CN101759977B - Halogen-free flame-retardant enhancement type polycarbonate composition - Google Patents
Halogen-free flame-retardant enhancement type polycarbonate composition Download PDFInfo
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Abstract
The invention relates to a halogen-free flame-retardant enhancement type polycarbonate composition, which belongs to the field of polymer alloy, and consists of the following ingredients in parts by weight: 606-805 parts of PC-based resin, 100-300 parts of glass fiber, 40-60 parts of main flame retardant, 20-40 parts of flexibilizer, 3 parts of anti-dripping agent, 5-10 parts of lubricant and 4-6 parts of antioxidant. The halogen-free flame-retardant enhancement type polycarbonate composition proposed by the technical scheme not only has the characteristics of high rigidity, heat resistance and good dimensional stability, but also has good processibility and fire resistance, and also has beautiful appearance, has no glass fiber exposed to the outside, and can be served as the special material of electrical products.
Description
Technical field
The present invention relates to a kind of halogen-free flame-retardant enhancement type polycarbonate composition, belong to the high polymer alloy field.
Background technology
The application relates to the method that makes glass enhanced polycarbonate resin have flame retardant properties, relates to the compsn that is used for this method, and passes through this type flame-retarded polycarbonate resin that this method is produced.
Glass enhanced polycarbonate resin has very high intensity, and good surface appearance is widely used in the shell of various electrical equipment, is particularly useful for the injection molding of thin wall component.Yet spun glass enhanced polycarbonate resin self has combustibility and material can also melted by heat and drip, and causes that adjacent material catches fire.Therefore, in order in plurality of applications, to use spun glass enhanced polycarbonate safely, must in material, add effective fire retardant.Fire retardant needs not influence the performance of material significantly, and can not improve the cost of material in a large number.The multiple differing materials that is used to produce fire-retardant and/or dirp-proof polycarbonate compsn has been described.In U.S. Pat 3 971756,4 025 297,4,130 530,5,218 027 and 5 508 323, these examples of material have been described.Though have various open, these materials or cost an arm and a leg, or performance is not so good, still has the leeway of improving fire-retardant glass enhanced poly carbonate resin composition prescription.
Commercial these additives that are widely used in fire-retarded polycarbonate resin composition are organofluorine compounds.Fluorine cpd cost an arm and a leg, and these materials are independent and glass enhanced polycarbonate resin result of use is not fine, and in fact need other additive, generally use bromated fire retardant.Because the processing temperature of glass fiber reinforced PC is higher, require to be mostly the bromination superpolymer so be used for the fire retardant of PC than higher heat decomposition temperature, like brominated polycarbonate etc., thereby cost an arm and a leg.
Implementation along with the ROHS of European Union instruction; Cry to material is non-halogen is increasingly high; More and more factories requires can not contain halogen in the electric equipment products; Therefore each big material produce manufacturer commodity of all halogen-free flameproof of reinforced polyester having been carried out research and released oneself in recent years, but prevailing price is expensive.
Summary of the invention
The halogen-free flame-retardant enhancement type polycarbonate composition of the present invention seeks to have very good mechanical properties in order to provide a kind of, have good appearance, cost is moderate can be widely used in various electric equipment products.
Above-mentioned purpose of the present invention can realize through following technical scheme:
This halogen-free flame-retardant enhancement type polycarbonate composition; Be made up of PC base resin, glass, main flame retardant, anti-dripping agent PTFE, toughner, lubricant and oxidation inhibitor Hinered phenols and phosphorous acid esters, it is formed and proportioning is: PC base resin 606～805 weight parts, spun glass 100～300 weight parts, main flame retardant 40～60 weight parts, toughner 20～40 weight parts, anti-dripping agent 3 weight parts, lubricant 5～10 weight parts, oxidation inhibitor 4～6 weight parts.
Described PC base resin is that melting index is a kind of PC of 5-24 or the mixture of several kinds of PC.
Described spun glass is a roving, and diameter is the 8-15 micron.
