CN102634176A - Flame retardant polybutylene terephthalate resin composite with high comparative tracking index (CTI) - Google Patents
Flame retardant polybutylene terephthalate resin composite with high comparative tracking index (CTI) Download PDFInfo
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- CN102634176A CN102634176A CN2012101261090A CN201210126109A CN102634176A CN 102634176 A CN102634176 A CN 102634176A CN 2012101261090 A CN2012101261090 A CN 2012101261090A CN 201210126109 A CN201210126109 A CN 201210126109A CN 102634176 A CN102634176 A CN 102634176A
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- polybutylene terephthalate
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- terephthalate resin
- retardant
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Abstract
The invention discloses an flame retardant polybutylene terephthalate resin composite with high comparative tracking index (CTI), consisting of polybutylene terephthalate, a high-CTI synergist, a flame retardant, an auxiliary flame retardant, an inorganic filler, a toughening agent, a main antioxidant, an auxiliary antioxidant, an antifogging agent, a black masterbatch and glass fiber. The flame retardant polybutylene terephthalate resin composite has favorable flame retardance and high CTI.
Description
Technical field:
The present invention relates to a kind of polymeric material field, is a kind of resin combination.
Background technology:
PBT (enhancing, modified PBT) is mainly used in fields such as automobile, electronic apparatus, mechanical industry.The component parts that wherein is used for electronic apparatus industry mainly contains the deflection skeleton of televisor, output transformer skeleton, switch connector, electricrefrigerator, motor for washer end cap etc.These electronic products need all that flame retardant properties is high, electrical insulation capability is good; Requirement is under wet environment, and plastic paste also will keep good insulating property, is exactly that thermoplastic engineering plastic has higher electric relatively trace index (CTI).This to present application the most widely bromine system strengthen the flame-retardant PBT system and proposed new requirement.
Concerning strengthening flame-retardant PBT, open source information shows that common bromine is that the CTI of flame-retardant PBT G30 true qualities is about 250V, and bromine is that the CTI of flame-retardant PBT G30 black is 175-200V.Therefore, developing the high bromine of electric relatively trace index (CTI) that is widely used in the white domestic appliances industry is that flame-retardant enhanced PBT material is the task of top priority.
Summary of the invention:
The object of the present invention is to provide a kind of good flame retardancy that has, the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index is high.
Technical solution of the present invention is:
The fire-retardant polybutylene terephthalate resin combination of a kind of high electric relatively trace index (CTI) is characterized in that: calculate by weight, be made up of following component:
The viscosity of described polybutylene terephthalate is 0.6-1.3dl/g.The present invention uses the PBT resin (Nantong star morning synthetic materials ltd production) of viscosity as 0.85-1.1dl/g.
Described high CTI synergist is a borate, is 3.5 hydrate zinc borates or high temperature resistant zinc borate (the same and chemical company's production in Jiangyin, Jiangsu).
Described fire retardant is decabromodiphynly oxide, hexabromocyclododecane, tetrabromo-bisphenol, brominated Polystyrene, brominated epoxy resin or TDE; Described auxiliary flame retardant is the oxide compound or the stibnate of antimony.
Described toughner is polyolefin elastomer POE, ethylene-propylene acid butyl ester 3135, ethylene-ethyl acrylate copolymer EEA, TEB 3K-butadiene-styrene MBS, ethylene-methyl acrylate-SY-Monomer G random terpolymer AX8900 or thermoplastic elastomer TPR.
Described primary antioxidant is 2; 6-di-t-butyl-4-cresols, 3; 5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, 4 ' 4-thiobis (6-tert-butyl o cresols), 2 ' 2 '-methylene-bis (4-methyl-6-tert butyl phenol) or four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described auxiliary antioxidant is thio-2 acid 2 stearyl ester, Tyox B, tricresyl phosphite (2,4-di-tert-butyl phenolic ester) or triphenyl phosphite.
Described oxidation inhibitor also can be B215, B225, B900, JC1215, JC1225 etc. for having the compound of primary antioxidant and auxiliary antioxidant effect simultaneously.
