CN102952379A - Environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof - Google Patents
Environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof Download PDFInfo
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- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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Abstract
The invention discloses an environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value, which comprises the raw material components by weight percent: 45-68% of PBT, 6-20% of compound fire retardant, 3-15% of antimonous oxide, 20-30% of glass fiber, 2-10% of toughening agent, 0.1-1% of antioxidant and 0.1-1% of oxide, wherein the compound fire retardant comprises brominated polystyrene, magnesium hypophosphite and talcum powder. The invention also discloses a preparation method of the environment-friendly flame retardant glass fiber reinforced PBT material with high CTI value and high GWIT value. The composite material is higher in GWIT value and CTI value, better in flame retardant effect, environment-friendly in composite material and balanced in combination properties, thus being widely applied to products in the field of electronic electric appliances such as a low-voltage electronic capacitor shell, a load break switch, a carbon brush bracket, a moulded case circuit breaker and the like.
Description
Technical field
The present invention relates to technical field of composite materials, specifically, is that a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen PBT material and preparation method thereof.
Background technology
Polybutylene terephthalate (English name Polybutylene Terephthalate is called for short PBT) is that oyster white is translucent to opaque, crystalline thermoplastic polyester.It has high heat resistance, toughness, resistance to fatigue, self-lubricating, low-friction coefficient, and weathering resistance, water-intake rate are low, still keep various physical property (comprising electrical property) in wet environment, electrical insulating property, good forming ability.Shortcoming is that notched Izod impact strength is low, and molding shrinkage is large.Therefore most of glass fibre that adopts strengthens or the inorganic fill modification, its tensile strength, flexural strength can be enhanced about more than once, and heat-drawn wire also significantly improves.Can through after flame-retardant modified, can be widely used in the Low-voltage Electronic electric components 140 ℃ of lower long term operations, the present domestic more research that had.
21 century electronics, electric, communication, household electrical appliances, electromechanical equipment are to the high-performance micro development, and more and more higher to the requirement of anti-flaming PBT composite, simultaneously, along with the understanding of the mankind to environmental protection, Green Product is subject to common concern.Therefore, the anti-flaming PBT composite developing direction is: the performance function anti-flaming PBT composite becomes main flow; The kind of environmental type anti-flaming PBT composite and demand are more and more; The production of anti-flaming PBT composite is to many variety series future development; The use of fire retardant is to diversification, compound development.Traditional bromide fire retardant can not satisfy the requirement of high standard product, the fire retardant compound system that some are traditional, for example glass fibre+TDE+antimonous oxide compound system, glass fibre+brominated Polystyrene+antimonous oxide compound system, the CTI value of these compound systems (comparative tracking index, the relative discharge tracking index) and GWIT value (glow-wire ignition temperature, glow-wire ignition temperature) not high, be not suitable for the power utilization environment of high request.
Chinese patent literature application number 201210247419.8, open day on November 14th, 2012, a kind of high CTI, the low property separated out flame-proof glass fibre enhancing PBT composition and preparation thereof are disclosed, said composition comprises each component of following weight percent content: PBT 35～70%, compatilizer 1～8%, compositional flame-retardant master batch 1～12%, glass fibre 20～45%, oxidation inhibitor 0.1～1%, lubrication dispersing agent 0.1～1%, described compositional flame-retardant master batch comprises each component of following mass percentage content: deironing red phosphorus master batch 50%, antimigration agent 25%, high CTI auxiliary agent 25%.But yet there are no report about the matrix material that integrates the advantages such as high GWIT value, high CTI value, environmental protection, over-all properties equilibrium.
Summary of the invention
The objective of the invention is for deficiency of the prior art, provide a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass to strengthen the PBT material.This matrix material glow wire temperature is higher, environmental protection, and over-all properties is balanced, is applicable to the Low-voltage Electronic capacitor case, load break switch, carbon brush supports, the electronic applications such as breaker of plastic casing.
Again one purpose of the present invention is to provide a kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass to strengthen PBT material preparation method.
