CN106700387A - Flame-retardant master batch, preparation method and application of master batch to flame-retardant PC and alloy materials - Google Patents
Flame-retardant master batch, preparation method and application of master batch to flame-retardant PC and alloy materials Download PDFInfo
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- CN106700387A CN106700387A CN201510779048.1A CN201510779048A CN106700387A CN 106700387 A CN106700387 A CN 106700387A CN 201510779048 A CN201510779048 A CN 201510779048A CN 106700387 A CN106700387 A CN 106700387A
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Abstract
The invention relates to flame-retardant master batch, a preparation method and an application of the master batch to flame-retardant PC and alloy materials. The flame-retardant master batch is prepared from 300-500 parts of ABS resin, 400-500 parts of a flame retardant, 100-200 parts of a toughening agent, 20-50 parts of an anti-dripping agent, 10-20 parts of an antioxidant and 5-10 parts of a lubricant through mixing and extrusion granulation. Meanwhile, the flame-retardant master batch is used as a flame retardant to be added to PC or PC alloy materials, directly mixing is performed, and a flame-retardant PC material or a flame-retardant PC alloy material are obtained. The flame-retardant master batch is small in dosage, has excellent flame retardance, exerts smaller influence on material performance and can be directly blended with PC and PC alloys for injection molding without extrusion granulation, an intermediate processing link is omitted, and the processing cost is reduced.
Description
Technical field：
The present invention relates to polymer processing field, a kind of fire-retardant master granule, preparation method and its application in fire retardation PC and alloy material are specifically related to.
Background technology：
Makrolon（PC）With good mechanical property, excellent low-temperature flexibility, dimensional stability, there is temperature in use higher, the fields such as automobile, electronic apparatus, household electrical appliances, food containers are mainly used in, while the alloy such as PC/ABS, PC/ASA, PC/PBT based on PC also has being widely applied very much.PC also has excellent anti-flammability, itself has the anti-flammability of V2, just can reach V0 grades after a small amount of fire retardant is added, and can as requested provide halogen fire-retardant or halogen-free flameproof fire retardation PC and its alloy product.But the processing temperature of PC is higher, and the processing temperature of conventional bromide fire retardant is relatively low, therefore the problems such as uneven fire retardant dispersion, fire retardant degraded, product turn to be yellow occurs in extruding pelletization and processing.
To solve this problem, the invention provides a kind of fire-retardant master granule, it is molded after directly being mixed with PC or PC alloy materials charge, dispersiveness of the fire retardant in PC can be improved, improves processing characteristics.
The content of the invention：
Technological deficiency of the present invention for existing fire retardation PC, there is provided a kind of fire-retardant master granule, preparation method and its application in fire retardation PC and alloy material.The fire-retardant master granule has excellent fire resistance, and consumption is few, and mixed water injection modeling is directly criticized with raw material, and fire-retardant master granule can be dispersed, reduces middle processing link.
To achieve the above object, the technical scheme that the present invention is used is as follows：
A kind of fire-retardant master granule, it is characterised in that：It is prepared from by weight by following components：
ABS resin 300-500 parts,
Fire retardant 400-500 parts,
Toughener 100-200 parts,
Anti-dripping agent 20-50 parts,
Antioxidant 10-20 parts,
Lubricant 5-10 parts,
The ABS resin, fire retardant and toughener weight portion sum are 1000 parts.
Further scheme, the ABS resin is the one kind in substance law ABS or emulsion method ABS, and its melt index is not more than 35g/10min under the conditions of 220 DEG C/10kg.
The fire retardant is bromide fire retardant.
The bromide fire retardant is the one kind in brominated epoxy resin, brominated triazine, TDE.
The toughener is MBS（MBS）.
The anti-dripping agent is polytetrafluoroethylene powder（PTFE）.
The antioxidant is N, N'- couples-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine（Antioxidant 1098）、β-（3,5- di-tert-butyl-hydroxy phenyls）The positive octadecanol ester of propionic acid（Antioxidant 1076）With three [2.4- di-tert-butyl-phenyls] phosphite esters（Irgasfos 168）In two kinds of compounds.
The lubricant is N, N '-ethylene bis stearamide（EBS）, calcium stearate or pentaerythrite stearate (PETS).
Present invention also offers the preparation method of the fire-retardant master granule, the method is：It is sufficiently mixed uniformly during ABS, fire retardant, toughener, anti-dripping agent, antioxidant and lubricant are added into high-speed mixer first, then by well mixed material feeding double screw extruder, material is sufficiently fused under shearing, mixing and the conveying of screw rod, and fire-retardant master granule is granulated to obtain after extruding wire drawing finally by die orifice；Each section of temperature of wherein double screw extruder is set as 170-220 DEG C.
It is sufficiently mixed uniformly during ABS, fire retardant, toughener, anti-dripping agent, antioxidant and lubricant are added into high-speed mixer first, then by well mixed material feeding double screw extruder, material is sufficiently fused under shearing, mixing and the conveying of screw rod, finally by granulation after die orifice extrusion wire drawing.Each section of temperature of wherein double screw extruder is set as 170-220 DEG C.
