CN104710735A - Phosphor halogen-free flame-retardant PC/PET alloy - Google Patents
Phosphor halogen-free flame-retardant PC/PET alloy Download PDFInfo
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- CN104710735A CN104710735A CN201310673261.5A CN201310673261A CN104710735A CN 104710735 A CN104710735 A CN 104710735A CN 201310673261 A CN201310673261 A CN 201310673261A CN 104710735 A CN104710735 A CN 104710735A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a phosphor halogen-free flame-retardant PC/PET alloy, which is composed of the following components in percentage by weight: 50 to 75% of PC, 5 to 30% of PET, 5 to 10% of phosphor halogen-free flame retardant, 2 to 4% of compatilizer, 0.1 to 1% of anti-dripping agent, 0.5 to 1% of hydrolysis resistant agent, 0.1 to 0.5% of antioxidant, and 0.1 to 1% of lubricant. Compared to the prior art, the prepared compounded phosphor halogen-free flame retardant and PET flame-retardant master batch are used to modify the flame retardant performance of PC, so that the prepared phosphor halogen-free flame-retardant PC/PET alloy has the excellent properties of PC and PET, also has an excellent flame-retardant performance and processability, and has the advantages of lasting flame-retardant effect, no halogen, smoke suppression, and no molten droplet. The flame retardant performance can reach the UL94V-0 level. Furthermore, the cost is low, and thus the alloy has a good prospect and prominent social and economic benefits.
Description
Technical field
The present invention relates to technical field of polymer materials, specifically a kind of phosphorus series non-halogen fire retardation PC/PET alloy.
Background technology
PC/PET alloy (polycarbonate/polyethylene terephthalate) is the ideal engineering plastics of a kind of over-all properties, and it has the excellent properties that PC, PET single component does not possess, and all can use in a lot of occasion.The flame retardant resistance of PC itself can reach UL94 V-2 level, but practical application often requires higher flame retardant properties, and PET add the flame retardant resistance reducing PC, in order to meet PC/PET alloy fire safety demands in actual applications, usually need add fire retardant carry out modification.Phosphorus flame retardant is one of most important kind in PC/PET alloy, and have fire-retardant and plasticising double effects, the obnoxious flavour of generation is few, is development in recent years a kind of high-performance refractory agent rapidly.At present, on market, phosphorous flame-retardant PC/PET alloy is adopt organophosphorus system flame-retardant modified mostly, and majority adopts single fire retardant and has compared with high volatile volatile and water-soluble, affects flame retardant effect.
Summary of the invention
The object of the present invention is to provide the phosphorus series non-halogen fire retardation PC/PET alloy of a kind of fire-retardant efficient, high stability and high heat resistance.
The technical solution adopted for the present invention to solve the technical problems is: phosphorus series non-halogen fire retardation PC/PET alloy, and its component by mass percent proportioning is: PC 50% ~ 75%, PET 5% ~ 30%, phosphorus series non-halogen fire retardant 5% ~ 10%, compatilizer 2% ~ 4%, anti-dripping agent 0.1% ~ 1%, hydrolysis agent 0.5% ~ 1%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.
Described PC is bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 20000 ~ 35000g/mol.
Described PET is polyethylene terephthalate, and its intrinsic viscosity is 0.6 ~ 1.0dL/g.
The compound phosphorus series non-halogen fire retardant that described phosphorus series non-halogen fire retardant is dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP) of mass ratio 4:3:3, triphenylphosphate (TPP) and ammonium polyphosphate (APP) three mix composition.
Described compatilizer is styrene-grafted copolymer-maleic anhydride (SMA).
Described anti-dripping agent is the one in tetrafluoroethylene, polyvinylidene difluoride (PVDF), poly-hexafluoroethylene.
Described hydrolysis agent is the one in phenyl glycidyl ether, dihydroxyphenyl propane bisglycidyl ether, carbodiimide, 2-oxazoline.
