CN1807506A - Self-extinguishing type halogen-free flame-retardant PC/ABS alloy and its preparation process - Google Patents
Self-extinguishing type halogen-free flame-retardant PC/ABS alloy and its preparation process Download PDFInfo
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- CN1807506A CN1807506A CN 200610049606 CN200610049606A CN1807506A CN 1807506 A CN1807506 A CN 1807506A CN 200610049606 CN200610049606 CN 200610049606 CN 200610049606 A CN200610049606 A CN 200610049606A CN 1807506 A CN1807506 A CN 1807506A
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Abstract
This invention discloses a kind of self-extinguished non-halogen PC/ABS alloy, which contains: 40-95 weight percent aromatic polycarbonate or polyestercarbonate, 5-60 weight percent ABS graft copolymer modified by silicon resin, 1-20 weight percent phosphonitryl expansible flame-resistant agant. The silicon resin modified ABS graft copolymer graft copolymer prepare by melting reaction between silicon resin and ABS. The PC/ABS alloy in this invention is prepard by blending the modified ABS and aother two materials, which has high flame-resistant efficiency, mechanical property good, non-halogen, low fume, non-corrodibility, environment-friendly, and can be used as materials of electrical appliances widely.
Description
Technical field
The present invention relates to the preparation technology of a kind of self-extinguishing type halogen-free flame-retardant PC/ABS alloy and this alloy, especially relate to a kind of PC/ABS alloy that adopts silicone resin modified graft copolymer preparation technology preparation with high efficiency flame retardance.
Background technology
With PC and ABS is that the PC/ABS alloy of main raw material is a kind of important engineering polyblend, and this material has good processability, low-temperature impact-resistant performance and higher heat-drawn wire and light stability.Can be widely used in production such as automobile, electronics, office equipment.
Because the PC/ABS material itself has combustibility, therefore limited the range of application and the safety in utilization of PC/ABS alloy, for a long time, it is fire-retardant that PC/ABS adopts halogenated flame retardant to implement always, as decabromodiphenyl oxide, tetrabromo-bisphenol and antimonous oxide etc.The fire retardant of even now shows good flame, but when burning, discharge a large amount of smog, produce objectionable impurities two oxa-glutinous rehmannias, simultaneously since their velocity of diffusion much larger than the velocity of diffusion of flame, in fire, hindered withdrawing and fire-fighting work of people, made lives and properties suffer heavy losses.
Though phosphorus-nitrogen expanding fire retardant price is higher relatively, because therefore the synergistic effect of nitrogen element and phosphoric demonstrates excellent flame-retardant performance, and the amount of being fuming is little, basically do not produce toxic gas, and self-extinguishing is arranged, be considered to the direction of fire retardant development from now on.Relate to material preparation process and mainly contain following a few class:
1.CN1382181, CN1307608 described and selected phosphonic acid ester amine and the phosphonitrile class fire retardant as the polycarbonate/ABS moulding material for use, improve the processing flow characteristics when giving the material excellent flame-retardant, improve sedimental formation on modulus of elasticity and the minimizing instrument.Such graftomer is produced by using body, body-solution or body one suspension polymerization.
2.CN1459470 described a kind of Halogenless flaming retarding cold resistant PC/ABS alloy.It is made up of PC, ABS, halogen-free flame retardants NP, toughner E, reactive monomer M, initiator C, antioxidant, anti UV agent, processing aid, this fire retardation PC/ABS alloy is composited by single stage method, the low-temperature impact resistance excellence, flame retarding efficiency is lower.
3.CN1266449, CN1266450, CN1266451, CN1266452 described nonflammable Themoplastic molding materials, this material comprises polycarbonate, vinyl (being total to) polymkeric substance, graftomer, fluoro polyolefine, contains the inorganic powder and the phosphorus compound of the fine granular of mean diameter≤200nm.
4.US3505431, US3711577, US4054544 described the acyclic tri methylene phosphonic acid ester-amine series of part halo and done fire retardant.
5.US5061745 described by aromatic polycarbonate, ABS graft copolymer, contained the polymeric blends that styrol copolymer and phosplate flame-retardant additive are formed.This mixture does not also reach the anti-stress cracking standard of thin-wall case at present.