Described main flame retardant is a kind of among BDP and the RDXP.BDP (dihydroxyphenyl propane biphosphonate) is a thick liquid, need be with the hydraulic fluid side to reinforced; RDXP is the polymkeric substance of RDP (Resorcinol biphosphonate), and thermostability is high, and phosphorus content is high, and because be solid, easy to process.
Described anti-dripping agent is the PTFE micro mist that AS (acrylonitrile styrene copolymer) coats, and PTFE content is 50-80%.
Described toughner is a kind of among HDPE, the LLDPE, preferred HDPE.
Described lubricant is one or more in OP wax, PETS, ethylene-acrylic acid copolymer and the silicone powder.
Described oxidation inhibitor is one or both in organic Hinered phenols, amine, the phosphite ester kind antioxidant, and Hinered phenols is 1076,1098,1010 etc., and phosphorous acid esters are 168,626 etc.
Fire-retardant reinforced polycarbonate compsn of the present invention can be selected twin screw extruder, and general processing temperature scope can be controlled between 240-250 ℃.
Halogen-free flame-proof reinforced poly carbonate composition according to above technical scheme proposition; Owing to not only have the good characteristics of rigidity height, thermotolerance and dimensional stability and possess good processibility and flame retardant resistance; And has a good surface appearance; No spun glass exposes, so can be used as the proprietary material of electric equipment products.
Embodiment
Further set forth technical characterstic of the present invention below in conjunction with embodiment, but said embodiment only is used to explain the present invention rather than restriction the present invention.
PC resin and various additive are behind high mixer high speed mixing; Melt extrude through twin screw extruder, glass is added by side direction glass charging opening, and BDP is added by side direction liquid charging opening; Just can get said composition through cooling granulation again, technological temperature is 230-250 ℃.The reference examples processing temperature is 250～260 ℃.
Adopt following material:
PC Japan Supreme Being people, trade mark 100C
The PC LG-DOW, the trade mark 301-5
Glass megalith group produces, trade mark ER-988
Brominated polycarbonate U.S. big lake trade mark BC-52
BDP Nanjing Heng Qiao industrial and trading company
RDXP Japan is big by eight
PTFE Shanghai still dimerization worker produces PTFE content 75%
HDPE 6070 Daqing petrochemical
The trade mark TR065 of ethylene propylene diluted acid multipolymer U.S. Honeywell company
Industrial and trading company is synthesized in PETS Guangzhou
The Irganox 1076 that antioxidant 1076 Switzerland Ciba produces
The 619F that oxidation inhibitor 619F U.S. Chemtura company produces
Tensile strength is tested according to ASTM D638.
Flexural strength and modulus are pressed ASTM D790 test.
Shock strength and notched Izod impact strength are pressed ASTM D256 test.
Heat-drawn wire is pressed ASTM D1525 test
According to U.S. UL94 standard testing vertical combustion performance.