Described oxidation inhibitor is the Hinered phenols antioxidant 1010 or 1076 of mass ratio 1:2 and the compound of phosphite ester kind antioxidant 168.
Described lubricant is the one in Zinic stearas, calcium stearate, ethylene bis stearamide, pentaerythritol stearate.
The preparation method of above-mentioned phosphorus series non-halogen fire retardation PC/PET alloy, comprises the following steps:
(1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by;
(2), by dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP), triphenylphosphate (TPP) and ammonium polyphosphate (APP) in mass ratio 4:3:3 take and add in high-speed mixer and stir, namely obtained compound phosphorus series non-halogen fire retardant, stand-by after drying;
(3) the compound phosphorus series non-halogen fire retardant, will dry PET and step (2) be taken by weight ratio obtaining, add in high-speed mixer, stir 2 ~ 4 minutes, then add take by weight ratio anti-dripping agent, hydrolysis agent, oxidation inhibitor and lubricant, continue stirring 3 ~ 10 minutes, after making fully to mix, discharging adds in twin screw extruder, extrude after melt blending at 240 DEG C ~ 275 DEG C, cooling granulation, and dry after obtained PET fire-retardant master granule, stand-by;
(4), PET fire-retardant master granule obtained to the PC and step (3) that take drying is by weight ratio added in high-speed mixer, add the compatilizer taken by weight ratio simultaneously, after making to stir 3 ~ 15 minutes premixs together, discharging adds in twin screw extruder, extrude after abundant melt blending at 230 DEG C ~ 280 DEG C, cooling granulation, obtain phosphorus series non-halogen of the present invention fire retardation PC/PET alloy.
The invention has the beneficial effects as follows, compared with prior art, the present invention carries out flame-retardant modified by preparing compound phosphorus series non-halogen fire retardant and making PET fire-retardant master granule to PC, make the phosphorus series non-halogen fire retardation PC/PET alloy obtained, while the original premium properties of maintenance PC/PET alloy, there is excellent flame retardant properties and processing characteristics, and flame retardant effect is lasting, Halogen, press down cigarette, without molten drop and Ke Da UL94 V-0 level performance, cost is also low, and thus its application has good prospect and remarkable economic results in society.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with concrete preferred embodiment.
Embodiment 1:
A kind of phosphorus series non-halogen fire retardation PC/PET alloy, its component by mass percent proportioning is: the Hinered phenols antioxidant 1010 of PC 60%, PET 24%, phosphorus series non-halogen fire retardant 10%, styrene-grafted copolymer-maleic anhydride (SMA) 3%, tetrafluoroethylene 0.7%, carbodiimide 1%, mass ratio 1:2 and compound 0.3%, the calcium stearate 1% of phosphite ester kind antioxidant 168.Wherein, described PC is bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 20000 ~ 35000g/mol; Described PET is polyethylene terephthalate, and its intrinsic viscosity is 0.6 ~ 1.0dL/g; The compound phosphorus series non-halogen fire retardant that described phosphorus series non-halogen fire retardant is dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP) of mass ratio 4:3:3, triphenylphosphate (TPP) and ammonium polyphosphate (APP) three mix composition.
Preparation method: (1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by, (2), by dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP), triphenylphosphate (TPP) and ammonium polyphosphate (APP) in mass ratio 4:3:3 take and add in high-speed mixer and stir, namely obtained compound phosphorus series non-halogen fire retardant, stand-by after drying, (3), by the compound phosphorus series non-halogen fire retardant that the PET and step (2) that take drying by weight ratio obtain, add in high-speed mixer, stir 2 ~ 4 minutes, then the tetrafluoroethylene taken by weight ratio is added, carbodiimide, the Hinered phenols antioxidant 1010 of mass ratio 1:2 and the compound of phosphite ester kind antioxidant 168, calcium stearate, continue stirring 3 ~ 10 minutes, after making fully to mix, discharging adds in twin screw extruder, extrude after melt blending at 240 DEG C ~ 275 DEG C, cooling granulation, and dry rear obtained PET fire-retardant master granule, stand-by, (4), PET fire-retardant master granule obtained to the PC and step (3) that take drying is by weight ratio added in high-speed mixer, add the styrene-grafted copolymer-maleic anhydride (SMA) taken by weight ratio simultaneously, after making to stir 3 ~ 15 minutes premixs together, discharging adds in twin screw extruder, extrude after abundant melt blending at 230 DEG C ~ 280 DEG C, cooling granulation, obtain phosphorus series non-halogen of the present invention fire retardation PC/PET alloy.
