CN101671470B - Fire-retardant high-ductility composite material and manufacturing method thereof - Google Patents
Fire-retardant high-ductility composite material and manufacturing method thereof Download PDFInfo
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- CN101671470B CN101671470B CN2009100194330A CN200910019433A CN101671470B CN 101671470 B CN101671470 B CN 101671470B CN 2009100194330 A CN2009100194330 A CN 2009100194330A CN 200910019433 A CN200910019433 A CN 200910019433A CN 101671470 B CN101671470 B CN 101671470B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/04—Particle-shaped
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/36—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
- B29C48/395—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders
- B29C48/40—Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using screws surrounded by a cooperating barrel, e.g. single screw extruders using two or more parallel screws or at least two parallel non-intermeshing screws, e.g. twin screw extruders
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/918—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling
- B29C48/9185—Thermal treatment of the stream of extruded material, e.g. cooling characterized by differential heating or cooling in the direction of the stream of the material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/92—Measuring, controlling or regulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92504—Controlled parameter
- B29C2948/92704—Temperature
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C2948/00—Indexing scheme relating to extrusion moulding
- B29C2948/92—Measuring, controlling or regulating
- B29C2948/92819—Location or phase of control
- B29C2948/92857—Extrusion unit
- B29C2948/92876—Feeding, melting, plasticising or pumping zones, e.g. the melt itself
- B29C2948/92895—Barrel or housing
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Abstract
The invention provides a fire-retardant high-ductility composite material and a manufacturing method thereof, which can solve the problems that halogen decomposes harmful gas, the material cost is high, the use range of the material is limited and the like existing in the prior art. The components of the composite material are weighed in parts by weight: 40-70 parts of modified ABS particle, 20-60 parts of PC, 3-8 parts of toughener, 12-20 parts of ammonium polyphosphate, 8-12 parts of polyfluortetraethylene, 1-5 parts of magnesium hydrate and 0.1-0.4 part of ethylene bis stearamide. The ABS content in the composite material is improved, the material impact property is improved, the cost is lowered, and a fire-retardant system is improved.
Description
Technical field
The present invention relates to material, specifically, relate to a kind of fire-retardant high-ductility composite material and manufacture method.
Background technology
The patent No. is 200610036252 prior art, and its technical scheme mainly comprises following parts by weight proportion raw material component: PC40～60 part, ABS25～40 part, 2～5 parts of compatilizers, 3～8 parts of full acrylic acid or the like core-shell type impact modifying agents, 6～15 parts of bromide fire retardants, 2～5 parts of Sb system fire retardants, 0.2～0.5 part of tetrafluoroethylene, 0.1～0.3 part in oxidation inhibitor, 0.05～0.15 part of processing stabilizers, 0.3～1 part of lubricant.Technique scheme can effectively improve the notched Izod impact strength of fire retardation PC/ABS material, to draw a kind of high tenacity fire retardation PC/ABS alloy material by using a kind of full acrylic acid or the like core-shell type impact modifying agent.But, though above-mentioned prior art scheme has improved the shock strength and the flame retardant properties of PC/ABS alloy material, owing to adopted bromine antimony composite flame retardant system, although can effectively prevent from use to take place combustion phenomena.But in fire-retardant process, will decomposite corrosive bromize hydrogen gas, human body and environment are formed pollution and harmful.Because the price of PC is apparently higher than ABS, and PC content obviously surpasses ABS content in the such scheme, has increased the cost of material.
The patent No. is 200610036258 prior art, a kind of ABS/PC modified alloy is provided, and it mainly comprises following mass fraction proportion raw material component: 50～80 parts of ABS, 20～40 parts of PC, 3～5 parts of toughner, 0.1～1 part of Resins, epoxy, 0.1～0.3 part of oxidation inhibitor.This technology has the ABS/PC modified alloy of high tenacity, with ABS and PC (polycarbonate) blend, is used the toughner with compatibilization, has improved the erosion-resisting characteristics of ABS greatly, and increase rate is the highest near more than 300%.But the main drawback of the prior art is the fire-retardant finish of not being correlated with, and has limited the use range of material.
Summary of the invention
The invention provides a kind of fire-retardant high-ductility composite material and manufacture method, the obnoxious flavour that halogen decomposited when it can solve the burning that prior art exists, high material cost, and the problems such as use range that limited material.And can be implemented in the resistance to impact shock that improves it on the basis of PC/ABS alloy material high-intensity performance.Improve flame-retardant formulations, make its requirement that meets green Halogen, realize fire-retardant purpose.