The prescription of embodiment 1～3
| Prescription | Reference examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Base resin | 100C | 690 | 710 | 610 | 510 |
| Base resin | 301-22 | 95 | 93 | 96 | |
| Toughener | Glass | 200 | 100 | 200 | 300 |
| Fire retardant | BDP | 60 | 50 | 40 | |
| Fire retardant | BC—52 | 70 | |||
| Anti-dripping agent | SN3300 | 3 | 5 | 4 | 3 |
| Toughner | HDPE | 30 | 20 | 30 | 40 |
| Lubricant | PETS | 3 | 3 | 3 | 3 |
| Lubricant | TR065 | 3 | 5 | 2 | |
| Oxidation inhibitor | 619F | 3 | 3 | 3 | 3 |
| Oxidation inhibitor | 1076 | 1 | 1 | 2 | 3 |
The test result of gained material is following:
| Reference examples | Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Tensile strength (MPa) | 100 | 98 | 108 | 120 |
| Flexural strength (MPa) | 110 | 100 | 115 | 130 |
| Modulus in flexure (MPa) | 5600 | 3790 | 5420 | 6850 |
| Shock strength (KJ/m2) | 60 | 55 | 52 | 50 |
| Notched Izod impact strength (KJ/m2) | 12 | 11 | 9.5 | 10 |
| Heat-drawn wire 1.82MPa | 135 | 130 | 131 | 132 |
| Flame retardant resistance UL94,1.6mm | V0 | V1 | V0 | V0 |
| Color | In vain | In vain | In vain | In vain |
| Outward appearance | Have and expose | Good | Good | Good |
The prescription of embodiment 4～6
| Prescription | Reference examples | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Base resin | 100C | 620 | 710 | 610 | 510 |
| Base resin | 301-22 | 99 | 95 | 93 | 96 |
| Toughener | Glass | 200 | 100 | 200 | 300 |
| Fire retardant | RDXP | 60 | 50 | 40 | |
| Fire retardant | TDE | 40 | |||
| Anti-dripping agent | SN3300 | 3 | 5 | 4 | 3 |
| Toughner | HDPE | 30 | 20 | 30 | 40 |
| Lubricant | PETS | 3 | 3 | 3 | 3 |
| Lubricant | TR065 | 3 | 5 | 2 | |
| Oxidation inhibitor | 619F | 3 | 3 | 3 | 3 |
| Oxidation inhibitor | 1076 | 2 | 1 | 2 | 3 |
The test result of gained material is following:
| Reference examples | Embodiment 4 | Embodiment 5 | Embodiment 6 | |
| Tensile strength (MPa) | 100 | 102 | 110 | 120 |
| Flexural strength (MPa) | 110 | 100 | 115 | 130 |
| Modulus in flexure (MPa) | 5600 | 3800 | 5500 | 7000 |
| Shock strength (KJ/m2) | 55 | 50 | 52 | 50 |
| Notched Izod impact strength (KJ/m2) | 12 | 11 | 9.5 | 10 |
| Heat-drawn wire 1.82MPa | 135 | 130 | 132 | 135 |
| Flame retardant resistance UL94,1.6mm | V0 | V0 | V0 | V1 |
| Color | In vain | In vain | In vain | In vain |
| Outward appearance | Have and expose | Good | Good | Good |
Know that by last table embodiment compares mechanical property and descends seldom with reference examples, embodiment has good outward appearance, and embodiment is halogen-free flameproof, and higher economic benefit is arranged.And BDP and RDXP add and improved flowability greatly, makes processing temperature 10-20 degree that descended, and reduced production cost, improved productivity and reasonably lubricant and compatilizer be used, improved product appearance greatly, reduced glass emergence on the surface.
Claims (9)
1. halogen-free flame-retardant enhancement type polycarbonate composition, it is formed and proportioning is: PC base resin 606～805 weight parts, spun glass 100～300 weight parts, main flame retardant 40～60 weight parts, toughner 20～40 weight parts, anti-dripping agent 3 weight parts, lubricant 5～10 weight parts, oxidation inhibitor 4～6 weight parts.
2. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described PC base resin is that melting index is a kind of PC of 5-24 or the mixture of several kinds of PC.
3. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described spun glass is a roving, and diameter is the 8-15 micron.
4. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described main flame retardant is a kind of among BDP and the RDXP.
5. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described anti-dripping agent is the PTFE micro mist that AS coats, and wherein PTFE content is 50-80%.
6. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described toughner is a kind of among HDPE and the LLDPE.
7. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 6 is characterized in that: described toughner is HDPE.
8. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described lubricant is one or more in OP wax, PETS, ethylene-acrylic acid copolymer and the silicone powder.
9. a kind of halogen-free flame-retardant enhancement type polycarbonate composition according to claim 1 is characterized in that: described oxidation inhibitor is one or both in organic Hinered phenols, amine and the phosphite ester kind antioxidant.