Third object of the present invention is to provide application of the above-mentioned fire-retardant master granule in fire retardation PC and fire retardation PC alloy material, using fire-retardant master granule as fire retardant add PC or PC alloy materials in, directly mix fire retardation PC material or fire retardation PC alloy material.
Compared with prior art, fire retardant accounting is moderate in fire-retardant master granule prepared by the present invention, it is readily extruded granulation processing, and because the processing temperature of ABS is relatively low, fire retardant used is not easily decomposed under cryogenic, and the processing temperature of fire retardation PC is higher at present, the problem often degraded in process, and can solve this problem with the fire-retardant master granule that the present invention is provided.
Fire-retardant master granule of the invention is added in PC and its alloy material, and its addition is few, excellent fireproof performance, influences smaller to material property, can be instructed by European Union ROHS.
Fire-retardant master granule of the invention directly with the blending injection of the PC alloys such as PC or PC/ABS, PC/PBT, without by extruding pelletization, reducing intermediate link again, reduce processing charges.
Specific embodiment：
The invention will be further described with reference to embodiments, and its purpose is only that the protection domain for being best understood from the object of the invention, being not intended to limit the present invention.
Raw material used is commercially available, the substance law ABS that wherein ABS is produced for Gaoqiao Petrochemical Company company in all embodiments and comparative example
8391, PC is the PC2800 of Beyer Co., Ltd's production, and PBT is the PBT1200 of Changchun chemical company production.
Embodiment 1：
300 parts of ABS, 500 parts of brominated epoxy resin, 200 parts of MBS, 35 parts of PTFE, 4 parts of antioxidant 1076,6 parts, lubricant PETS5 parts of irgasfos 168；It is sufficiently mixed uniformly during ABS, brominated epoxy resin, MBS, PTFE, antioxidant 1076, irgasfos 168 and lubricant PETS are added into high-speed mixer, then by well mixed material feeding double screw extruder, material is sufficiently fused under shearing, mixing and the conveying of screw rod, fire-retardant master granule 1# is obtained finally by granulation after die orifice extrusion wire drawing, each section of temperature of wherein double screw extruder is set as 170-210 DEG C.
Embodiment 2：
400 parts of ABS, 450 parts of brominated triazine, 150 parts of MBS, 20 parts of PTFE, 7 parts of antioxidant 1076,13 parts of irgasfos 168,8 parts of Lubricate EBS；It is sufficiently mixed uniformly during ABS, brominated triazine, MBS, PTFE, antioxidant 1076, irgasfos 168 and Lubricate EBS are added into high-speed mixer, then by well mixed material feeding double screw extruder, material is sufficiently fused under shearing, mixing and the conveying of screw rod, fire-retardant master granule 2# is obtained finally by granulation after die orifice extrusion wire drawing, each section of temperature of wherein double screw extruder is set as 180-215 DEG C.
Embodiment 3：
500 parts of ABS, 400 parts of TDE, 100 parts of MBS, 50 parts of PTFE, 10985 parts of antioxidant, 10 parts of irgasfos 168,10 parts of lubricant stearic acid calcium；It is sufficiently mixed uniformly during ABS, brominated triazine, MBS, PTFE, antioxidant 1098, irgasfos 168 and lubricant stearic acid calcium are added into high-speed mixer, then by well mixed material feeding double screw extruder, material is sufficiently fused under shearing, mixing and the conveying of screw rod, fire-retardant master granule 3# is obtained finally by granulation after die orifice extrusion wire drawing, each section of temperature of wherein double screw extruder is set as 190-220 DEG C.
Embodiment 4-10：
Directly stirring mixing is carried out during fire-retardant master granule prepared by above-described embodiment 1-3 is added into PC materials or PC, ABS or PC, PBT mixing materials as fire retardant respectively, then embodiment 4-10 is obtained through being molded into batten.
Existing flame retardant brominated epoxy resin is added directly into PC materials or PC, ABS or PC, PBT mixing materials simultaneously, first be well mixed in adding extruder afterwards, melted, extruding pelletization, then obtain comparative example 1-2 through being molded into batten again.
Component formula and the performance of test see the table below shown in 1 in embodiment 4-10 and comparative example 1-2, and wherein Mechanics Performance Testing standard is ASTM, and fire resistance testing standard is UL94.