Embodiment 2:
A kind of phosphorus series non-halogen fire retardation PC/PET alloy, its component by mass percent proportioning is: the Hinered phenols antioxidant 1076 of PC 65%, PET 24%, phosphorus series non-halogen fire retardant 5%, styrene-grafted copolymer-maleic anhydride (SMA) 4%, polyvinylidene difluoride (PVDF) 0.5%, 2-oxazoline 0.5%, mass ratio 1:2 and compound 0.3%, the pentaerythritol stearate 0.7% of phosphite ester kind antioxidant 168.Wherein, described PC is bisphenol A-type aromatic copolycarbonate, and weight-average molecular weight is 20000 ~ 35000g/mol; Described PET is polyethylene terephthalate, and its intrinsic viscosity is 0.6 ~ 1.0dL/g; The compound phosphorus series non-halogen fire retardant that described phosphorus series non-halogen fire retardant is dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP) of mass ratio 4:3:3, triphenylphosphate (TPP) and ammonium polyphosphate (APP) three mix composition.
Preparation method: (1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by, (2), by dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP), triphenylphosphate (TPP) and ammonium polyphosphate (APP) in mass ratio 4:3:3 take and add in high-speed mixer and stir, namely obtained compound phosphorus series non-halogen fire retardant, stand-by after drying, (3), by the compound phosphorus series non-halogen fire retardant that the PET and step (2) that take drying by weight ratio obtain, add in high-speed mixer, stir 2 ~ 4 minutes, then the polyvinylidene difluoride (PVDF) taken by weight ratio is added, 2-oxazoline, the Hinered phenols antioxidant 1076 of mass ratio 1:2 and the compound of phosphite ester kind antioxidant 168, pentaerythritol stearate, continue stirring 3 ~ 10 minutes, after making fully to mix, discharging adds in twin screw extruder, extrude after melt blending at 240 DEG C ~ 275 DEG C, cooling granulation, and dry rear obtained PET fire-retardant master granule, stand-by, (4), PET fire-retardant master granule obtained to the PC and step (3) that take drying is by weight ratio added in high-speed mixer, add the styrene-grafted copolymer-maleic anhydride (SMA) taken by weight ratio simultaneously, after making to stir 3 ~ 15 minutes premixs together, discharging adds in twin screw extruder, extrude after abundant melt blending at 230 DEG C ~ 280 DEG C, cooling granulation, obtain phosphorus series non-halogen of the present invention fire retardation PC/PET alloy.
Claims (6)
1. phosphorus series non-halogen fire retardation PC/PET alloy, it is characterized in that, its component by mass percent proportioning is: PC 50% ~ 75%, PET 5% ~ 30%, phosphorus series non-halogen fire retardant 5% ~ 10%, compatilizer 2% ~ 4%, anti-dripping agent 0.1% ~ 1%, hydrolysis agent 0.5% ~ 1%, oxidation inhibitor 0.1% ~ 0.5%, lubricant 0.1% ~ 1%.
2. phosphorus series non-halogen fire retardation PC/PET alloy according to claim 1, it is characterized in that, described phosphorus series non-halogen fire retardant is the compound phosphorus series non-halogen fire retardant that the dihydroxyphenyl propane of mass ratio 4:3:3-bis-(diphenyl phosphoester) (BDP), triphenylphosphate (TPP) and ammonium polyphosphate (APP) three mix composition.
3. phosphorus series non-halogen fire retardation PC/PET alloy according to claim 1, is characterized in that, described compatilizer is styrene-grafted copolymer-maleic anhydride (SMA).