Described Antidrip agent is a tetrafluoroethylene.Black agglomerate is U.S.'s Cabot black agglomerate.
The spun glass of described spun glass for handling through interface modifier.
Material of the present invention has good flame retardancy, electric relatively trace index (CTI) height.
Below in conjunction with embodiment the present invention is described further.
Embodiment:
Each raw material weight umber is seen table 1, the brominated Polystyrene PBT621 that fire retardant A produces for U.S. Albemarle Corporation in the embodiment of the invention and the Comparative Examples, and fire retardant B is a brominated epoxy resin.Auxiliary flame retardant C is an Antimony Trioxide: 99.5Min.
Comparative Examples 1
100 parts of polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts of fire retardant B, 7 parts of auxiliary flame retardant Antimony Trioxide: 99.5Mins, 3135,0.3 part of primary antioxidant AT10 of 2 parts of toughner, 0.3 part of auxiliary antioxidant AT168,0.4 part of Antidrip agent tetrafluoroethylene and 1.5 parts of black masterbatch are added the high mixer high speed and mix 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; The alkali free glass fibre that in twin screw extruder, adds simultaneously 30% weight, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
Embodiment 1
100 weight part polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts by weight of flame retardant A, 7 weight part auxiliary flame retardant Antimony Trioxide: 99.5Mins, 2 weight part toughner, 3135,0.3 weight part primary antioxidant AT10,0.3 weight part auxiliary antioxidant AT168,0.4 weight part Antidrip agent tetrafluoroethylene and 1.5 weight part black masterbatch are added the high mixer high speed and mix 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; In twin screw extruder, add simultaneously 58 weight part alkali free glass fibres, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
Embodiment 2
100 weight part polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts by weight of flame retardant A, 5 weight part auxiliary flame retardant Antimony Trioxide: 99.5Mins, the high temperature resistant zinc borate of 2 weight part CTI synergists (the same and chemical company's production in Jiangyin, Jiangsu), 2 weight part toughner, 3135,0.3 weight part primary antioxidant AT10,0.3 weight part auxiliary antioxidant AT168,0.4 weight part Antidrip agent tetrafluoroethylene and 1.5 weight part black masterbatch are added the high mixer high speed and mix 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; The alkali free glass fibre that in twin screw extruder, adds simultaneously 58 weight parts, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
Embodiment 3
100 weight part polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts by weight of flame retardant A, 4 weight part auxiliary flame retardant Antimony Trioxide: 99.5Mins, the high temperature resistant zinc borate of 3 weight part CTI synergists (Jiangyin, Jiangsu is with producing with chemical company), 2 weight part toughner, 3135,0.3 weight part primary antioxidant AT10,0.3 weight part auxiliary antioxidant AT168,0.4 part of weight Antidrip agent tetrafluoroethylene and 1.5 weight part black masterbatch are added high mixer high speed mixing 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; The alkali free glass fibre that in twin screw extruder, adds simultaneously 30% weight, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
Embodiment 4
100 weight part polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts by weight of flame retardant A, 3.5 weight part auxiliary flame retardant Antimony Trioxide: 99.5Mins, the high temperature resistant zinc borate of 3.5 weight part CTI synergists (the same and chemical company's production in Jiangyin, Jiangsu), 2 weight part toughner, 3135,0.3 weight part primary antioxidant AT10,0.3 weight part auxiliary antioxidant AT168,0.4 weight part Antidrip agent tetrafluoroethylene and 1.5 weight part black masterbatch are added the high mixer high speed and mix 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; The alkali free glass fibre that in twin screw extruder, adds simultaneously 30% weight, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
Embodiment 5