For achieving the above object, the technical scheme taked of the present invention is:
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, and described material comprises the feed composition of following weight percent content:
PBT 45%～68%，
Compound flame redundant 6%～20%,
Antimonous oxide 3%～15%,
Glass fibre 20%～30%,
Toughner 2%～10%,
Oxidation inhibitor 0.1%～1%,
Oxide compound 0.1%～1%,
Described compound flame redundant is comprised of brominated Polystyrene, magnesium hypophosphite and talcum powder.
Described PBT is polybutylene terephthalate, and its limiting viscosity is 1.0 dL/g.
Described compound flame redundant is comprised of the feed composition of following weight percent content: brominated Polystyrene 50%, magnesium hypophosphite 25%, talcum powder 25%.
Described glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface.
Described toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
Described oxidation inhibitor is Hinered phenols antioxidant.
Described oxidation inhibitor is oxidation inhibitor 1330.
Described oxide compound is ferric oxide.
For realizing above-mentioned second purpose, the technical scheme that the present invention takes is:
A kind of high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen PBT material preparation method, comprise the steps:
(1) takes by weighing each raw material according to weight percent claimed in claim 1;
The various raw materials that (2) will weigh up are put into high mixer, mix 2～5 minutes, and then discharging uses the twin screw extruder extruding pelletization.
The processing temperature of described twin screw extruder is 230～240 ℃, and the screw rod revolution is 30～40Hz.
The invention has the advantages that:
1, the present invention adopts the BACN compound system, compares with traditional flame-retardant system, in the situation that the fire retardant percentage composition is identical, the novel built system can make the GWIT value of material improve 50 ℃ to 100 ℃, can pass through 850 ℃ of glowing filaments;
2, the adding of glass fibre can make the GWIT value of material obviously improve, and toughner can improve the impact property of material, improves the materials processing flowability, reduces frictional coefficient, improves slipping;
3, Hinered phenols antioxidant can improve matrix material in the antioxidant property of the course of processing and the ageing resistance in the use procedure, adopts oxide compound as the auxiliary agent of carrying high CTI value;
4, the present invention is under specific processing conditions, and raw material is better dispersed, and the residence time is short, adopts and shears slightly weak combination, prevents that fire retardant from decomposing, thereby has guaranteed the steady quality of material; GWIT value and the CTI value of the matrix material for preparing are higher, flame retardant effect is better, the matrix material environmental protection, over-all properties is balanced, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
Embodiment
The below elaborates to embodiment provided by the invention.
High CTI value of the present invention, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, and described PBT is commercially available polybutylene terephthalate, and its limiting viscosity is preferably 1.0 dL/g, also can be other value of 0.8～1.2 dL/g scope; Described compound flame redundant is comprised of brominated Polystyrene (being called for short BPS), magnesium hypophosphite and talcum powder, and weight percent content is preferably BPS 50%, magnesium hypophosphite 25%, talcum powder 25%, the GWIT value of this fire retardant energy Effective Raise matrix material; Described glass fibre is preferably the alkali free glass fibre that process through silane coupling agent on the surface, and glass fibre is added in the silane coupling agent, and its surface is processed through silane coupling agent, and it can make the GWIT value of material obviously improve; Described toughner can improve the impact property of material, can be ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, ethylene-methyl acrylate copolymer, ethylene-vinyl acetate copolymer etc., be preferably the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer; Described oxidation inhibitor is preferably the oxidation inhibitor 1330 in the Hinered phenols antioxidant, can also be antioxidant 1010, antioxidant 300, thio-2 acid dibasic acid esters etc., all can block, suppress or delay polymkeric substance oxidation or autoxidation process, can improve matrix material in the course of processing antioxidant property and the ageing resistance in the use procedure; Described oxide compound is as the auxiliary agent of carrying high CTI value, can be aluminum oxide, magnesium oxide etc., is preferably ferric oxide.
In the PBT composite manufacture process of the present invention, the various raw materials that weigh up are put into high mixer, mixed 2～5 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 30～40Hz.
Embodiment 1 PBT composite manufacture ()
The limiting viscosity of PBT is 1.0 dL/g, compound flame redundant is that the raw material of BPS 50%, magnesium hypophosphite 25% and talcum powder 25% forms by weight percent content, glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface, toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Take by weighing each feed composition: PBT 45% by following weight percent content, compound flame redundant 20%, antimonous oxide 4%, glass fibre 20%, toughner 10%, oxidation inhibitor 0.1%, oxide compound 0.9%.Each raw material that weighs up is put into high mixer, mixed 2 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 30Hz.
