CN105315642A - Polycarbonate composition and preparation method thereof - Google Patents
Polycarbonate composition and preparation method thereof Download PDFInfo
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- CN105315642A CN105315642A CN201510277653.9A CN201510277653A CN105315642A CN 105315642 A CN105315642 A CN 105315642A CN 201510277653 A CN201510277653 A CN 201510277653A CN 105315642 A CN105315642 A CN 105315642A
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Abstract
The invention discloses a polycarbonate composition. The polycarbonate composition is prepared from, by weight, 44-85 parts of polycarbonate a, 8-50 parts of rubber-modified graft polymers b and 5-25 parts of fire retardant c, wherein the weight percentage sum of the three components of a, b and c is 100 wt%. When the special-content rubber-modified graft polymers pretreated through a 0.001 wt%-1 wt% phenol type matter methanol solution is selected to be added to the formulation of the polycarbonate composition, the obtained polycarbonate composition has excellent low-temperature toughness and high glossiness and is especially suitable for occasions with high use environment requirements; the structural formula of the phenol type matter is shown in the formula (1) shown in the specification, 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 conventional graftomer can be added, 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, be usually used in electronic apparatus shell and office material.The polycarbonate of current routine and can meet conventional toughness reguirements based on the polycarbonate compositions of ABS toughening modifying, can not meet the requirement of low-temperature flexibility; At present in order to obtain higher low-temperature flexibility, most of patent is all the multipolymer adding siliceous class, as patent CN103958573; But when injection product, due to the restriction of mobility, often meeting glossiness is inadequate, and produce defect, if select low-molecular-weight silicone resin, although can improve mobility a little, low-temperature flexibility can incur loss again.
Up to the present, the graftomer about the pretreated modified rubber of phenol type substances methanol solution of interpolation 0.001wt%-1wt% have not been reported with the impact of the low-temperature flexibility and glossiness of improving described polycarbonate compositions.
The present inventor surprisingly finds through great many of experiments, when selecting the graftomer of the pretreated modified rubber of phenol type substances methanol solution with 0.001wt%-1wt% adding certain content in polycarbonate compositions formula, the polycarbonate compositions obtained has excellent low-temperature flexibility and high glossiness, is specially adapted to environment for use and requires higher occasion.
Summary of the invention
In order to the shortcoming overcoming prior art is with not enough, the object of the present invention is to provide and a kind of there is excellent low-temperature flexibility and the polycarbonate compositions of high glossiness.
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 44 parts-85 parts;
B, the graftomer of modified rubber of 8 parts-50 parts;
C, the fire retardant of 5 parts-25 parts;
Wherein, the weight percent sum of a, b, c tri-kinds of components is 100wt%.
Preferably, a kind of polycarbonate compositions, by weight percentage, comprises following composition:
A, the polycarbonate of 55 parts-80 parts;
B, the graftomer of modified rubber of 8 parts-50 parts;
C, the fire retardant of 5 parts-20 parts;
Wherein, the weight percent sum of a, b, c tri-kinds of components is 100wt%,
The graftomer of described modified rubber is made up of one or more mixtures in component I and/or component I I:
Component I: with the graftomer of the pretreated modified rubber of phenol type substances methanol solution of 0.001wt%-1wt%;
Component I I: the graftomer not making pretreated modified rubber;
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 percentage, comprises following composition:
A, the polycarbonate of 55 parts-80 parts;
B, the graftomer of modified rubber of 10 parts-40 parts;
C, the fire retardant of 5 parts-20 parts;
Wherein, the weight percent sum of a, b, c tri-kinds of components is 100wt%,
The graftomer of described modified rubber is made up of one or more mixtures in component I and/or component I I:
Component I: with the graftomer of the pretreated modified rubber of phenol type substances methanol solution of 0.001wt%-1wt%;
Component I I: the graftomer not making pretreated modified rubber;
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.
In the graftomer of described modified rubber, the per-cent that component I accounts for the graftomer gross weight of modified rubber is 30wt%-50wt%; The per-cent that component I I accounts for the graftomer gross weight of modified rubber is 50wt%-70wt%.
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.
In the graftomer of described modified rubber, the second-order transition temperature <10 DEG C of component I.
The testing method of second-order transition temperature: the graftomer (about 10 milligrams) of modified rubber is put into a crucible; with differential scanning calorimeter (DSC-2C; PerKinElmer company manufactures) make DSC curve; temperature rises to preset temp with the temperature rise rate of 5 DEG C/min from room temperature; moving phase is nitrogen gas stream protection, and second-order transition temperature is the temperature starting to raise on DSC curve.
Wherein, the graftomer of described modified rubber is selected from one or more of the graftomer of the standby modified rubber 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, the graftomer of described modified rubber, 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 containing 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.
Preferably, the graftomer of described modified rubber 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 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.
