CN104530677A - Bicyclic caged phenyl phosphate silicone modified flame-retardant PC/ABS (polycarbonate/acrylnitrile-butadiene-styrene) alloy and preparation method thereof - Google Patents
Bicyclic caged phenyl phosphate silicone modified flame-retardant PC/ABS (polycarbonate/acrylnitrile-butadiene-styrene) alloy and preparation method thereof Download PDFInfo
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- CN104530677A CN104530677A CN201410770745.6A CN201410770745A CN104530677A CN 104530677 A CN104530677 A CN 104530677A CN 201410770745 A CN201410770745 A CN 201410770745A CN 104530677 A CN104530677 A CN 104530677A
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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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
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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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
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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Abstract
The invention discloses a bicyclic caged phenyl phosphate silicone modified flame-retardant PC/ABS (polycarbonate/acrylnitrile-butadiene-styrene) alloy and a preparation method thereof. The flame-retardant PC/ABS alloy is prepared from the following raw materials in percentage by mass: 55-60% of polycarbonate, 20-25% of an ABS copolymer, 7-9% of phosphate, 5-7% of bicyclic caged phenyl phosphate silicone, 5-7% of a polydimethylsiloxane-styrene-methyl methacrylate copolymer, 0.3-0.5% of an anti-dripping agent and 0.2%-0.4% of an antioxidant. The flame retardant rating of the flame-retardant PC/ABS alloy disclosed by the invention is UL94V-0@1.6mm, the heat deflection temperature is above 92 DEG C, the notched impact strength is above 31kJ/m<2>, and the melt flow rate is above 16g/10min. The flame-retardant PC/ABS alloy has the advantages of high flame retardant rating, good heat resistance, excellent mechanical properties and good processing fluidity.
Description
Technical field
The present invention relates to fire-retardant polycarbonate/Acrylnitrile-Butadiene-Styrene (PC/ABS) alloy material, be specifically related to a kind of Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material and preparation method thereof, belong to field of high polymer material modification.
Background of invention
PC has that shock strength is high, the advantage such as thermal stability and good insulation preformance, ABS has good chemical proofing and excellent moulding processability, both blended PC/ABS alloys obtained then have both advantage concurrently, good combination property, therefore obtains widespread use in the manufacture of electric, auto parts.Because application scenario like this requires higher to the resistance toheat of material, flame retardant properties and mechanical strength etc., and PC/ABS alloy flame retardant properties is poor, the alloy easy firing that particularly ABS proportion is higher, and therefore flame-retardant modified becoming must need.Phosphate ester flame retardants (diphenyl phosphoester) (RDP) as two in Resorcinol, two (diphenyl phosphoester) (BDP) of dihydroxyphenyl propane obtains more application in PC/ABS alloy, (the Levchik S V such as Levchik S V, Bright D A, Alessio G R, et al.New halogen-free fire retardantfor engineering plastic applications [J] .Journal of Vinyl and Additive Technology, 2001, 7 (2): 98-103) research shows that at mass ratio be the RDP fire retardant adding 13wt% (mass percent) in the PC/ABS alloy of 70:30, the thick batten vertical combustion of 1.6mm can be made by UL-94V-0 flame retardant rating, but make alloy hot temperature (HDT) be down to 72 DEG C, and RDP, the phosphate flame retardants such as BDP are thick liquid, consumption is more than after 10wt%, reinforced more difficult, easy precipitation.Different flame retardant is composite can reduce consumption, Chinese invention patent CN 200910040557 adopts 1wt% triphenylphosphate and 5wt% solid phthalic acid-1,3-dimethylphenylphosphate oligopolymer compositional flame-retardant modification PC/ABS alloy, when PC and ABS quality proportioning is 80:20, the thick batten of 1.6mm is by UL-94V-0 flame retardant rating, but the heat-drawn wire of alloy drops to 83 DEG C from 116 DEG C, reduce 33 DEG C.Chinese invention patent CN 200610123184 adopts the flame-retardant modified mass ratio of the triphenylphosphate of the magnesium hydroxide of 2wt% and 10wt% to be the PC/ABS alloy of 70:30, the batten making 1.6mm thick is by UL-94V-0 grade, but the interpolation of rigid inorganic flame retardant magnesium hydroxide makes alloy processing fluidity decline, and melt flow rate is down to 13.3g/10min.In sum, there is such as problem such as reduction PC/ABS alloy material heat-drawn wire and flowing property etc. in existing flame-retardant modified technology.