In order to reach the purpose that solves the problems of the technologies described above, technical scheme of the present invention is, a kind of fire-retardant high-ductility composite material is characterized in that: described matrix material takes by weighing following component by weight: 40～70 parts on modified ABS particle, 20～60 parts of PC, 3～8 parts of toughner, 12～20 parts of ammonium polyphosphates, 8～12 parts of tetrafluoroethylene, 1～5 part of magnesium hydroxide, 0.1～0.4 part of lubricant.
Described modified ABS particle is prepared burden ABS and ABS-g-MAH respectively according to the scope of parts by weight 93-97 part and 3-7 part, dry back adds the forcing machine granulation, obtains the modified ABS particle.
Also comprise 0.1～0.3 part in oxidation inhibitor in the described matrix material, described oxidation inhibitor is at least a in antioxidant 1010, antioxidant 1076, the oxidation inhibitor 168.
Described toughner is at least a among MBS, SBS, POE, EVA or the DOP.
Described lubricant is at least a in ethylene bis stearic acid amide, stearic acid, stearic amide or the stearylamide.
A kind of manufacture method of fire-retardant high-ductility composite material, described method is carried out according to following step:
1), ABS and ABS-g-MAH ratio of weight and number are according to the rules joined the high-speed mixer batch mixing, join in the forcing machine after mixing, and control extruder temperature scope is 200 ℃-230 ℃, be cooled to normal temperature through tank after extruding, by the dicing machine granulation, again the gained pellet is put into baking oven, temperature range is 80 ℃-90 ℃, dry 3.5-4.5 hour, obtain the modified ABS particle;
2), PC being put into baking oven descended dry 3.5-4.5 hour for 100 ℃-110 ℃; measure in accordance with regulations with dried modified ABS particle then and prepare burden; take by weighing quantitative toughner successively; ethylene bis stearic acid amide; antioxidant 1010; ammonium polyphosphate; tetrafluoroethylene; magnesium hydroxide joins above component in the high speed mixing roll, mixes; join in the twin screw extruder then and extrude; the extrusion temperature scope is: 215 ℃-260 ℃, the extruded stock bar is cooled to normal temperature by circulating water channel, through entering the dicing machine granulation after the Hairdryer drying.
Described forcing machine is a twin screw extruder.
The present invention compared with prior art has the following advantages and positively effect:
1, on the basis of the present invention's content of ABS in improving the PC/ABS matrix material, improves the material impact performance, improved flame-retardant system.
2, at first granulation helps to improve the consistency of PC and ABS with ABS with expanding material ABS-g-MAH, material still has good toughness when having guaranteed that the ABS consumption equals or exceeds PC in the matrix material, because the corresponding minimizing of PC consumption, thereby reduced raw-material cost.
3, adopt phosphorus flame retardant, have the incomparable advantage of other Halogen products, reduced the harm that produces dusty gas in the combustion processes, avoided environmental pollution, widened the range of application of material.
4, the Different Effects of material preparation section the final properties result.Depend primarily on ester group and the polyhutadiene among the ABS (PB) part on the PC chain for the consistency of PC and ABS.Can realize being connected by chemical physical action with ester group on the PC chain by the MAH group on the ABS-g-MAH, ABS long-chain wherein be deep into ABS quite in, so guarantee ABS and PC biphase consistency.At first prepare ABS and ABS-g-MAH particle and just can guarantee that both fully act on together.For follow-up adding PC provides enough " tie point ", also just reached compatible purpose.Therefore, the order of addition(of ingredients) among the present invention more can guarantee the over-all properties of material.
Description of drawings
Below in conjunction with drawings and Examples the present invention is described in detail.
Fig. 1 is the technological process of production figure of a kind of fire-retardant high-ductility composite material of the present invention.
Embodiment
Referring to Fig. 1, a kind of production craft step of fire-retardant high-ductility composite material is as follows:
1, ABS and ABS-g-MAH (ABS grafted maleic anhydride) are prepared burden according to the scope of weight fraction 93-97 part and 3-7 part respectively, dry back adds the forcing machine granulation, obtains the modified ABS particle, and is standby.
2, mark takes by weighing following component by weight: 40～70 parts on gained modified ABS particle in the step 1, PC20～60 part, toughner, 3～8 parts, 12～20 parts of ammonium polyphosphates, 8～12 parts of tetrafluoroethylene, 1～5 part of magnesium hydroxide, 0.1～0.4 part of lubricant, antioxidant 1010,0.1～0.3 part.
3, getting material is carried out processing according to the process for producing composite material schema among Fig. 1.
