic acid C1-C8-alkyl ester, vinylformic acid C1-C8-alkyl ester one or more;
B.2,5 parts-95 parts polyhutadiene, polyisoprene, styrene butadiene random copolymer and segmented copolymer, acrylonitrile-butadiene random copolymers and segmented copolymer, polyhutadiene and polyisoprene copolymers, ethene and a-olefin copolymer, ethene and a-unsaturated carboxylic acid ester copolymer, ethylene-propylene-non-conjugated diene terpolymer, acryloyl rubber, organopolysiloxane elastomer one or more.
10. polycarbonate compositions according to claim 9, described graft copolymer is selected from one or more in acrylonitritrile-styrene resin AS, acrylonitrile-butadiene-phenylethene grafted copolymer ABS, methyl methacrylate-nitrile-butadiene-styrene multipolymer MABS, acrylonitrile-styrene-acrylic terpolymer ASA, MBS graft copolymer MBS; Be preferably acrylonitrile-butadiene-phenylethene grafted copolymer ABS; The wherein preferred 0.1um-0.5um of the particle diameter of MBS, the preferred 0.1um-2um of mass polymerization ABS particle diameter, the preferred 0.05um-0.2um of emulsion polymerization ABS particle diameter.
11. polycarbonate compositions according to any one of claim 1-3, it is characterized in that, described fire retardant is selected from halogenated flame retardant or halogen-free flame retardants, preferred halogen-free flame retardants; Described halogenated flame retardant is selected from one or more of brominated Polystyrene, brominated polyphenylether, brominated bisphenol a type epoxy resin, brominated styrene-copolymer-maleic anhydride, brominated epoxy resin, bromination phenoxy resin, decabromodiphynly oxide, decabromodiphenyl, brominated polycarbonate, perbromo-three cyclopentadecane or brominated aromatic cross-linked polymer, is preferably brominated Polystyrene; Described halogen-free flame retardants is selected from one or more in the fire retardant of nitrogenous flame ratardant, phosphonium flame retardant, nitrogenous and phosphorus, is preferably phosphonium flame retardant.
12. polycarbonate compositions according to claim 11, it is characterized in that, described phosphonium flame retardant is selected from Triphenyl phosphate, lindol, tricresyl phosphate base diphenyl, tricresyl phosphate xylyl ester, tricresyl phosphate (2, 4, 6-trimethylphenyl) ester, tricresyl phosphate (2, 4-di-tert-butyl-phenyl) ester, tricresyl phosphate (2, 6-di-tert-butyl-phenyl) ester, Resorcinol two (diphenyl phoshate), Resorcinol two (diphenyl phoshate), dihydroxyphenyl propane-bis-(diphenyl phoshate), Resorcinol two (2, 6-di-tert-butyl-phenyl phosphoric acid ester), Resorcinol two (2, 6-dimethylphenylphosphate) one or more.
13. polycarbonate compositions according to any one of claim 1-3, is characterized in that, other auxiliary agent of described component d be selected from stablizer, retardant synergist, anti-dripping agent, lubricant, releasing agent, softening agent, filler, tinting material one or more.
The preparation method of 14. 1 kinds of polycarbonate compositions as described in any one of claim 1-13, is characterized in that, comprises the steps:
1) phenol type substances and standard manganese solution and phenyl siloxane are made into the phenyl siloxane solution that massfraction is 12.5ppm-2000ppm;
2) phenyl siloxane solution and polycarbonate are carried out blended in high mixer, obtain pretreated polycarbonate;
3) after pretreated polycarbonate, graft copolymer, fire retardant, other auxiliary agent proportionally being weighed, complete blended, extrude by high mixer or mixing machine, cross water cooling, granulation obtains the polycarbonate compositions of cylindrical particle.
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| WO2016188474A1 (en) * | 2015-05-27 | 2016-12-01 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor |
| WO2016197907A1 (en) * | 2015-06-09 | 2016-12-15 | 金发科技股份有限公司 | Polycarbonate composition and preparation method therefor |
| 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 |
| CN111349304A (en) * | 2020-04-30 | 2020-06-30 | 上海锦湖日丽塑料有限公司 | Polycarbonate styrene resin alloy and preparation method thereof |
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| 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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| CN105440624B (en) * | 2015-05-27 | 2019-05-07 | 金发科技股份有限公司 | A kind of polycarbonate compositions 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 |
| 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 |
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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 |
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