Summary of the invention
Exist for existing flame-retardant modified technology and reduce the problem such as PC/ABS alloy material heat-drawn wire and flowing property, the invention provides a kind of flame retardant properties, resistance toheat and mechanical property all higher, phenyl Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material of excellent combination property and preparation method thereof, when alloy flame retardant rating reaches UL94V-0@1.6mm, limiting oxygen index(LOI) reaches more than 33%, and heat-drawn wire is more than 92 DEG C.
Phenyl Caged bicyclic phosphate siloxane (PPSi) is the BACN containing phosphorus and silicon two kinds of ignition-proof elements in a kind of molecular structure, expand after being heated and form loose porous cellular layer of charcoal, between barrier material inside and outside atmosphere, fire retardation is played in the exchange of air and heat, it adds the impact of PC/ABS heat-drawn wire less, but consumption just can make the PC/ABS of 70:30 reach UL94V-0 1.6mm, large usage quantity when being about 20wt%; The phosphate flame retardants such as RDP, BDP have good fire retardation to PC/ABS alloy, and reaching same effect consumption only needs 13wt%; Polydimethylsiloxane-styrene-methylmethacrylate copolymer is then mainly used as expanding material.The present invention is with the flame-retardant modified PC/ABS alloy of PPSi, phosphoric acid ester and polydimethylsiloxane-styrene-methylmethacrylate copolymer, effect based on following three aspects obtains the PC/ABS alloy of fire-retardant, high heat-resisting, good mechanical performance: the first, liquid phosphoric acid ester has the good ability to material surface migration, migrate to surface when being heated and resolve into polyphosphoric acid and promote into charcoal, blocking oxygen enters inside, PPSi then forms complete bubble in alloy inside, intercept the exchange of internal heat, both have good cooperative flame retardant effect; The second, phosphoric acid ester small molecules has plastification, and polymer segment is slided easily, and cause alloy hot temperature to reduce, the PPSi particle of rigidity then has certain enhancement, thus makes the heat-drawn wire that alloy still keeps higher; Three, polydimethylsiloxane-styrene-methylmethacrylate copolymer contains a certain amount of element silicon, except compatibilization, also has certain cooperative flame retardant effect with PPSi, phosphoric acid ester.
In order to realize the object of the invention, the present invention adopts following technical scheme:
Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material, by mass percentage, its composition of raw materials is made up of following component: 55% ~ 60% polycarbonate, 20% ~ 25% Acrylnitrile-Butadiene-Styrene, 7% ~ 9% phosphoric acid ester, 5% ~ 7% phenyl Caged bicyclic phosphate siloxane, 5% ~ 7% polydimethylsiloxane-styrene-methylmethacrylate copolymer, 0.3% ~ 0.5% anti-dripping agent and 0.2% ~ 0.4% oxidation inhibitor;
Described phosphoric acid ester is triphenylphosphate, Resorcinol two (diphenyl phosphoester) or dihydroxyphenyl propane two (diphenyl phosphoester);
Described phenyl Caged bicyclic phosphate siloxane is white powder, and molecular structural formula is:
Described anti-dripping agent be Ben Yi Xi ?the coated tetrafluoroethylene of acrylonitrile copolymer;
Described oxidation inhibitor is four [methyl-β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3; 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N; N'-is two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester in one or two kinds.
For realizing the object of the invention further, preferably, by mass percentage, the mass percent that described phosphoric acid ester and phenyl Caged bicyclic phosphate siloxane are shared total is 12% ~ 14%.