1), ABS and ABS-g-MAH are joined the high-speed mixer batch mixing according to specified weight mark ratio, joins in the twin screw extruder after mixing and extrude.Each warm area temperature of forcing machine is: 225 ℃/230 ℃/230 ℃/222 ℃/200 ℃/200 ℃.Be cooled to normal temperature through tank, by the dicing machine granulation.The gained pellet was put into 85 ℃ of dryings of baking oven 4 hours again, obtained the modified ABS particle.
2), PC was put into 110 ℃ in baking oven dry 4 hours down, measure in accordance with regulations with dried modified ABS particle then and prepare burden.Take by weighing quantitative toughner successively, lubricant, antioxidant 1010, tetrafluoroethylene, magnesium hydroxide.Above component is joined in the high speed mixing roll, mix.Join in the twin screw extruder then and extrude extrusion temperature: 260 ℃/260 ℃/245 ℃/230 ℃/215 ℃/215 ℃.The extruded stock bar is cooled to normal temperature by circulating water channel, through entering the dicing machine granulation after the Hairdryer drying.
Related embodiment and performance index are as follows:
Embodiment 1, unit: kg.
40 parts on modified ABS particle, 60 parts of PC, toughner are selected 6 parts of MBS, 15 parts of ammonium polyphosphates, 8 parts of tetrafluoroethylene, 3 parts of magnesium hydroxides, 0.2 part of ethylene bis stearic acid amide, antioxidant 1010 for use, 0.2 part, wherein, the modified ABS particle is formed: ABS and ABS-g-MAH ratio of weight and number are 95: 5.
Embodiment 2, unit: kg.
50 parts on modified ABS particle, 50 parts of PC, toughner are selected 4 parts of MBS, 18 parts of ammonium polyphosphates, 8 parts of tetrafluoroethylene, 3 parts of magnesium hydroxides, 0.2 part of ethylene bis stearic acid amide, antioxidant 1010,0.2 part for use.Wherein, the modified ABS particle is formed: ABS and ABS-g-MAH ratio of weight and number are 95: 5.
Embodiment 3, unit: kg.
60 parts on modified ABS particle, 40 parts of PC, toughner are selected 4 parts of MBS, 18 parts of ammonium polyphosphates, 8 parts of tetrafluoroethylene, 3 parts of magnesium hydroxides, 0.2 part of stearic amide, antioxidant 1010 for use, 0.2 part, wherein, the modified ABS particle is formed: ABS is 95: 5 with ABS-g-MAH weight fraction ratio.
Embodiment 4, unit: kg.
65 parts on modified ABS particle, 35 parts of PC, toughner are selected 4 parts of EVA, 18 parts of ammonium polyphosphates, 8 parts of tetrafluoroethylene, 3 parts of magnesium hydroxides, 0.2 part of ethylene bis stearic acid amide, antioxidant 1010 for use, 0.2 part, wherein, the modified ABS particle is formed: ABS is 95: 5 with ABS-g-MAH weight fraction ratio.
Embodiment 5, unit: kg.
70 parts on modified ABS particle, 30 parts of PC, toughner are selected 4 parts of POE, 15 parts of ammonium polyphosphates, 8 parts of tetrafluoroethylene, 3 parts of magnesium hydroxides, 0.2 part of ethylene bis stearic acid amide, antioxidant 1010 for use, 0.2 part, wherein, the modified ABS particle is formed: ABS is 95: 5 with ABS-g-MAH weight fraction ratio.
| Embodiment | The simply supported beam notch shock by force/(kJ/m2) | Tensile strength/MPa | Tensile yield/% | Flexural strength/Mpa | Flame retardant resistance |
| 1 | 70.5 | 64.5 | 27.3 | 79.2 | V0 |
| 2 | 65.5 | 60.1 | 30.6 | 78.8 | V0 |
| 3 | 58.7 | 56.9 | 32.1 | 75.5 | V0 |
| 4 | 68.2 | 59.6 | 32.6 | 77.8 | V0 |
| 5 | 65.3 | 55.7 | 31.5 | 76.1 | V0 |
Dependence test method and standard:
1GB/T1040-1992: tensile strength testing standard, " plastic tensile method for testing performance ".
2GB/T9341-2000: flexural strength testing standard, " plastics bending property test method ".
3GB/T1043-1993: impact property testing standard, " rigid plastics charpy impact test method ".
4 adopt the UL-94 touchstone that the flame retardant resistance of material is tested.
Among technique scheme and the embodiment, PC: polycarbonate.
ABS: vinyl cyanide, divinyl and styrene copolymer.