Embodiment 2 PBT composite manufactures (two)
The limiting viscosity of PBT is 0.8 dL/g, compound flame redundant is that the raw material of BPS 50%, magnesium hypophosphite 25% and talcum powder 25% forms by weight percent content, glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface, toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is antioxidant 1010, and oxide compound is ferric oxide.
Take by weighing each feed composition: PBT 55% by following weight percent content, compound flame redundant 8%, antimonous oxide 3%, glass fibre 30%, toughner 2%, oxidation inhibitor 1%, oxide compound 1%.Each raw material that weighs up is put into high mixer, mixed 5 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 35Hz.
Embodiment 3 PBT composite manufactures (three)
The limiting viscosity of PBT is 1 dL/g, compound flame redundant is that the raw material of BPS 50%, magnesium hypophosphite 25% and talcum powder 25% forms by weight percent content, toughner is the ethylene-methyl acrylate copolymer, and oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is aluminum oxide.
Take by weighing each feed composition: PBT 50% by following weight percent content, compound flame redundant 13%, antimonous oxide 3%, glass fibre 25%, toughner 8%, oxidation inhibitor 0.5%, oxide compound 0.5%.Each raw material that weighs up is put into high mixer, mixed 3 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 40Hz.
Embodiment 4 PBT composite manufactures (four)
The limiting viscosity of PBT is 1 dL/g, compound flame redundant is that the raw material of BPS 60%, magnesium hypophosphite 20% and talcum powder 20% forms by weight percent content, glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface, toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Take by weighing each feed composition: PBT 68% by following weight percent content, compound flame redundant 6%, antimonous oxide 3%, glass fibre 20%, toughner 2%, oxidation inhibitor 0.9%, oxide compound 0.1%.Each raw material that weighs up is put into high mixer, mixed 4 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 38Hz.
Embodiment 5 PBT composite manufactures (five)
The limiting viscosity of PBT is 1.0 dl/g, compound flame redundant is that the raw material of BPS 50%, magnesium hypophosphite 25% and talcum powder 25% forms by weight percent content, glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface, toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is antioxidant 300, and oxide compound is ferric oxide.
Take by weighing each feed composition: PBT 45% by following weight percent content, compound flame redundant 10%, antimonous oxide 15%, glass fibre 24%, toughner 5%, oxidation inhibitor 0.4%, oxide compound 0.6%.Each raw material that weighs up is put into high mixer, mixed 5 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 30Hz.
Embodiment 6 PBT composite manufactures (six)
The limiting viscosity of PBT is 1.0 dl/g, compound flame redundant is that the raw material of BPS 45%, magnesium hypophosphite 30% and talcum powder 25% forms by weight percent content, toughner is the ethylene-vinyl acetate copolymer, and oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is magnesium oxide.
Take by weighing each feed composition: PBT 47% by following weight percent content, compound flame redundant 16%, antimonous oxide 10%, glass fibre 22%, toughner 4%, oxidation inhibitor 0.7%, oxide compound 0.3%.Each raw material that weighs up is put into high mixer, mixed 4 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 40Hz.
Embodiment 7 PBT composite manufactures (seven)
The limiting viscosity of PBT is 1.2 dl/g, compound flame redundant is that the raw material of BPS 50%, magnesium hypophosphite 25% and talcum powder 25% forms by weight percent content, glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface, toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer, oxidation inhibitor is oxidation inhibitor 1330, and oxide compound is ferric oxide.
Take by weighing each feed composition: PBT 60% by following weight percent content, compound flame redundant 7%, antimonous oxide 6%, glass fibre 23%, toughner 3%, oxidation inhibitor 0.6%, oxide compound 0.4%.Each raw material that weighs up is put into high mixer, mixed 3 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, and two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw rod revolution is 35Hz.
Need to prove, the fiber glass reinforced PBT matrix material that embodiment 1-7 is obtained carries out performance test, adopt the ASTM standard, test result shows: the PBT matrix material of preparation has higher GWIT value and CTI value, and the flame retardant resistance of matrix material, tensile strength and flexural strength all meet the requirements.
