CN105315641A - Polycarbonate composition and preparation method thereof - Google Patents
Polycarbonate composition and preparation method thereof Download PDFInfo
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- CN105315641A CN105315641A CN201510277632.7A CN201510277632A CN105315641A CN 105315641 A CN105315641 A CN 105315641A CN 201510277632 A CN201510277632 A CN 201510277632A CN 105315641 A CN105315641 A CN 105315641A
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Abstract
The invention discloses a polycarbonate composition. The polycarbonate composition is prepared from, by weight, 30-87 parts of polycarbonate a, 8-50 parts of grafted copolymers b, 5-25 parts of fire retardant c and 0-10 parts of other auxiliaries d. The weight sum of the four components of a, b, c and d is 100. When the content of phenol type matter added to a formulation of the polycarbonate composition is selected to be not larger than 80 ppm in the total weight of the polycarbonate composition, the long-term thermo-oxidative aging and weather fastness performance of the polycarbonate composition can be obviously improved, the polycarbonate composition is especially suitable for occasions with high use environment requirements, and the structural formula of the phenol type matter is shown in the formula (1) shown in the specification, wherein R1 and R5 in the formula (1) represent the hydrogen group, the alkyl group, alkoxy, hydroxyl, carboxyl or carbonyl and the ester group except for blocked groups, and R2, R3 and R 4 represent substitute groups containing hydrogen atoms, preferably the 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, ACR and silicon rubber 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.
Patent US20130289177A1 discloses the PC/ABS composition with good heat and chemical stability, the use of dihydroxyphenyl propane adds the colour stability of composition, but dihydroxyphenyl propane is defectiveness in environmental protection, dihydroxyphenyl propane can to performance simultaneously, and particularly impact property brings hidden danger.
Patent CN1218070 discloses the ABS selecting emulsion method to synthesize can improve resistance toheat, but the use only limiting emulsion method ABS is unpractiaca in a lot of application scenario, and rubber size distribution is different in emulsion method ABS, cause physical strength stability inadequate, also can be restricted in the application.
Up to the present, the content about phenol type substances has no report to the long term thermal oxygen aging of described polycarbonate compositions and the impact of weather resistance.
The present inventor surprisingly finds through great many of experiments, select the content adding phenol type substances in polycarbonate compositions formula based on when being no more than 80ppm in the gross weight of polycarbonate compositions, long term thermal oxygen aging and the weather resistance of polycarbonate compositions can be significantly improved after pre-treatment and through the phenol type substances of modified trace level retention, and be specially adapted to the higher occasion of environment for use requirement.
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 the polycarbonate compositions providing a kind of long term thermal oxygen aging and weather resistance to significantly improve.
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-87 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 50 parts-75 parts;
B, the graftomer of 8 parts-35 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,
Be less than or equal to 80ppm based on the content of phenol type substances in the gross weight of polycarbonate compositions and be more than or equal to 0.1ppm;
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 50 parts-70 parts;
B, the graftomer 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,
Be less than or equal to 80ppm based on the content of phenol type substances in the gross weight of polycarbonate compositions and be more than or equal to 0.1ppm; 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.
When the content of phenol type substances is more than 80ppm in based on the gross weight of polycarbonate compositions, the goods colour stability obtained is poor, and yellowness index is high, and because small-molecule substance can produce surface appearance defects in the course of processing.
Preferably, be less than or equal to 70ppm based on the content of phenol type substances in the gross weight of polycarbonate compositions and be more than or equal to 10ppm; Be more preferably and be less than or equal to 50ppm and be more than or equal to 25ppm.
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.
Preferably, 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 refer to rubber polymer exist under pass through styrene monomer, the polymkeric substance of acrylic monomer and silicon class monomer copolymerization and acquisition, 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 pre-polymerization axe, 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 add polymerization regulator and radical initiator simultaneously; 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 graftomer 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.
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; Wherein, the preferred 0.1um-0.5um of 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) phenol type substances and methylsiloxane are made into the phenol type substances methylsiloxane solution that massfraction is 0.15ppm-300ppm;
2) phenol type substances methylsiloxane 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 to polycarbonate resin, the phenol type substances retained through modification trace level after pre-treatment can catch polycarbonate and shear at post-treatment and shaping middle hot oxygen the active site formed, stablize phenolic hydroxyl group, the mobility simultaneously making polycarbonate keep excellent, avoids the general phenol type substances that adopts 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 content adding phenol type substances in polycarbonate compositions formula based on when being no more than 80ppm in the gross weight of polycarbonate compositions, the phenol type substances retained through modification trace level after pre-treatment can significantly improve long term thermal oxygen aging and the weather resistance of polycarbonate compositions, is specially adapted to environment for use and requires 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 measuring method of UV aging resistance chromatic aberration: under the processing temperature of polycarbonate compositions, injection moulding is carried out to this combination room, preparing thickness is 2mm, width is 40nn and length is the plate of 100mm, and mold temperature set is 100 DEG C, sheet material is put ageing oven standard into and is tested according to ISO4892, digestion time is defined as 150h, aging rear use " SM color computer " (manufacture of SUGA testing tool company), by the method proposed in JISZ8730, determine the brightness (value: L) of plate, red (value: a), yellow (value: b).Chromatic aberration is calculated by following equation:
Chromatic aberration=100-[(100-L) 2+a2+b2] 1/2 aberration is larger, and colour stability is poorer.；
The measuring method of 150 DEG C of impact property conservation rate 500h: 80 tons of injection moulding machines that test bars is manufactured by Nissei Plastic Industrial Co., Ltd, after obtaining under the condition of barrel temperature 280 DEG C with die temperature 100 DEG C, according to ASTMD265, use lzod impact tester (Toyo Co., Ltd.'s essence mechanism is done manufactured), measure notched Ai Zuode impact value, put into after preset temp is the aging 500h of constant temperature oven of 150 DEG C by batten, according to aforesaid testing method record aging after Ai Zuode impact value, 150 DEG C of impact property conservation rates are obtained according to the calculation formula of conservation rate, numerical value is larger, property retention is better.