ABS-g-MAH:ABS terpolymer grafted maleic anhydride.
MBS: methyl methacrylate-butadiene-styrene terpolymer.
SBS: styrene-butadiene copolymer.
EVA: ethylene-vinyl acetate copolymer.
DOP: o-phthalic acid dibutyl ester.
POE: polyethylene octene.
APP: ammonium polyphosphate.
EBS: ethylene bis stearic acid amide.
The above only is preferred embodiment of the present invention, is not to be the restriction of the present invention being made other form, and any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the equivalent embodiment of equivalent variations.But every technical solution of the present invention content that do not break away to any simple modification, equivalent variations and remodeling that above embodiment did, still belongs to the protection domain of technical solution of the present invention according to technical spirit of the present invention.
Claims (6)
1. fire-retardant high-ductility composite material, it is characterized in that: described matrix material takes by weighing following component by weight: 40～70 parts on modified ABS particle, 20～60 parts of PC, 3～8 parts of toughner, 12～20 parts of ammonium polyphosphates, 8～12 parts of tetrafluoroethylene, 1～5 part of magnesium hydroxide, 0.1～0.4 part of lubricant;
Described modified ABS particle is that ABS and ABS-g-MAH are prepared burden according to the scope of parts by weight 93-97 part and 3-7 part respectively, and dry back adds the forcing machine granulation, obtains the modified ABS particle.
2. a kind of fire-retardant high-ductility composite material according to claim 1 is characterized in that: also comprise 0.1～0.3 part in oxidation inhibitor in the described matrix material, described oxidation inhibitor is at least a in antioxidant 1010, antioxidant 1076, the oxidation inhibitor 168.
3. a kind of fire-retardant high-ductility composite material according to claim 1 is characterized in that: described toughner is at least a among MBS, SBS, POE, EVA or the DOP.
4. a kind of fire-retardant high-ductility composite material according to claim 1 is characterized in that: described lubricant is at least a in ethylene bis stearic acid amide, stearic acid or the stearylamide.
5. the manufacture method of the described fire-retardant high-ductility composite material of claim 2 is characterized in that, described method is carried out according to following step:
1), ABS and ABS-g-MAH ratio of weight and number are according to the rules joined the high-speed mixer batch mixing, join in the forcing machine after mixing, and control extruder temperature scope is 200 ℃-230 ℃, be cooled to normal temperature through tank after extruding, by the dicing machine granulation, again the gained pellet is put into baking oven, temperature range is 80 ℃-90 ℃, dry 3.5-4.5 hour, obtain the modified ABS particle;
2), PC being put into baking oven descended dry 3.5-4.5 hour for 100 ℃-110 ℃; measure in accordance with regulations with dried modified ABS particle then and prepare burden; take by weighing quantitative toughner successively; ethylene bis stearic acid amide; antioxidant 1010; ammonium polyphosphate; tetrafluoroethylene; magnesium hydroxide joins above component in the high speed mixing roll, mixes; join in the twin screw extruder then and extrude; the extrusion temperature scope is 215 ℃-260 ℃, and the extruded stock bar is cooled to normal temperature by circulating water channel, through entering the dicing machine granulation after the Hairdryer drying.
6. according to the described method of claim 5, it is characterized in that: described forcing machine is a twin screw extruder.
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| CN102002206A (en) * | 2010-12-21 | 2011-04-06 | 四川大学 | High-glossiness high-toughness scratch resistant molding composition |
| CN102850712A (en) * | 2012-02-03 | 2013-01-02 | 深圳市富恒塑胶新材料有限公司 | Anti-dropping flame-retardant ABS material and preparation method thereof |
| CN103194033A (en) * | 2013-04-07 | 2013-07-10 | 烟台市有利塑料有限公司 | Blend modified resin capable of being applied to lead-acid battery housing and preparation method of blend modified resin |
| CN105633561A (en) * | 2016-01-04 | 2016-06-01 | 深圳市维力谷无线技术股份有限公司 | Antenna comprising polymer material |
| CN106589931A (en) * | 2016-11-16 | 2017-04-26 | 马鞍山市华能电力线路器材有限责任公司 | High-toughness flame-retardant nylon composite for electric power fitting and preparation method of nylon composite |
| CN108752835A (en) * | 2018-04-16 | 2018-11-06 | 常州轻工职业技术学院 | A kind of plastics resistant to chemical etching |
| CN108410150A (en) * | 2018-04-17 | 2018-08-17 | 中山市绿浪助剂有限公司 | Flame-retardant PC/ABS composite material and preparation method thereof |
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