CN103073864A - High-impact low-smoke density halogen-free flame-retardant PC polycarbonate composition - Google Patents
High-impact low-smoke density halogen-free flame-retardant PC polycarbonate composition Download PDFInfo
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- CN103073864A CN103073864A CN2012105699649A CN201210569964A CN103073864A CN 103073864 A CN103073864 A CN 103073864A CN 2012105699649 A CN2012105699649 A CN 2012105699649A CN 201210569964 A CN201210569964 A CN 201210569964A CN 103073864 A CN103073864 A CN 103073864A
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- 239000000779 smoke Substances 0.000 title claims abstract description 38
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 36
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 33
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 239000003063 flame retardant Substances 0.000 title claims abstract description 22
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 7
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 239000003112 inhibitor Substances 0.000 claims description 6
- -1 dihydroxyphenyl Chemical group 0.000 claims description 5
- 229930185605 Bisphenol Natural products 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical group CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 claims description 3
- 239000003963 antioxidant agent Substances 0.000 claims description 3
- 230000003078 antioxidant effect Effects 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 150000003014 phosphoric acid esters Chemical class 0.000 claims description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 6
- 238000005516 engineering process Methods 0.000 abstract description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000004566 building material Substances 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000002148 esters Chemical class 0.000 abstract 1
- 229920001296 polysiloxane Polymers 0.000 abstract 1
- 229920007019 PC/ABS Polymers 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000006872 improvement Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 4
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000800 acrylic rubber Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 231100000517 death Toxicity 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 235000012438 extruded product Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005453 pelletization Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a high-impact low-smoke density halogen-free flame-retardant PC polycarbonate composition which comprises the following components by weight percent: 50 to 97 percent of PC polycarbonate, 0-30 percent of ABS resin, 0 to 15 percent of phosphoric ester fire retardant, 1.5 to 5 percent of silicone, 0-1 percent of zinc borate, 0 to1.5 percent of drip-proof agent, 0 to 0.5 percent of antioxygen and 0-0.5 percent of lubricant. The composition not only has lower smoke density, but also has better mechanical property, is halogen-free and environment-friendly, and can effectively meet the requirements of cars, household appliances, building materials and other products on lower smoke density. Besides, the composition provided by the invention is simple in preparation technology and low in cost, meets the industrialized production requirement and has a wide application prospect in the market.
Description
Technical field
The present invention relates to a kind of polycarbonate compositions, specifically relate to a kind of HI high impact, low smoke density, halogen-free flame-retardant polycarbonate composition, be applicable to the industries such as various automobiles, household electrical appliances.
Background technology
It is good that polycarbonate (PC) plastics have transparency, and thermotolerance is high, good toughness, and still, there are following technical disadvantages in the advantages such as good flame resistance, at first, its poor fluidity, difficult forming; Secondly, its goods are very responsive to breach, produce easily stress cracking; Again, its not anti-solvent, and also expensive.For overcoming defects, usually adopt the method for preparing the PC polyblend to improve its performance, the PC/ABS polyblend is exactly wherein modal a kind of.
It is low that the PC/ABS alloy has melt viscosity, good processability, the high good over-all properties of shock strength.But be accompanied by the adding of ABS, the smoke density during the PC/ABS Plastics Combustion significantly promotes.The patent No. be CN1978528A bibliographical information reduce the technical scheme of the smoke density in PC/ABS when burning with decabromodiphenyl oxide and activation zinc borate, but, because decabromodiphenyl oxide contains halogen, the right material of halogen-containing resistance is when presence of fire, cause easily the corrosion of Circuits System switch and other metal objects, replaced by the phosphorus flame retardant of more environmental protection gradually.The patent No. is to have reported the technical scheme of the smoke density when reducing the PC/ABS burning with talcum, silicone-acrylic elastomer, inorganic puff etc. in the document of CN101405127, this material product rigidity is higher, but exist toughness not enough, use the problem of relative narrower.
At present, the smoke density of a lot of industries after to material combustion had requirement, especially in automobile industry and building trade, when the selection of a lot of main engine plants is arranged the smoke density behind the material combustion there have been clear and definite regulation and higher requirement, such as school bus standard-required smoke density≤75, but, the smoke density of the polycarbonate compositions that obtains from prior art can't satisfy above-mentioned requirements, therefore, in the urgent need to a kind of halogen-free flame-retardant polycarbonate composition with lower smoke density and mechanical property excellence, to reduce the injures and deaths that too much cause because of smog when the accidents such as presence of fire.