6.EP0363608, EP0640655 described by aromatic polycarbonate, contained the polymeric blends that styrol copolymer or graft copolymer, monomer or low polyphosphate are formed.The thermal stability of this mixture is not enough.
All introduced the single flame-retardant additive that contains phosphoric in the preparation process of above-mentioned fire retardation PC/ABS alloy, the material flame retarding efficiency is not high, and the interpolation of a certain amount of fire retardant has certain influence to the mechanical property of PC/ABS alloy.
Summary of the invention
The invention provides a kind of self-extinguishing type halogen-free flame-retardant PC/ABS alloy, this alloy has self-extinguishing, the flame retarding efficiency height.
The present invention also provides the preparation technology of above-mentioned PC/ABS alloy, overcome prior art raising flame retardant properties that exists and the defective that guarantees that the original mechanical property of alloy can not get both, by silicone resin melt modification ABS graft copolymer, improve the consistency of PC and ABS on the one hand, strengthen on the other hand and the cooperative flame retardant action effect of phosphorus-nitrogen expanding fire retardant the PC/ABS alloy.
Silicone resin is as a kind of BACN, and it can not rely on the halogen based compound fully and brings into play fire retardation, and the few cigarette of polymkeric substance that contains silicone resin is nontoxic, combustion heat value is low, flame propagation velocity is slow, and development and application potential are wide.Experimental results show that; impel fused PC/ABS alloy to be dehydrated into charcoal under the phosphorus-nitrogen expanding fire retardant high temperature; silica group in the silicone resin helps to form successive, oxidation resistant silicate protective layer; base material under the protection charcoal layer exempts from destruction, living cigarette amount and corrosive gases content when reducing material combustion.
PC and ABS have certain consistency, but because ABS is a two phase structure, comprising disperse phase PB and external phase SAN.And PC and PB consistency are very poor, and therefore after introducing silicone resin among the ABS, rubber phase is wrapped, and solubility parameter and PC that SAN and silicone resin blend form external phase are close, thereby have improved both consistency and bonding force.The introducing amount of silicone resin is relevant with the content of SAN among the ABS in the ABS graft copolymer, takes all factors into consideration the cooperative flame retardant effect of silicone resin and phosphorus-nitrogen expanding fire retardant, and the introducing amount of silicone resin is no more than 25% of grafts gross weight.
A kind of self-extinguishing type halogen-free flame-retardant PC/ABS alloy comprises:
The aromatic copolycarbonate of (1) 40～95 weight part or polyestercarbonate;
(2) 5～60 weight parts ABS graft copolymer of silicone resin modification;
(3) 1～20 weight part phosphorus-nitrogen expanding fire retardants.
The ABS graft copolymer of described silicone resin modification is that silicone resin and ABS graft copolymer make by the frit reaction grafting, and the introducing amount of silicone resin is 1～25% of an ABS graft copolymer gross weight.
Described silicone resin is methyl phenyl silicone resin or methyl vinyl silicone.
Described phosphorus-nitrogen expanding fire retardant is triphenyl, Resorcinol biphosphonate, 2,4,8,10-four oxygen-3,9-hosphospiro [5,5] undecane-3,9-dioxy-3, one or more in 9-two melamine salts.
Self-extinguishing type halogen-free flame-retardant PC of the present invention/ABS alloy is preparation like this:
(1) preparation of silicone resin modified ABS graft copolymer: take by weighing silicone resin and ABS, the introducing amount of silicone resin is 1～25% of an ABS graft copolymer gross weight; With silicone resin and ABS in blending equipment in 100～130 ℃ of following blend 1～60 minute, after cooling off, add the screw rod machine at 160～200 ℃ of following melt blending extruding pelletizations;
(2) aromatic copolycarbonate of 40～95 weight parts or polyestercarbonate, 5～60 weight parts on twin screw extruder are melt extruded granulation behind 90～100 ℃ of following premixs with the ABS graft copolymer of silicone resin modification, 1～20 part of weight phosphorus-nitrogen expanding fire retardant in high-speed mixer.