The embodiment test result of table 1
| Embodiment 4 | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Comparative example 1 | Comparative example 2 | |
| PC | 1000 | 1000 | 1000 | 900 | 950 | 900 | 950 | 1000 | 900 |
| ABS | 100 | 50 | 100 | ||||||
| PBT | 100 | 50 | |||||||
| Fire-retardant master granule 1# | 30 | 120 | 100 | ||||||
| Fire-retardant master granule 2# | 30 | 70 | |||||||
| Fire-retardant master granule 3# | 30 | 50 | |||||||
| Brominated epoxy resin | 20 | 70 | |||||||
| Bending strength MPa | 100 | 101 | 97 | 86 | 82 | 89 | 95 | 98 | 86 |
| Bending modulus MPa | 2240 | 2320 | 2300 | 2320 | 2210 | 2110 | 2160 | 2180 | 2270 |
| Simply supported beam notch impact strength KJ/m2 | 76 | 78 | 65 | 58 | 68 | 54 | 44 | 73 | 52 |
| It is fire-retardant（3.2mm） | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 | V0 |
Be can be seen that according to experimental result in table 1, add a small amount of fire-retardant master granule to can reach fire-retardant effect in PC materials, and its mechanical performance with fire resistance compared with the fire retardation PC of comparative example 1 substantially close to.But because fire-retardant master granule prepared by the present invention directly can be mixed with PC materials, without by extrusion extruding pelletization, so as to reduce more processing cost, while reducing the analysis that fire retardant is degraded during extruding pelletization, the stability of processing is improved.And for PC alloy materials, the addition of fire-retardant master granule need to take the circumstances into consideration to increase, according to the results show of upper table 1, embodiment 7-10 adds fire-retardant master granule of the invention, its excellent fireproof performance.
The above-mentioned description to embodiment is to be understood that and apply the present invention for ease of those skilled in the art.Person skilled in the art obviously can easily make various modifications to these embodiments, and General Principle described herein is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art's announcement of the invention, does not depart from improvement that scope made and modification all should be within protection scope of the present invention.
Claims (10)
1. a kind of fire-retardant master granule, it is characterised in that：It is prepared from by weight by following components：
ABS resin 300-500 parts,
Fire retardant
400-500 parts,
Toughener
100-200 parts,
Anti-dripping agent
20-50 parts,
Antioxidant
10-20 parts,
Lubricant
5-10 parts,
The ABS resin, fire retardant and toughener weight portion sum are 1000 parts.
2. the fire-retardant master granule according to claim 1, it is characterised in that：The ABS resin is the one kind in substance law ABS or emulsion method ABS, and its melt index is not more than 35g/10min under the conditions of 220 DEG C/10kg.
3. the fire-retardant master granule according to claim 1, it is characterised in that：The fire retardant is bromide fire retardant.
4. the fire-retardant master granule according to claim 3, it is characterised in that：The bromide fire retardant is the one kind in brominated epoxy resin, brominated triazine, TDE.
5. the fire-retardant master granule according to claim 1, it is characterised in that：The toughener is MBS.
6. the fire-retardant master granule according to claim 1, it is characterised in that：The anti-dripping agent is polytetrafluoroethylene powder.
7. the fire-retardant master granule according to claim 1, it is characterised in that：The antioxidant is N, N'- is double-(3- (3,5- di-tert-butyl-hydroxy phenyls) propiono) hexamethylene diamine, β-（3,5- di-tert-butyl-hydroxy phenyls）Two kinds of compounds in the positive octadecanol ester of propionic acid and three [2.4- di-tert-butyl-phenyls] phosphite esters.
8. the fire-retardant master granule according to claim 1, it is characterised in that：The lubricant is N, N '-ethylene bis stearamide, calcium stearate or pentaerythrite stearate.
9. the preparation method of a kind of fire-retardant master granule as described in claim any one of 1-8, it is characterised in that：It is sufficiently mixed uniformly during ABS, fire retardant, toughener, anti-dripping agent, antioxidant and lubricant are added into high-speed mixer first, then by well mixed material feeding double screw extruder, material is sufficiently fused under shearing, mixing and the conveying of screw rod, and fire-retardant master granule is granulated to obtain after extruding wire drawing finally by die orifice；Each section of temperature of wherein double screw extruder is set as 170-220 DEG C.
10. application of a kind of fire-retardant master granule as described in claim any one of 1-8 in fire retardation PC and fire retardation PC alloy material, it is characterised in that：Using the fire-retardant master granule described in claim any one of 1-8 as fire retardant add PC or PC alloy materials in, directly mix fire retardation PC material or fire retardation PC alloy material.
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| CN110408154A (en) * | 2019-08-19 | 2019-11-05 | 南京天诗实验微粉有限公司 | A kind of modified ptfe anti-dripping agent and preparation method thereof |
| CN111234445A (en) * | 2020-02-18 | 2020-06-05 | 东莞市高能高分子材料有限公司 | Weather-resistant flame-retardant ABS plastic master batch and preparation method thereof |
| CN112724588A (en) * | 2020-12-25 | 2021-04-30 | 广东宇星阻燃新材股份有限公司 | Preparation method and application of ABS (acrylonitrile-butadiene-styrene) efficient flame-retardant toughening master batch |
| CN113831716A (en) * | 2021-10-09 | 2021-12-24 | 江苏建筑职业技术学院 | Flame-retardant polycarbonate material with high metal texture and preparation method thereof |
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| CN113831716A (en) * | 2021-10-09 | 2021-12-24 | 江苏建筑职业技术学院 | Flame-retardant polycarbonate material with high metal texture and preparation method thereof |
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Application publication date: 20170524 |