4. phosphorus series non-halogen fire retardation PC/PET alloy according to claim 1, is characterized in that, described anti-dripping agent is the one in tetrafluoroethylene, polyvinylidene difluoride (PVDF), poly-hexafluoroethylene.
5. phosphorus series non-halogen fire retardation PC/PET alloy according to claim 1, is characterized in that, described hydrolysis agent is the one in phenyl glycidyl ether, dihydroxyphenyl propane bisglycidyl ether, carbodiimide, 2-oxazoline.
6. the preparation method of phosphorus series non-halogen fire retardation PC/PET alloy according to claim 1, is characterized in that, comprise the following steps:
(1), by PC in blast drier at 110 DEG C ~ 130 DEG C temperature dry 3 ~ 4 hours, PET at 130 DEG C ~ 150 DEG C dry 3 ~ 4 hours, stand-by;
(2), by dihydroxyphenyl propane-bis-(diphenyl phosphoester) (BDP), triphenylphosphate (TPP) and ammonium polyphosphate (APP) in mass ratio 4:3:3 take and add in high-speed mixer and stir, namely obtained compound phosphorus series non-halogen fire retardant, stand-by after drying;
(3) the compound phosphorus series non-halogen fire retardant, will dry PET and step (2) be taken by weight ratio obtaining, add in high-speed mixer, stir 2 ~ 4 minutes, then add take by weight ratio anti-dripping agent, hydrolysis agent, oxidation inhibitor and lubricant, continue stirring 3 ~ 10 minutes, after making fully to mix, discharging adds in twin screw extruder, extrude after melt blending at 240 DEG C ~ 275 DEG C, cooling granulation, and dry after obtained PET fire-retardant master granule, stand-by;
(4), PET fire-retardant master granule obtained to the PC and step (3) that take drying is by weight ratio added in high-speed mixer, add the compatilizer taken by weight ratio simultaneously, after making to stir 3 ~ 15 minutes premixs together, discharging adds in twin screw extruder, extrude after abundant melt blending at 230 DEG C ~ 280 DEG C, cooling granulation, obtain phosphorus series non-halogen of the present invention fire retardation PC/PET alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310673261.5A CN104710735A (en) | 2013-12-12 | 2013-12-12 | Phosphor halogen-free flame-retardant PC/PET alloy |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201310673261.5A CN104710735A (en) | 2013-12-12 | 2013-12-12 | Phosphor halogen-free flame-retardant PC/PET alloy |
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| CN104710735A true CN104710735A (en) | 2015-06-17 |
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| CN201310673261.5A Pending CN104710735A (en) | 2013-12-12 | 2013-12-12 | Phosphor halogen-free flame-retardant PC/PET alloy |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924949A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Flame-retardant plastic material |
| CN105924948A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Novel plastic material |
| CN106674965A (en) * | 2016-12-27 | 2017-05-17 | 上海锦湖日丽塑料有限公司 | Efficient smoke-suppressing anti-flaming modified aromatic polyester and preparation method thereof |
| CN110698835A (en) * | 2019-11-08 | 2020-01-17 | 江苏沃特新材料科技有限公司 | PC/PBT composite flame-retardant material for vehicle interior trim and preparation method thereof |
-
2013
- 2013-12-12 CN CN201310673261.5A patent/CN104710735A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105924949A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Flame-retardant plastic material |
| CN105924948A (en) * | 2016-07-12 | 2016-09-07 | 广西南宁桂尔创环保科技有限公司 | Novel plastic material |
| CN106674965A (en) * | 2016-12-27 | 2017-05-17 | 上海锦湖日丽塑料有限公司 | Efficient smoke-suppressing anti-flaming modified aromatic polyester and preparation method thereof |
| CN110698835A (en) * | 2019-11-08 | 2020-01-17 | 江苏沃特新材料科技有限公司 | PC/PBT composite flame-retardant material for vehicle interior trim and preparation method thereof |
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