Self-extinguishing type fire retardation PC of the present invention/ABS alloy flame retarding efficiency height, good mechanical property, Halogen, low cigarette, non-corrosiveness, environmentally friendly can be widely used in the manufacturing of electric appliance component.
Embodiment
The preparation 1 of the ABS graft copolymer of embodiment 1 silicone resin modification
17.5 parts of methyl phenyl silicone resins and 82.5 parts of ABS were joined in the high-speed mixer 110 ℃ of following high-speed mixing 15 minutes, during be interrupted and bleed three times, on twin screw extruder, melt extrude granulation subsequently.Five interval temperature of forcing machine: 175 ℃ in an interval, 180 ℃ in two intervals, 190 ℃ in three, four, five intervals.Forcing machine rotating speed 80r/min, feeding quantity is 40% of a feed hopper.
The preparation 2 of the ABS graft copolymer of embodiment 2 silicone resin modifications
12 parts of methyl vinyl silicone and 88 parts of ABS were joined in the high-speed mixer 105 ℃ of following high-speed mixing 15 minutes, during be interrupted and bleed three times, on twin screw extruder, melt extrude granulation subsequently.Five interval temperature of forcing machine: 175 ℃ in an interval, 180 ℃ in two intervals, 190 ℃ in three, four, five intervals.Forcing machine rotating speed 80r/min, feeding quantity is 40% of a feed hopper.
Embodiment 3: the preparation of self-extinguishing type halogen-free flame-retardant PC/ABS alloy
The modified ABS graft copolymer of 25 parts of embodiment 1 preparation, 65 parts of PC and 10 parts of triphenyl are joined in the high-speed mixer 100 ℃ of following premixs 5 minutes, on twin screw extruder, melt extrude granulation subsequently.Five interval temperature of forcing machine: 215 ℃ in an interval, 225 ℃ in two, three intervals, 230 ℃ in four, five intervals.Forcing machine rotating speed 240r/min, feeding quantity is 40% of a feed hopper.230 ℃ of shaped by fluid pressures on thermocompressor, omnipotent sampling machine sample preparation.Measure the flame retardant properties and the mechanical property of fire retardant material.Detected result: oxygen index is 31%, and the UL94 testing vertical flammability reaches the V0 level, and tensile strength is 45.6MPa, and elongation at break is 38.5%.
Embodiment 4-6: the preparation of self-extinguishing type halogen-free flame-retardant PC/ABS alloy
Press the identical technology of embodiment 3, methyl phenyl silicone resin introducing amount is 17.5% of a modified ABS graft copolymer gross weight, phosphorus-nitrogen expanding fire retardant is a triphenyl, measures the flame retardant properties and the mechanical property of fire retardant material after the different proportioning raw materials sample preparations, and the result is as shown in the table:
| The set of dispense ratio of fire retardation PC/ABS alloy | LOI /％ | UL94 vertical combustion grade | Mechanical property | ||||
| Embodiment | PC | Silicone resin modified ABS graft copolymer | Phosphorus-nitrogen expanding fire retardant | ||||
| Tensile strength/MPa | Elongation at break/% | ||||||
| 4 | 70 | 20 | 10 | 29.6 | V0 | 48.8 | 42.6 |
| 3 | 65 | 25 | 10 | 31.0 | V0 | 45.6 | 38.5 |
| 5 | 65 | 20 | 15 | 32.8 | V0 | 43.7 | 40.2 |
| 6 | 60 | 20 | 20 | 35.2 | V0 | 41.3 | 36.8 |
Embodiment 7: the preparation of self-extinguishing type halogen-free flame-retardant PC/ABS alloy
The modified ABS graft copolymer of 25 parts of embodiment 1 preparation, 65 parts of PC and 10 parts of Resorcinol biphosphonates are joined in the high-speed mixer 90 ℃ of following premixs 5 minutes, on twin screw extruder, melt extrude granulation subsequently.Five interval temperature of forcing machine: 215 ℃ in an interval, 225 ℃ in two, three intervals, 230 ℃ in four, five intervals.Forcing machine rotating speed 240r/min, feeding quantity is 40% of a feed hopper.230 ℃ of shaped by fluid pressures on thermocompressor, omnipotent sampling machine sample preparation.Measure the flame retardant properties and the mechanical property of fire retardant material.Detected result: oxygen index is 30.3%, and the UL94 testing vertical flammability reaches the V0 level, and tensile strength is 47.2MPa.