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Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101875770B (en) * | 2010-07-14 | 2012-06-13 | 深圳市科聚新材料有限公司 | Glass fiber reinforced PC/PE alloy material and preparation method thereof |
| CN101974218B (en) * | 2010-11-12 | 2012-07-11 | 大河宝利材料科技(苏州)有限公司 | Special plastic/acrylonitrile butadiene styrene (PC/ABS) alloy for notebook computer shell |
| CN103013088A (en) * | 2012-12-29 | 2013-04-03 | 东莞市奥能工程塑料有限公司 | High-rigidity polycarbonate composite material and preparation method thereof |
| US10017640B2 (en) * | 2013-03-08 | 2018-07-10 | Covestro Llc | Halogen free flame retarded polycarbonate |
| CN103421292A (en) * | 2013-08-07 | 2013-12-04 | 金发科技股份有限公司 | High-liquidity halogen-free flame retardant glass fiber reinforced PC (Poly Carbonate) resin and preparation method thereof |
| CN104371293B (en) * | 2013-08-13 | 2016-06-01 | 广东宝塑科技有限公司 | A kind of glass fibre toughen and intensify polycarbonate composite material and preparation method |
| CN103408913B (en) * | 2013-08-16 | 2015-12-09 | 惠州市沃特新材料有限公司 | Composite flame-retardant polycarbonate material and preparation method thereof and application |
| CN103435997A (en) * | 2013-08-23 | 2013-12-11 | 北京化工大学常州先进材料研究院 | Continuous long-fiber enhanced halogen-free flame-retardant polycarbonate composite material and preparation method thereof |
| CN103554866A (en) * | 2013-10-14 | 2014-02-05 | 上海俊尓新材料有限公司 | Halogen-free flame-retardant polycarbonate composite material and its preparation method and application thereof |
| CN103554889B (en) * | 2013-10-29 | 2016-05-11 | 上海骏齐新材料科技有限公司 | A kind of fiber glass reinforced halogen-free flame retardant polycarbonate composite material and preparation method thereof |
| CN103589043A (en) * | 2013-11-12 | 2014-02-19 | 上海瀚氏模具成型有限公司 | HDPE (high-density polyethylene)/PC (poly carbonate) fire retardant alloy plastic |
| CN104497532A (en) * | 2014-12-17 | 2015-04-08 | 安徽科聚新材料有限公司 | Halogen-free flame-retardant high-gloss high-glass fiber reinforced PC material and preparation method thereof |
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| CN1400249A (en) * | 2001-08-01 | 2003-03-05 | 上海杰事杰新材料股份有限公司 | High-toughness glass fibre reinforced poly carbonate composite |
| CN1413228A (en) * | 1999-12-24 | 2003-04-23 | 拜尔公司 | Flame-resistant polycarbonate molding compositions containing high-purity talc |
| CN101213255A (en) * | 2005-09-13 | 2008-07-02 | 通用电气公司 | Fatigue resistant thermoplastic composition, method of making, and articles formed therefrom |
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Patent Citations (3)
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| CN1413228A (en) * | 1999-12-24 | 2003-04-23 | 拜尔公司 | Flame-resistant polycarbonate molding compositions containing high-purity talc |
| CN1400249A (en) * | 2001-08-01 | 2003-03-05 | 上海杰事杰新材料股份有限公司 | High-toughness glass fibre reinforced poly carbonate composite |
| CN101213255A (en) * | 2005-09-13 | 2008-07-02 | 通用电气公司 | Fatigue resistant thermoplastic composition, method of making, and articles formed therefrom |
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Effective date of registration: 20190104 Address after: 402560 No. 18 Longyun Road, Pulu Industrial Park, Tongliang County, Chongqing Co-patentee after: Shanghai Pret Compound Material Co., Ltd. Patentee after: CHONGQNG PRET NEW MATERIAL CO., LTD. Co-patentee after: ZHEJIANG PRET NEW MATERIAL CO., LTD. Address before: 200081 2nd Floor, 421 Lane, Siping Road, Hongkou District, Shanghai Patentee before: Shanghai Pret Compound Material Co., Ltd. |
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