The mass ratio of described phenyl Caged bicyclic phosphate siloxane and phosphoric acid ester is 0.8:1 ~ 0.9:1.
The consumption of described polydimethylsiloxane-styrene-methylmethacrylate copolymer be phenyl Caged bicyclic phosphate siloxane and phosphoric acid ester quality and 30% ~ 50%.
The preparation method of described Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material: by composition of raw materials mass percent, after polycarbonate, Acrylnitrile-Butadiene-Styrene, phosphoric acid ester, phenyl Caged bicyclic phosphate siloxane, polydimethylsiloxane-styrene-methylmethacrylate copolymer, anti-dripping agent and oxidation inhibitor dispersing and mixing, by twin screw extruder melting at 240 DEG C ~ 270 DEG C, mixing, extrude, cool, pelletizing and drying.
The present invention compared with prior art, has following effect:
The present invention utilizes the cooperative flame retardant effect of phosphoric acid ester and PPSi, and with polydimethylsiloxane-styrene-methylmethacrylate copolymer for expanding material, PC/ABS alloy flame retardant rating is made to reach UL94V-0@1.6mm, limiting oxygen index(LOI) reaches 33%, and heat-drawn wire is more than 92 DEG C, notched Izod impact strength is at more than 31kJ/m2, and melt flow rate (MFR), at more than 16g/10min, has that flame retardant rating is high, resistance toheat good, good mechanical performance and an advantage such as processing fluidity is good.
Embodiment
Below in conjunction with embodiment, the invention will be further described, but the present invention's scope required for protection is not limited to the scope that embodiment is stated.
Embodiment PC used selects LG polycarbonate company limited of Korea S product below, and the trade mark is PC-122; ABS selects LG Chemical Co., Ltd. of Korea S product, and the trade mark is XR401; Fire retardant PPSi reference literature Chen J, Liu S, Zhao J.Synthesis, application and flame retardancy mechanism of a novel flame retardant containingsilicon and caged bicyclic phosphate for polyamide 6 [J] .Polymer Degradation and Stability, 2011,96 (8): 1508-1515.) method preparation; RDP and TPP is Shouguang De Run Chemical Co., Ltd. product, and RDP (product code DHPF009) viscosity is 500-800mPas (25 DEG C), TPP (product code DHPF005) zero pour>=47.0 DEG C; BDP is Zhejiang Wansheng Co., Ltd.'s product, viscosity 2000-2600Pas (40 DEG C); Polydimethylsiloxane-styrene-methylmethacrylate copolymer is Mitsubishi Co., Ltd. trade mark is METABLEN SRK-200A product, particle size range 10 μm ~ 50 μm; MBS is that Korea S LG produces product, and the trade mark is
eM500; Anti-dripping agent provides for Daikin Industries,Ltd., and the trade mark is PTFE LK-6102; Oxidation inhibitor all represents with the trade mark: antioxidant 1010 is four (β-(3,5-di-tert-butyl-hydroxy phenyl) propionic acid) pentaerythritol ester, antioxidant 1076 be β-positive octadecanol ester of (4-hydroxy phenyl-3,5-di-t-butyl) propionic acid; Oxidation inhibitor 1098 is N, N'-pair-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine; Irgasfos 168 is that phosphite ester kind antioxidant has tricresyl phosphite (2,4-di-tert-butyl-phenyl) ester; Oxidation inhibitor B215 is that antioxidant 1010 is prepared than compound with the quality of 1:2 with irgasfos 168, this antioxidant 1010 of oxidation inhibitor B225 is prepared than compound with the quality of 1:1 with irgasfos 168.
Select mainly for embodiment sake of clarity above about raw material, the raw material of available this area other trades mark corresponding.