Summary of the invention
In order to solve the problems of the technologies described above, the present invention proposes a kind of HI high impact, low smoke density, halogen-free flame-retardant polycarbonate composition, when having lower smoke density, also has very good mechanical properties, can be widely used in injection moulding, the extruded products such as automobile, household electrical appliances.
Technical scheme of the present invention is achieved in that
A kind of HI high impact, low smoke density, halogen-free flame-retardant polycarbonate composition, percentage composition is composed of the following components by weight:
As a further improvement on the present invention, described polycarbonate is the bisphenol A-type aromatic copolycarbonate, and described bisphenol A-type aromatic copolycarbonate is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
As a further improvement on the present invention, the weight-average molecular weight of described linear polycarbonate is 20000 g/mol～40000g/mol.
As a further improvement on the present invention, the weight percent content of the divinyl in the described ABS resin is 12%-24%.
As a further improvement on the present invention, described phosphoric acid ester fire retardant is at least a in dihydroxyphenyl propane-two (BDP) and the triphenylphosphate (TPP).
As a further improvement on the present invention, described dripping inhibitor is tetrafluoroethylene.
As a further improvement on the present invention, described oxidation inhibitor is the mixture of hindered phenol antioxygen and phosphite ester kind antioxidant.
As a further improvement on the present invention, described lubricant is pentaerythritol stearate.
The invention has the beneficial effects as follows: the present invention proposes a kind of HI high impact, low smoke density, halogen-free flame-retardant polycarbonate composition, compared with prior art, when the present invention has lower smoke density, also have more excellent mechanical property, and a halogen-free environmental, can the to satisfy effectively automobile, the demand of the lower smoke density of product needed such as household electrical appliances, building materials, in addition, the preparation technology of product of the present invention is simple, with low cost, meets industrialization production requirements, has wide market application foreground.
Embodiment
Be doing further in detail of how realizing, clearly and completely explanation below in conjunction with specific embodiment to the present invention, listed embodiment only is further described the present invention, and is not thereby limiting the invention.
Select among the embodiment:
Polycarbonate is to be provided by Korea S LG production derived from the linear PC of dihydroxyphenyl propane photoreactive gas, and the trade mark is 1300-10; ABS resin is the ABS resin that is made by emulsion polymerization, and being produced by BASF AG provides, and the trade mark is GP-22; Methacrylate butadi ene styrene copolymer MBS is provided by the LG chemistry, trade mark M-521; Oxidation inhibitor is the mixture of hindered phenol antioxygen and phosphite ester kind antioxidant, is to be produced by Ciba company to provide; Lubricant is pentaerythritol stearate, and being produced by LOZA company provides, and the trade mark is GLYCOLUBE-P; Siloxanes is deep eventually MR-01; Zinc borate is the HT-207 of the safe chemical industry of ring;
The compositing formula of embodiment 1～6 and reference examples l～2 is as shown in table 1.
Table 1 compositing formula (weight percentage)
The preparation method of HI high impact of the present invention, low smoke density, halogen-free flame-retardant polycarbonate composition is as follows:
At first, to after mixing by the compositing formula in the table 1, the PC of super-dry resin, ABS resin, MBS, siloxanes, zinc borate, oxidation inhibitor, lubricant join in the main barrel of twin screw extruder, then BDP is injected in the main barrel by oil filler pipe, the complete processing of twin screw extruder is as follows: screw diameter is 35mm, length-to-diameter ratio L/D is 36, export from charging opening to head, each section of main barrel control temperature is respectively 220 ℃, 240 ℃, 255 ℃, 260 ℃, 250 ℃, and the twin screw rotating speed is 300 rev/mins.At last, twin screw extruder extrude material strip through pelletizing after the tank cooling, namely get product of the present invention.
The said products after 4 hours, is injection molded into standard batten with plastic-injection moulding machine in 90 ℃ of dryings in convection oven, injection temperature is 250 ℃; The batten of injection formed is carried out performance test at least in 50% relative humidity, 23 ℃ of placements after 24 hours.
The product performance testing method is as follows:
Melting index: press ISO 1133 methods, test under 260 ℃, the 2.16 kilograms load.
Tensile property: press ISO 527 methods, draw speed 50 mm/min.
Bending property: press ISO 178 methods, trial speed 2 mm/min.
Notched Izod impact strength: press ISO 179/1eA method, the sample of 4 mm thick, simply supported beam notch shock.
Vicat softening temperature: press ISO 306 methods, 50 ℃/minute of temperature rise rates are tested under 5 kilograms of load.
Smoke density grade: press GB/T 8627 methods, size of sample 25mm*25mm*6mm.
Combustioncharacteristics: according to the UL94 method, batten thickness 1.6mm.
The performance test results of each embodiment sample is as shown in table 2.