100 weight part polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts by weight of flame retardant A, 3.5 weight part auxiliary flame retardant Antimony Trioxide: 99.5Mins, 3.5 weight part CTI synergists, 3.5 hydrate zinc borates, 2 weight part toughner, 3135,0.3 weight part primary antioxidant AT10,0.3 weight part auxiliary antioxidant AT168,0.4 weight part Antidrip agent tetrafluoroethylene and 0.8 weight part black masterbatch are added the high mixer high speed and mix 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; The alkali free glass fibre that in twin screw extruder, adds simultaneously 30% weight, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
Embodiment 6
100 weight part polybutylene terephthalates (PBT) were descended dry 2-3 hour at 120 ℃, the control moisture content＜below 0.05%, high-speed mixer and mixing 3min; Subsequently 24 parts by weight of flame retardant A, 3.5 weight part auxiliary flame retardant Antimony Trioxide: 99.5Mins, 6 weight part CTI synergists, 3.5 hydrate zinc borates, 2 weight part toughner, 3135,0.3 weight part primary antioxidant AT10,0.3 weight part auxiliary antioxidant AT168,0.4 weight part Antidrip agent tetrafluoroethylene and 0.8 weight part black masterbatch are added the high mixer high speed and mix 5min; Get into twin screw extruder plasticizing, fusion from the metering feeding device; The alkali free glass fibre that in twin screw extruder, adds simultaneously 59 weight parts, through routine extrude, tie rod, cooling, pelletizing, all mix, packing.Pellet prepares test bars by injection moulding machine then at 120 ℃ of dry 4h of air dry oven.
The composition properties test result is seen table 2 in embodiment and the Comparative Examples.
The raw material weight umber proportioning of table 1 embodiment 1～6, Comparative Examples 1
Composition properties test result in table 2 embodiment and the Comparative Examples
The clear product of the present invention of above-mentioned data sheet has excellent performance.
Claims (9)
1. fire-retardant polybutylene terephthalate resin combination that electric relatively trace index is high is characterized in that: calculate by weight, be made up of following component:
Polybutylene terephthalate 50-100
High CTI synergist 0-50
Fire retardant 10-30
Auxiliary flame retardant 5-15
Mineral filler 0-20
Toughner 0-10
Primary antioxidant 0-0.5
Auxiliary antioxidant 0-0.5
Antidrip agent 0-0.5
Masterbatch 0-4
Spun glass 40-80.
2. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 is high is characterized in that: the viscosity of described polybutylene terephthalate is 0.6-1.3dl/g.
3. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high is characterized in that: described CTI synergist is 3.5 hydrate zinc borates or high temperature resistant zinc borate.
4. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high is characterized in that: described fire retardant is decabromodiphynly oxide, hexabromocyclododecane, tetrabromo-bisphenol, brominated Polystyrene, brominated epoxy resin or TDE; Described auxiliary flame retardant is the oxide compound or the stibnate of antimony.
5. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high is characterized in that: described mineral filler is Marinco H or white lake.
6. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high is characterized in that: described toughner is polyolefin elastomer POE, ethylene-propylene acid butyl ester 3135, ethylene-ethyl acrylate copolymer EEA, TEB 3K-butadiene-styrene MBS, ethylene-methyl acrylate-SY-Monomer G random terpolymer AX8900 or thermoplastic elastomer TPR.
7. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high; It is characterized in that: described primary antioxidant is 2; 6-di-t-butyl-4-cresols, 3; 5-di-tert-butyl-hydroxy phenyl propionic acid stearyl alcohol ester, 4 ' 4-thiobis (6-tert-butyl o cresols), 2 ' 2 '-methylene-bis (4-methyl-6-tert butyl phenol) or four [β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic acid] pentaerythritol ester; Described auxiliary antioxidant is thio-2 acid 2 stearyl ester, Tyox B, tricresyl phosphite (2,4-di-tert-butyl phenolic ester) or triphenyl phosphite.
8. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high is characterized in that: described Antidrip agent is a tetrafluoroethylene.