Embodiment 8: the preparation of self-extinguishing type halogen-free flame-retardant PC/ABS alloy
With the modified ABS graft copolymer of 25 parts of embodiment 1 preparation, 65 parts of PC and 10 part 2,4,8,10-four oxygen-3,9-hosphospiro [5,5] undecane-3,9-dioxy-3,9-two melamine salts joined in the high-speed mixer 90 ℃ of following premixs 5 minutes, melt extruded granulation subsequently on twin screw extruder.Five interval temperature of forcing machine: 215 ℃ in an interval, 225 ℃ in two, three intervals, 230 ℃ in four, five intervals.Forcing machine rotating speed 240r/min, feeding quantity is 40% of a feed hopper.230 ℃ of shaped by fluid pressures on thermocompressor, omnipotent sampling machine sample preparation.Measure the flame retardant properties and the mechanical property of fire retardant material.Detected result: oxygen index is 32.7%, and the UL94 testing vertical flammability reaches the V0 level, and tensile strength is 42.0MPa.
Application examples 1:
Self-extinguishing type halogen-free flame-retardant PC/ABS the alloy and the Masterbatch blend injection moulding of embodiment 3,4,5 preparations, can be used for making all kinds of electric appliance components, as LCD TV and display casing, notebook computer casing, duplicating machine shell, printer casing, photographing equipment parts, mobile phone outer casing, microwave oven component, gas-cooker parts, water-heater parts etc.
Claims (6)
1. self-extinguishing type halogen-free flame-retardant PC/ABS alloy, form by following raw material:
The aromatic copolycarbonate of (1) 40～95 weight part or polyestercarbonate;
(2) 5～60 weight parts ABS graft copolymer of silicone resin modification;
(3) 1～20 weight part phosphorus-nitrogen expanding fire retardants.
2. self-extinguishing type halogen-free flame-retardant PC according to claim 1/ABS alloy, it is characterized in that: the ABS graft copolymer of described silicone resin modification is that silicone resin and ABS make by the frit reaction grafting, and the introducing amount of silicone resin is 1～25% of an ABS graft copolymer gross weight.
3. self-extinguishing type halogen-free flame-retardant PC according to claim 1/ABS alloy is characterized in that: described silicone resin is methyl phenyl silicone resin or methyl vinyl silicone, is linear oligomer.
4. self-extinguishing type halogen-free flame-retardant PC according to claim 1/ABS alloy, it is characterized in that: described phosphorus-nitrogen expanding fire retardant is triphenyl, Resorcinol biphosphonate, 2,4,8,10-four oxygen-3,9-hosphospiro [5,5] undecane-3,9-dioxy-3, one or more in 9-two melamine salts.
5. the preparation technology of self-extinguishing type halogen-free flame-retardant PC/ABS alloy comprises:
(1) preparation of silicone resin modified ABS graft copolymer: take by weighing silicone resin and ABS, the introducing amount of silicone resin is 1～25% of an ABS graft copolymer gross weight; With silicone resin and ABS in blending equipment in 100～130 ℃ of following blend 1～60 minute, after cooling off, add the screw rod machine at 160～200 ℃ of following melt blending extruding pelletizations;
(2) aromatic copolycarbonate of 40～95 weight parts or polyestercarbonate, 5～60 weight parts on twin screw extruder are melt extruded granulation behind 90～100 ℃ of following premixs with the ABS graft copolymer of silicone resin modification, 1～20 part of weight phosphorus-nitrogen expanding fire retardant in high-speed mixer.
6. according to the arbitrary described self-extinguishing type halogen-free flame-retardant PC of the claim 1～4/application of ABS alloy in the electrical equipment manufactured materials.