Embodiment 8～9 and Comparative Examples 1～7
The limiting viscosity of PBT is 1.0 dL/g; Compound flame redundant is that the raw material of BPS 50%, magnesium hypophosphite 25% and talcum powder 25% forms by weight percent content; Common fire retardant can be triphenylphosphate, TDE, decabromodiphynly oxide, magnesium hydroxide, red phosphorus etc., and the present invention all adopts TDE; Glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface; Toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer; Oxidation inhibitor is oxidation inhibitor 1330; Oxide compound is ferric oxide.
(%) takes by weighing each feed composition by the weight percent content shown in the table 1.Each raw material that weighs up is put into high mixer, mixed 5 minutes, then discharging uses the twin screw extruder extruding pelletization; The processing temperature of described twin screw extruder is 230～240 ℃, and forcing machine comprises nine warm areas, wherein one section 230 ℃, two sections 230 ℃, three sections 235 ℃, four sections 235 ℃, five sections 240 ℃, six sections 240 ℃, seven sections 235 ℃, eight sections 235 ℃, nine sections 230 ℃, the screw host revolution is 35Hz, and the feeding revolution is 13 Hz.
Each composition of raw materials in table 1 embodiment 8～9 and the Comparative Examples 1～7
Embodiment 10 performance tests
Adopt the ASTM standard, the PBT matrix material that embodiment 8～9, Comparative Examples 1～7 are prepared carries out performance test, and test result is as shown in table 2.
The performance test results of table 2 matrix material
Associative list 1 and table 2, as can be known, the present invention adopts the BACN compound system from table, compares the GWIT value of novel built fire retardant energy Effective Raise material with traditional common fire retardant; The adding of alkali free glass fibre can make the GWIT value of matrix material obviously improve, and toughner can improve the impact property of material; Ferric oxide has considerable influence to carrying high CTI value.
GWIT value and the CTI value of matrix material of the present invention are higher, flame retardant effect is better, the matrix material environmental protection, over-all properties is balanced, can be widely used in the product of the field of electronics such as Low-voltage Electronic capacitor case, load break switch, carbon brush supports, breaker of plastic casing.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the inventive method; can also make some improvement and replenish, these improvement and replenish and also should be considered as protection scope of the present invention.
Claims (10)
1. a high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described material comprises the feed composition of following weight percent content:
PBT 45%～68%，
Compound flame redundant 6%～20%,
Antimonous oxide 3%～15%,
Glass fibre 20%～30%,
Toughner 2%～10%,
Oxidation inhibitor 0.1%～1%,
Oxide compound 0.1%～1%,
Described compound flame redundant is comprised of brominated Polystyrene, magnesium hypophosphite and talcum powder.
2. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described PBT is polybutylene terephthalate, and its limiting viscosity is 1.0 dL/g.
3. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described compound flame redundant is comprised of the feed composition of following weight percent content: brominated Polystyrene 50%, magnesium hypophosphite 25%, talcum powder 25%.
4. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described glass fibre is the alkali free glass fibre that process through silane coupling agent on the surface.
5. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described toughner is the ethylene-methyl acrylate-glyceryl methacrylate random terpolymer.
6. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described oxidation inhibitor is Hinered phenols antioxidant.
7. high CTI value according to claim 6, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described oxidation inhibitor is oxidation inhibitor 1330.
8. high CTI value according to claim 1, high GWIT value environment-protection flame-proof fiberglass strengthen the PBT material, it is characterized in that, described oxide compound is ferric oxide.
9. a high CTI value, high GWIT value environment-protection flame-proof fiberglass strengthen PBT material preparation method, it is characterized in that, comprise the steps:
(1) takes by weighing each raw material according to weight percent claimed in claim 1;
The various raw materials that (2) will weigh up are put into high mixer, mix 2～5 minutes, and then discharging uses the twin screw extruder extruding pelletization.
10. preparation method according to claim 9 is characterized in that, the processing temperature of described twin screw extruder is 230～240 ℃, and the screw rod revolution is 30～40Hz.