9. the fire-retardant polybutylene terephthalate resin combination that electric relatively trace index according to claim 1 and 2 is high is characterized in that: the spun glass of described spun glass for handling through interface modifier.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2012101261090A CN102634176A (en) | 2012-04-26 | 2012-04-26 | Flame retardant polybutylene terephthalate resin composite with high comparative tracking index (CTI) |
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| CN2012101261090A CN102634176A (en) | 2012-04-26 | 2012-04-26 | Flame retardant polybutylene terephthalate resin composite with high comparative tracking index (CTI) |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105199337A (en) * | 2015-09-22 | 2015-12-30 | 苏州博利迈新材料科技有限公司 | PBT for reinforcement and toughness and preparation method thereof |
| CN107849338A (en) * | 2015-07-16 | 2018-03-27 | 胜技高分子株式会社 | Polybutylene terephthalate (PBT) resin combination |
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| US6248814B1 (en) * | 1998-03-25 | 2001-06-19 | Teijin Limited | Resin composition |
| EP1288260A1 (en) * | 2001-08-29 | 2003-03-05 | Albemarle Corporation | Flame retardant compositions |
| CN1749313A (en) * | 2005-08-03 | 2006-03-22 | 广州市花都科苑企业有限公司 | High CTI value no-halogen no-red phosphorus flame-retardant reinforced poly butanediol terephthate |
| CN1995134A (en) * | 2006-12-25 | 2007-07-11 | 浙江俊尔新材料有限公司 | High CTI value high fire resistance property reinforced polybutylene terephthalate |
| CN101885904A (en) * | 2010-07-19 | 2010-11-17 | 中山市纳普工程塑料有限公司 | Flame-retardant reinforced PBT plastic with non-combustible glowing filament at 750 DEG C and production method thereof |
| CN102093675A (en) * | 2010-12-10 | 2011-06-15 | 从化市聚赛龙工程塑料有限公司 | High comparative tracking index value flame-retardant and reinforced polybutylene terephthalate material and preparation method and application thereof |
| US20110319534A1 (en) * | 2010-06-29 | 2011-12-29 | Sabic Innovative Plastics Ip B.V. | Flame resistant polyester compositions, method of manufacture, and articles thereof |
| US20110319536A1 (en) * | 2010-06-29 | 2011-12-29 | Sabic Innovative Plastics Ip B.V. | Flame resistant polyester compositions, method of manufacture, and articles thereof |
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Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6248814B1 (en) * | 1998-03-25 | 2001-06-19 | Teijin Limited | Resin composition |
| EP1288260A1 (en) * | 2001-08-29 | 2003-03-05 | Albemarle Corporation | Flame retardant compositions |
| CN1749313A (en) * | 2005-08-03 | 2006-03-22 | 广州市花都科苑企业有限公司 | High CTI value no-halogen no-red phosphorus flame-retardant reinforced poly butanediol terephthate |
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| US20110319534A1 (en) * | 2010-06-29 | 2011-12-29 | Sabic Innovative Plastics Ip B.V. | Flame resistant polyester compositions, method of manufacture, and articles thereof |
| US20110319536A1 (en) * | 2010-06-29 | 2011-12-29 | Sabic Innovative Plastics Ip B.V. | Flame resistant polyester compositions, method of manufacture, and articles thereof |
| CN101885904A (en) * | 2010-07-19 | 2010-11-17 | 中山市纳普工程塑料有限公司 | Flame-retardant reinforced PBT plastic with non-combustible glowing filament at 750 DEG C and production method thereof |
| CN102093675A (en) * | 2010-12-10 | 2011-06-15 | 从化市聚赛龙工程塑料有限公司 | High comparative tracking index value flame-retardant and reinforced polybutylene terephthalate material and preparation method and application thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107849338A (en) * | 2015-07-16 | 2018-03-27 | 胜技高分子株式会社 | Polybutylene terephthalate (PBT) resin combination |
| US10336899B2 (en) | 2015-07-16 | 2019-07-02 | Wintech Polymer Ltd. | Polybutylene terephthalate resin composition |
| CN105199337A (en) * | 2015-09-22 | 2015-12-30 | 苏州博利迈新材料科技有限公司 | PBT for reinforcement and toughness and preparation method thereof |
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Application publication date: 20120815 |