Embodiment 1:
Control total quantity is 3Kg, by 56.3wt% (mass percent) PC, 24.1wt%ABS, 8.0wt%RDP, 6.0wt%PPSi, 5.0wt% polydimethylsiloxane-styrene-methylmethacrylate copolymer (trade mark is SRK-200A), 0.3wt% anti-dripping agent (trade mark is PTFE LK-6102), 0.3wt% oxidation inhibitor (trade mark is B225) joins in homogenizer, after being uniformly mixed, gained Preblend is by twin screw extruder melting at 240 ~ 270 DEG C of temperature, mixing, extrude, cooling, pelletizing and drying, obtain Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material.Change the proportioning (as table 1 and table 2) of each raw material, prepare other 7 embodiments of the present invention according to the method for embodiment 1.
Comparative example 1: the PPSi in embodiment 1 is replaced with the RDP of equivalent, when other component and processing conditions identical obtained single RDP fire retardation PC/ABS alloy material.
Comparative example 2: the polydimethylsiloxane-styrene-methylmethacrylate copolymer in embodiment 2 is replaced with the MBS expanding material of equivalent, when other component and processing conditions identical prepare the fire retardation PC/ABS alloy material of MBS increase-volume.
After the alloy material prepared is toasted 8 hours at 90 DEG C, be injection molded into test bars, according to GB 2406-80 standard testing limiting oxygen index(LOI), according to UL94-2009 standard testing vertical combustion grade, heat-drawn wire is tested according to GB/T1634.2-2004, according to GB/T 1040-2006 standard testing tensile strength, according to GB/T 9341-2000 standard testing flexural strength, according to GB/T 1843-1996 standard testing notched Izod impact strength.Gained results of property is as table 1 and table 2.
The composition of raw materials of table 1: embodiment 1-3 and comparative example 1-2 and material property
The composition of raw materials of table 2: embodiment 4-8 and material property
From above two tables, when the total consumption of fire retardant is 14wt%, compared with single RDP fire retardation PC/ABS (comparative example 1), Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material (embodiment 1) of the present invention, heat-drawn wire improves 30.6%, notched Izod impact strength improves 27.7%, and other performance also slightly improves; Compared with MBS increase-volume PC/ABS alloy material (comparative example 2), the present invention with polydimethylsiloxane-styrene-methylmethacrylate copolymer for expanding material, gained PC/ABS alloy material (embodiment 2) limiting oxygen index(LOI) improves 18.8%, 1.6mm batten vertical combustion brings up to V-0 grade from UL94V-1, and flame retardant properties significantly improves.Caged bicyclic phosphate siloxane fire retardation PC of the present invention/ABS alloy material 1.6mm batten vertical combustion is all by UL94V-0 grade, and limiting oxygen index(LOI) reaches more than 33%, heat-drawn wire more than 92 DEG C, notched Izod impact strength 31kJ/m
2above, melt flow rate (MFR), at more than 16g/10min, has the advantages such as flame retardant rating is high, resistance toheat good, mechanical property is excellent, processing fluidity is good, can meet the application demands such as household electrical appliance, auto parts, electric product well.
Claims (5)
1. Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material, it is characterized in that, by mass percentage, its composition of raw materials consists of: 55% ~ 60% polycarbonate, 20% ~ 25% Acrylnitrile-Butadiene-Styrene, 7% ~ 9% phosphoric acid ester, 5% ~ 7% phenyl Caged bicyclic phosphate siloxane, 5% ~ 7% polydimethylsiloxane-styrene-methylmethacrylate copolymer, 0.3% ~ 0.5% anti-dripping agent and 0.2% ~ 0.4% oxidation inhibitor;
Described phosphoric acid ester is triphenylphosphate, Resorcinol two (diphenyl phosphoester) or dihydroxyphenyl propane two (diphenyl phosphoester);
The molecular structural formula of described phenyl Caged bicyclic phosphate siloxane is:
Described anti-dripping agent be Ben Yi Xi ?the coated tetrafluoroethylene of acrylonitrile copolymer;
Described oxidation inhibitor is four [methyl-β-(3; 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, β-(3; 5-di-tert-butyl-hydroxy phenyl) the positive octadecanol ester of propionic acid, N; N'-is two-(3-(3,5-di-tert-butyl-hydroxy phenyl) propionyl) hexanediamine and three [2.4-di-tert-butyl-phenyl] phosphorous acid ester in one or two kinds.
2. Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material according to claim 1, is characterized in that, by mass percentage, the shared total mass percent of described phosphoric acid ester and phenyl Caged bicyclic phosphate siloxane is 12% ~ 14%.
3. Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material according to claim 1, is characterized in that, the mass ratio of described phenyl Caged bicyclic phosphate siloxane and phosphoric acid ester is 0.8:1 ~ 0.9:1.
4. Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material according to claim 1, it is characterized in that, the consumption of described polydimethylsiloxane-styrene-methylmethacrylate copolymer be phenyl Caged bicyclic phosphate siloxane and phosphoric acid ester quality and 30% ~ 50%.
5. the preparation method of the Caged bicyclic phosphate siloxane fire retardation PC/ABS alloy material according to any one of claim 1-4, it is characterized in that: by composition of raw materials mass percent, after polycarbonate, Acrylnitrile-Butadiene-Styrene, phosphoric acid ester, phenyl Caged bicyclic phosphate siloxane, polydimethylsiloxane-styrene-methylmethacrylate copolymer, anti-dripping agent and oxidation inhibitor dispersing and mixing, by twin screw extruder melting at 240 DEG C ~ 270 DEG C, mixing, extrude, cool, pelletizing and drying.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206818A1 (en) * | 2016-05-31 | 2017-12-07 | 金发科技股份有限公司 | Environmentally-friendly and energy-saving structural layer for refrigeration device, and applications thereof |
| WO2017206821A1 (en) * | 2016-05-31 | 2017-12-07 | 金发科技股份有限公司 | Environment-friendly, energy-saving structural layer for refrigeration equipment and application thereof |
| CN109456355A (en) * | 2018-10-23 | 2019-03-12 | 苏州科技大学 | Three silicon cage alcohol ester compounds of organic silicon flame-retardant benzene siliconic acid and preparation method thereof |
| CN110627974A (en) * | 2019-09-30 | 2019-12-31 | 铨盛聚碳科技股份有限公司 | High-heat-resistance phosphorus-silicon flame retardant, and preparation method and application thereof |
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| EP1069157A1 (en) * | 1999-07-14 | 2001-01-17 | Cheil Industries Inc. | Flameproof thermoplastic resin composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206818A1 (en) * | 2016-05-31 | 2017-12-07 | 金发科技股份有限公司 | Environmentally-friendly and energy-saving structural layer for refrigeration device, and applications thereof |
| WO2017206821A1 (en) * | 2016-05-31 | 2017-12-07 | 金发科技股份有限公司 | Environment-friendly, energy-saving structural layer for refrigeration equipment and application thereof |
| CN109456355A (en) * | 2018-10-23 | 2019-03-12 | 苏州科技大学 | Three silicon cage alcohol ester compounds of organic silicon flame-retardant benzene siliconic acid and preparation method thereof |
| CN109456355B (en) * | 2018-10-23 | 2020-12-04 | 苏州科技大学 | Organosilicon flame-retardant charring agent phenyl silicic acid trisilacyl alcohol ester compound and preparation method thereof |
| CN110627974A (en) * | 2019-09-30 | 2019-12-31 | 铨盛聚碳科技股份有限公司 | High-heat-resistance phosphorus-silicon flame retardant, and preparation method and application thereof |
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Effective date of registration: 20191211 Address after: 511442 No. 4-1, He Xi Road, Nan Cao Tang Village, Panyu District South Village, Guangzhou, Guangdong Patentee after: Guangzhou Guanghua Plastic Pipe Co. Ltd. Address before: 510640 Tianhe District, Guangdong, No. five road, No. 381, Patentee before: South China University of Technology |
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