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| CNB200610049606XA CN100400595C (en) | 2006-02-23 | 2006-02-23 | Self-extinguishing type halogen-free flame-retardant PC/ABS alloy and its preparation process |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139459B (en) * | 2007-08-30 | 2011-12-21 | 上海金发科技发展有限公司 | Non-bittern flame-proof thermostable polycarbonate and acrylonitrile-butadiene-phenylethene grafted copolymer alloy resin and method for preparing same |
| CN103013079A (en) * | 2012-12-14 | 2013-04-03 | 上海锦湖日丽塑料有限公司 | Low smoke density PC/ABS (Poly Carbonate/Acrylonitrile Butadiene Styrene) alloy and preparation method thereof |
| CN103421294A (en) * | 2013-08-23 | 2013-12-04 | 苏州长盛机电有限公司 | Halogen-free flame-retardant enhanced PC/ABS alloy and preparation method thereof |
| CN111117198A (en) * | 2020-01-06 | 2020-05-08 | 上海交通大学 | PC/ABS flame-retardant composite material and preparation method thereof |
| CN112552636A (en) * | 2020-12-09 | 2021-03-26 | 重庆普利特新材料有限公司 | Halogen-free flame-retardant self-extinguishing ABS resin containing nanoscale flame retardant and preparation method thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| DE19801050A1 (en) * | 1998-01-14 | 1999-07-15 | Bayer Ag | Polycarbonate acrylonitrile-butadiene-styrene based thermoplastic molding composition useful in automotive, electrical and electronic applications |
| KR100329983B1 (en) * | 1999-07-14 | 2002-03-27 | 안복현 | Flameproof Thermoplastic Resin Composition |
| JP2000178402A (en) * | 1998-12-15 | 2000-06-27 | Daihachi Chemical Industry Co Ltd | Flame resistant rubber reinforced styrene based resin composition |
| KR100332853B1 (en) * | 1999-06-14 | 2002-04-17 | 성재갑 | Flame Retardant Thermoplastic Resin Composition with Excellent Environmental Stress Crack Resistance and Impact Resistance |
| DE19941824A1 (en) * | 1999-09-02 | 2001-03-08 | Bayer Ag | Flame retardant polycarbonate blends |
| US6767466B2 (en) * | 2002-04-08 | 2004-07-27 | Teva Medical Ltd. | Leukocyte filter construction |
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- 2006-02-23 CN CNB200610049606XA patent/CN100400595C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101139459B (en) * | 2007-08-30 | 2011-12-21 | 上海金发科技发展有限公司 | Non-bittern flame-proof thermostable polycarbonate and acrylonitrile-butadiene-phenylethene grafted copolymer alloy resin and method for preparing same |
| CN103013079A (en) * | 2012-12-14 | 2013-04-03 | 上海锦湖日丽塑料有限公司 | Low smoke density PC/ABS (Poly Carbonate/Acrylonitrile Butadiene Styrene) alloy and preparation method thereof |
| CN103421294A (en) * | 2013-08-23 | 2013-12-04 | 苏州长盛机电有限公司 | Halogen-free flame-retardant enhanced PC/ABS alloy and preparation method thereof |
| CN111117198A (en) * | 2020-01-06 | 2020-05-08 | 上海交通大学 | PC/ABS flame-retardant composite material and preparation method thereof |
| CN111117198B (en) * | 2020-01-06 | 2021-12-07 | 上海交通大学 | PC/ABS flame-retardant composite material and preparation method thereof |
| CN112552636A (en) * | 2020-12-09 | 2021-03-26 | 重庆普利特新材料有限公司 | Halogen-free flame-retardant self-extinguishing ABS resin containing nanoscale flame retardant and preparation method thereof |
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| CN100400595C (en) | 2008-07-09 |
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Assignee: Zhejiang Canbo environmental protection material Co Ltd Assignor: Zhejiang University Contract record no.: 2011330001420 Denomination of invention: Self extinguishing halogen-free flame retardant PC/ABS alloy and preparation process thereof Granted publication date: 20080709 License type: Exclusive License Open date: 20060726 Record date: 20111123 |
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