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: phenol: (Shanghai TCI);
P-methyl phenol class material: (Aladdin);
Dimethyl benzene phenols material: (Aladdin); 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:
Component d-1:PTFE(tetrafluoroethylene) as anti-dripping agent;
Component d-2:PETS(pentaerythritol stearate) as releasing agent.Wherein d1+d2 constant add-on in formula is 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 methylsiloxane solution that massfraction is 0.15ppm-300ppm; Phenol type substances methylsiloxane 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 150 DEG C of impact property conservation rates (0h, 150h) of polycarbonate compositions and UV aging resistance chromatic aberration (150h), data are in table 1.
The concrete proportioning (weight part) of table 1 embodiment 1-10 and comparative example 1-11 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 | |
| Component a-1 | 30 | 51 | 64 | 69 | 70 | 87 | ||||
| Component a-2 | 51 | 64 | 69 | 70 | ||||||
| Components b-1 | 50 | 15 | 11 | |||||||
| Components b-2 | 30 | 15 | 30 | 15 | ||||||
| Components b-3 | 20 | 20 | 15 | |||||||
| Amount of component b | 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 aging resistance chromatic aberration (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 | |||||||||||
| Components b-1 | 50 | 8 | 15 | 15 | 15 | 15 | |||||
| Components b-2 | 60 | 30 | 15 | ||||||||
| Components b-3 | 5 | 20 | |||||||||
| Amount of component b | 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 aging resistance chromatic aberration (500h) | 50 | 32 | 27 | 14 | 33 | 20 | 30 | 42 | 33 | 53 | 62 |
As can be seen from Table 1, select the content adding phenol type substances in polycarbonate compositions formula based on when being no more than 80ppm in the gross weight of polycarbonate compositions, the phenol type substances retained through modification trace level after pre-treatment can significantly improve long term thermal oxygen aging and the weather resistance of polycarbonate compositions.
Claims (13)
1. a polycarbonate compositions, by weight, comprises following composition:
A, the polycarbonate of 30 parts-87 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 50 parts-75 parts;
B, the graftomer of 8 parts-35 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,
Be less than or equal to 80ppm based on the content of phenol type substances in the gross weight of polycarbonate compositions and be more than or equal to 0.1ppm;
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 50 parts-70 parts;
B, the graftomer 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,
Be less than or equal to 80ppm based on the content of phenol type substances in the gross weight of polycarbonate compositions and be more than or equal to 0.1ppm;
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, is less than or equal to 70ppm and is more than or equal to 10ppm based on the content of phenol type substances in the gross weight of polycarbonate compositions; Preferably be less than or equal to 50ppm and be more than or equal to 25ppm.
5. the polycarbonate compositions according to any one of claim 1-3, it is characterized in that, described polycarbonate is selected from one or more in aromatic copolycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branching polycarbonate, siloxane copolycarbonate; Be preferably aromatic copolycarbonate.
6. the polycarbonate compositions according to any one of claim 1-3, is characterized in that, described polycarbonate is the aromatic copolycarbonate of viscosity-average molecular weight 13000-40000, is preferably the aromatic copolycarbonate of viscosity-average molecular weight 16000-28000.
7. 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.
8. the polycarbonate compositions according to any one of claim 1-3, is characterized in that, 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 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.
9. polycarbonate compositions according to claim 8, it is characterized in that, 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; Wherein, the particle diameter of MBS preferably at 0.1um-0.5um, the preferred 0.1um-2um of mass polymerization ABS particle diameter, the preferred 0.05um-0.2um of emulsion polymerization ABS particle diameter.
10. the polycarbonate compositions according to any one of claim 1-3, 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 or nitrogenous and phosphorus, is preferably phosphonium flame retardant.
11. polycarbonate compositions according to claim 10, 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.
12. 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 13. 1 kinds of polycarbonate compositions as described in any one of claim 1-12, is characterized in that, comprises the steps:
1) phenol type substances and methylsiloxane are made into the phenol type substances methylsiloxane solution that massfraction is 0.15ppm-300ppm;
2) phenol type substances methylsiloxane 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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| CN107793723A (en) * | 2016-11-25 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793722A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793724A (en) * | 2016-11-29 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793725A (en) * | 2016-11-30 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793721A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| WO2023160183A1 (en) * | 2022-02-25 | 2023-08-31 | 金发科技股份有限公司 | Polycarbonate composition, and preparation method therefor and use thereof |
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| CN107793722A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793721A (en) * | 2016-11-22 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793723A (en) * | 2016-11-25 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN107793724A (en) * | 2016-11-29 | 2018-03-13 | 金发科技股份有限公司 | A kind of polycarbonate compositions and preparation method thereof |
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