Table 2 the performance test results
By each embodiment the performance test results of table 2 as can be known: the polycarbonate compositions of the present invention's preparation is compared with reference examples 1, and can find out: mechanical property is suitable, and smoke density is much lower, and good flame retardant properties is also arranged simultaneously.Compare with reference examples 2, can find out: siloxanes and zinc borate have the effect of effective reduction smoke density, when being arranged at present, the selection of a lot of main engine plants has lower smoke density to requiring, such as school bus standard-required smoke density≤75, and the smoke density of reference examples 1 and reference examples 2 is more than 80, the smoke density that other non-fire retardation PC/ABS of general purpose grade and fire retardation PC/ABS are described all can not satisfy above-mentioned high requirement, the PC of the present invention preparation and the smoke density of PC/ABS alloy material can both reach≤75 standard-required, still kept simultaneously excellent mechanics and processing characteristics, therefore, can be widely used in making the lower automobile of smoke density requirement, household electrical appliances, the products such as building materials, in addition, the preparation technology of product of the present invention is simple, with low cost, meet industrialization production requirements, have wide market application foreground.
Those skilled in the art is by carrying out modification or the change on the various forms to above-described embodiment, but do not deviate from the situation of essence of the present invention, all drops within protection scope of the present invention.
Claims (8)
1. a HI high impact, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: percentage composition is composed of the following components by weight:
2. HI high impact according to claim 1, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: described polycarbonate is the bisphenol A-type aromatic copolycarbonate, and described bisphenol A-type aromatic copolycarbonate is the linear polycarbonate derived from the dihydroxyphenyl propane photoreactive gas.
3. HI high impact according to claim 2, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: the weight-average molecular weight of described linear polycarbonate is 20000 g/mol～40000g/mol.
4. HI high impact according to claim 1, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: the weight percent content of the divinyl in the described ABS resin is 12%-24%.
5. HI high impact according to claim 1, low smoke density, halogen-free flame-retardant polycarbonate composition is characterized in that: described phosphoric acid ester fire retardant is at least a in dihydroxyphenyl propane-two (BDP) and the triphenylphosphate (TPP).
6. HI high impact according to claim 1, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: described dripping inhibitor is tetrafluoroethylene.
7. HI high impact according to claim 1, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: described oxidation inhibitor is the mixture of hindered phenol antioxygen and phosphite ester kind antioxidant.
8. HI high impact according to claim 1, low smoke density, halogen-free flame-retardant polycarbonate composition, it is characterized in that: described lubricant is pentaerythritol stearate.
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| CN2012105699649A CN103073864A (en) | 2012-12-25 | 2012-12-25 | High-impact low-smoke density halogen-free flame-retardant PC polycarbonate composition |
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| CN2012105699649A CN103073864A (en) | 2012-12-25 | 2012-12-25 | High-impact low-smoke density halogen-free flame-retardant PC polycarbonate composition |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104262924A (en) * | 2014-09-02 | 2015-01-07 | 金发科技股份有限公司 | Flame-retardant aromatic polycarbonate composition with low precipitate and favorable appearance |
| CN109504056A (en) * | 2018-10-14 | 2019-03-22 | 金旸（厦门）新材料科技有限公司 | Low smell PC alloy plate special material of a kind of low smoke high flame retardant and preparation method thereof |
| CN112111142A (en) * | 2020-10-21 | 2020-12-22 | 横店集团得邦工程塑料有限公司 | Low-smoke-density flame-retardant PC/ABS alloy material and preparation method thereof |
| CN112143203A (en) * | 2020-10-21 | 2020-12-29 | 横店集团得邦工程塑料有限公司 | Moisture-heat-resistant PC/ABS flame-retardant composite material and preparation method thereof |
| CN114316561A (en) * | 2021-12-29 | 2022-04-12 | 上海品诚控股集团有限公司 | High-gloss low-filling halogen-free hybrid flame-retardant PC material and preparation and application thereof |
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| CN112111142A (en) * | 2020-10-21 | 2020-12-22 | 横店集团得邦工程塑料有限公司 | Low-smoke-density flame-retardant PC/ABS alloy material and preparation method thereof |
| CN112143203A (en) * | 2020-10-21 | 2020-12-29 | 横店集团得邦工程塑料有限公司 | Moisture-heat-resistant PC/ABS flame-retardant composite material and preparation method thereof |
| CN114316561A (en) * | 2021-12-29 | 2022-04-12 | 上海品诚控股集团有限公司 | High-gloss low-filling halogen-free hybrid flame-retardant PC material and preparation and application thereof |
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Application publication date: 20130501 |