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| CN2012105101419A CN102952379A (en) | 2012-12-04 | 2012-12-04 | Environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof |
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| CN2012105101419A CN102952379A (en) | 2012-12-04 | 2012-12-04 | Environment-friendly flame retardant glass fiber reinforced polybutylece terephthalate (PBT) material with high comparative tracking index (CTI) value and high glow wire ignition temperature (GWIT) value and preparation method thereof |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103756269A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | High temperature-resistant halogen-free flame retardant PBT (polybutylece terephthalate) material and preparation method thereof |
| CN103788598A (en) * | 2014-01-29 | 2014-05-14 | 厦门市天宇塑料工业有限公司 | Anti-yellowing anti-separation flame-retardant enhanced PBT composition and use thereof |
| CN107163518A (en) * | 2017-06-26 | 2017-09-15 | 东莞市东翔塑胶有限公司 | It is a kind of can laser marking high glowing filament ignition temperature flame-retardant PBT composite and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128541A (en) * | 2005-02-23 | 2008-02-20 | 宝理塑料株式会社 | Flame retardant resin composition |
| CN102040807A (en) * | 2009-10-22 | 2011-05-04 | 上海日之升新技术发展有限公司 | High-glowing filament environmental-friendly flame retardant reinforced PBT (Polybutylece Terephthalate) composite material and preparation method thereof |
-
2012
- 2012-12-04 CN CN2012105101419A patent/CN102952379A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101128541A (en) * | 2005-02-23 | 2008-02-20 | 宝理塑料株式会社 | Flame retardant resin composition |
| CN102040807A (en) * | 2009-10-22 | 2011-05-04 | 上海日之升新技术发展有限公司 | High-glowing filament environmental-friendly flame retardant reinforced PBT (Polybutylece Terephthalate) composite material and preparation method thereof |
Cited By (13)
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|---|---|---|---|---|
| CN103756269B (en) * | 2013-12-31 | 2015-12-09 | 东莞市松燊塑料科技有限公司 | A kind of high temperature resistant halogen-free flame-retardant PBT material and preparation method thereof |
| CN103756269A (en) * | 2013-12-31 | 2014-04-30 | 东莞市松燊塑料科技有限公司 | High temperature-resistant halogen-free flame retardant PBT (polybutylece terephthalate) material and preparation method thereof |
| CN103788598A (en) * | 2014-01-29 | 2014-05-14 | 厦门市天宇塑料工业有限公司 | Anti-yellowing anti-separation flame-retardant enhanced PBT composition and use thereof |
| CN110121525B (en) * | 2016-10-18 | 2021-04-02 | 溴化合物有限公司 | Flame-retardant polyester composition |
| CN110121525A (en) * | 2016-10-18 | 2019-08-13 | 溴化合物有限公司 | Flame retardant polyester composition |
| CN107418156A (en) * | 2017-04-21 | 2017-12-01 | 金旸（厦门）新材料科技有限公司 | A kind of high glow-wire enhancing flame retardant type PBT composite and preparation method thereof |
| CN107418156B (en) * | 2017-04-21 | 2019-12-03 | 金旸（厦门）新材料科技有限公司 | A kind of high glow-wire enhancing flame retardant type PBT composite and preparation method thereof |
| CN107163518A (en) * | 2017-06-26 | 2017-09-15 | 东莞市东翔塑胶有限公司 | It is a kind of can laser marking high glowing filament ignition temperature flame-retardant PBT composite and preparation method thereof |
| CN109735100A (en) * | 2018-12-28 | 2019-05-10 | 金发科技股份有限公司 | A kind of halogen flame-retardant polyamide composite material of no antimony and preparation method thereof |
| CN109749376A (en) * | 2019-01-18 | 2019-05-14 | 林建民 | A kind of high CTI fiber glass reinforced PBT composite material and its preparation process |
| CN111808405A (en) * | 2020-06-23 | 2020-10-23 | 金发科技股份有限公司 | Polyester material with high glowing filament ignition temperature resistance and preparation method thereof |
| CN114621571A (en) * | 2020-12-11 | 2022-06-14 | 湖南登科材料科技有限公司 | PC/PBT alloy CTI-passing plastic and preparation method thereof |
| CN112778710A (en) * | 2020-12-25 | 2021-05-11 | 金发科技股份有限公司 | high-PTI (polybutylene terephthalate) and high-toughness PBT (polybutylene terephthalate) composition as well as preparation method and application thereof |
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