Wherein, described polycarbonate is selected from one or more in aromatic copolycarbonate, aliphatic polycarbonate, aromatic-aliphatic polycarbonate, branching polycarbonate, siloxane copolycarbonate, is preferably aromatic copolycarbonate;
Preferably, described aromatic copolycarbonate is the aromatic copolycarbonate of viscosity-average molecular weight 13000-40000, is 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 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.
This polycarbonate compositions, can also comprise other auxiliary agent of 0-10 part, other auxiliary agent described 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 methyl alcohol are made into the phenol type substances methanol solution of 0.001wt%-1wt% mass concentration; 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;
2) by graftomer blended under agitation in high mixer of the phenol type substances methanol solution of 0.001wt%-1wt% mass concentration and modified rubber, component I is obtained;
3) component I is joined in forcing machine by feeding scale merge with component I I, aromatic copolycarbonate, fire retardant and extrude pelletizing, obtain described polycarbonate compositions.
Wherein, described step 2) in the rotating speed of blended under agitation be 280 revs/min-320 revs/min; Be preferably 300 revs/min.
Polycarbonate compositions of the present invention 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:
When the present invention selects the graftomer of the phenol type substances methanol solution pretreated modified rubber with 0.001wt%-1wt% adding certain content in polycarbonate compositions formula, the polycarbonate compositions obtained has excellent low-temperature flexibility and high glossiness, 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 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 low-temperature flexibility: use ASTMD256,51BF ,-40 DEG C represent low-temperature flexibility with 3.2mm thickness measurement notched Chalpy impact intensity and 23 DEG C with the relative different per-cent of 3.2mm thickness, and numerical value is higher, and its low-temperature flexibility is better.This evaluation method eliminates the impact of initial performance difference.
The test mode of glossiness: ASTMD2457, in the glossiness of at least 60 of 60 ° of measurements, glossiness lower than 60 does not then meet product standard requirement, and in the glossiness of at least 80 of 80 ° of measurements, the glossiness of product of the present invention all can higher than the glossiness of 90..
The polycarbonate used in the present invention:
Component a-1:PC1300-10(Korea S LG);
Component a-2:PC1225(Japan Supreme Being people);
The graftomer of the modified rubber used in the present invention:
Components b-1: component I: the phenol type substances methanol solution of preparation 0.001wt%-1wt%, being joined speed setting is in graftomer (ABS757 Taiwan the is very beautiful) high mixer being added with modified rubber of 300 revs/min, mixing time is 30 minutes, obtains the graftomer of pretreated modified rubber;
Components b-2: component I I:ABS757 Taiwan is very beautiful;
The phenol type substances that the present invention uses:
Phenol: (Shanghai TCI);
P-methyl phenol class material: (Aladdin);
Dimethyl benzene phenols material: (Aladdin);
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:AO168(tri-[2.4-di-tert-butyl-phenyl] phosphorous acid ester) as stablizer, (BASF);
Component d-2:PETS(pentaerythritol stearate) as lubricant, (U.S. dragon is husky);
Component d-3:PTFE(tetrafluoroethylene) as anti-dripping agent, (Guangzhou entropy energy).
embodiment 1-12 and comparative example 1-8: the preparation of polycarbonate compositions
Phenol type substances and methyl alcohol are made into the phenol type substances methanol solution of 0.001wt%-1wt% mass concentration; By graftomer blended under agitation in high mixer of the phenol type substances methanol solution of 0.00wt1%-1wt% mass concentration and modified rubber, obtain component I; Component I is joined in forcing machine by feeding scale and merges with component I I, aromatic copolycarbonate, fire retardant and extrude pelletizing, obtain described polycarbonate compositions; Wherein, the rotating speed of blended under agitation is 300 revs/min; Test the low-temperature flexibility of above-mentioned polycarbonate compositions, 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 | 44 | 55 | 65 | 85 | 44 | 85 | ||||||
| Component a-2 | 44 | 55 | 65 | 85 | 55 | 65 | ||||||
| Components b-1 | 25 | 15 | 9 | 4.5 | 20 | 12 | 7.2 | 3.6 | 15 | 9 | 5.4 | 2.7 |
| Components b-2 | 25 | 15 | 9 | 4.5 | 30 | 18 | 10.8 | 5.4 | 35 | 21 | 12.6 | 6.3 |
| Amount of component b | 5 | 14 | 16 | 5 | 5 | 14 | 16 | 5 | 5 | 14 | 16 | 5 |
| Component d-1 | 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-2 | 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-3 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Phenol type substances methanol solution (wt%) | 0.001 | 0.01 | 0.05 | 0.6 | 0.1 | 1 | 0.005 | 0.02 | 0.3 | 0.8 | 0.08 | 0.5 |
| Low-temperature flexibility (%) | 81 | 82 | 83 | 83 | 85 | 83 | 79 | 73 | 79 | 80 | 81 | 82 |
| Glossiness (%) | 91.46 | 91.88 | 91.23 | 93.45 | 92.12 | 96.54 | 93.33 | 90.34 | 89.93 | 90.12 | 91.27 | 92.14 |
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 | 44 | 55 | 65 | 85 | ||||
| Component a-2 | 44 | 55 | 65 | 85 | ||||
| Components b-1 | 25 | 15 | 9 | 4.5 | 20 | 12 | 7.2 | 3.6 |
| Components b-2 | 25 | 15 | 9 | 4.5 | 30 | 18 | 10.8 | 5.4 |
| Amount of component b | 5 | 14 | 16 | 5 | 5 | 14 | 16 | 5 |
| Component d-1 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 | 0.2 |
| Component d-2 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 | 0.3 |
| Component d-3 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 | 0.5 |
| Phenol type substances methanol solution (wt%) | 0.0001 | 2 | 3 | 0.0006 | 0 | 5 | 7 | 10 |
| Low-temperature flexibility (%) | 40 | 23 | 44 | 30 | 46 | 33 | 32 | 40 |
| Glossiness (%) | - | - | 60 | - | - | - | - | - |
It is undesirable that "-" represents glossiness;
As can be seen from the embodiment of table 1 and comparative example relatively, when the present invention selects the graftomer of the phenol type substances methanol solution pretreated modified rubber with 0.001wt%-1wt% adding certain content in polycarbonate compositions formula, the polycarbonate compositions obtained has excellent low-temperature flexibility and high glossiness, is specially adapted to environment for use and requires higher occasion.
Claims (14)
1. a polycarbonate compositions, by weight, comprises following composition:
A, the polycarbonate of 44 parts-85 parts;
B, the graftomer of modified rubber of 8 parts-50 parts;
C, the fire retardant of 5 parts-25 parts;
Wherein, the weight percent sum of a, b, c tri-kinds of components is 100wt%.
2. a polycarbonate compositions as claimed in claim 1, by weight, comprises following composition:
A, the polycarbonate of 55 parts-80 parts;
B, the graftomer of modified rubber of 8 parts-50 parts;
C, the fire retardant of 5 parts-20 parts;
Wherein, the weight percent sum of a, b, c tri-kinds of components is 100wt%,
The graftomer of described modified rubber is made up of one or more mixtures in component I and/or component I I:
Component I: with the graftomer of the pretreated modified rubber of phenol type substances methanol solution of 0.001wt%-1wt%;
Component I I: the graftomer not making pretreated modified rubber;
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 55 parts-80 parts;
B, the graftomer of modified rubber of 10 parts-40 parts;
C, the fire retardant of 5 parts-20 parts;
Wherein, the weight percent sum of a, b, c tri-kinds of components is 100wt%,
The graftomer of described modified rubber is made up of one or more mixtures in component I and/or component I I:
Component I: with the graftomer of the pretreated modified rubber of phenol type substances methanol solution of 0.001wt%-1wt%;
Component I I: the graftomer not making pretreated modified rubber;
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, in the graftomer of described modified rubber, the per-cent that component I accounts for the graftomer gross weight of modified rubber is 30wt%-50wt%; The per-cent that component I I accounts for the graftomer gross weight of modified rubber is 50wt%-70wt%.
5. the polycarbonate compositions according to Claims 2 or 3, is characterized in that, in the graftomer of described modified rubber, and the second-order transition temperature <10 DEG C of component I.
6. the polycarbonate compositions according to any one of claim 1-5, it is characterized in that, the graftomer of described modified rubber is selected from one or more of the graftomer of the standby modified rubber of mass polymerization, emulsion polymerization, bulk-suspension polymerization legal system.
7. the polycarbonate compositions according to any one of claim 1-4, is characterized in that, the graftomer of described modified rubber, 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 containing 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.
8. polycarbonate compositions according to claim 7, it is characterized in that, the graftomer of described modified rubber 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 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.
9. 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, is preferably aromatic copolycarbonate; Described aromatic copolycarbonate is the aromatic copolycarbonate of viscosity-average molecular weight 13000-40000, is preferably the aromatic copolycarbonate of viscosity-average molecular weight 16000-28000.
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, it is characterized in that, also comprise other auxiliary agent of 0-10 part, other auxiliary agent described 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 methyl alcohol are made into the phenol type substances methanol solution of 0.001wt%-1wt% mass concentration; 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;
2) by graftomer blended under agitation in high mixer of the phenol type substances methanol solution of 0.001wt%-1wt% mass concentration and modified rubber, component I is obtained;
3) component I is joined in forcing machine by feeding scale merge with component I I, polycarbonate, fire retardant and extrude pelletizing, obtain described polycarbonate compositions.
The preparation method of 14. polycarbonate compositions according to claim 13, is characterized in that, described step 2) in the rotating speed of blended under agitation be 280 revs/min-320 revs/min; Be preferably 300 revs/min.
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