CN107418177A - A kind of high-toughness halogen-free flame enhancing PC/ASA alloys and preparation method thereof - Google Patents
A kind of high-toughness halogen-free flame enhancing PC/ASA alloys and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of high-toughness halogen-free flame enhancing PC/ASA alloys and preparation method thereof, the alloy is made up of the raw material of following mass parts：10 20 parts of 55 65 parts of PC, ASA, 38 parts of compatilizer, 47 parts of toughener, 15 20 parts of Halogen compound flame retardant, 0.5 1 parts of anti-dripping agent, 0.1 0.5 parts of lubricant, 0.1 0.5 parts of antioxidant；Its preparation method is：Raw material is weighed by proportioning, raw material is put into double screw extruder dog-house after being well mixed, sets the rotating speed of double screw extruder to be extruded and be granulated for 100 300r/min, obtains high-toughness halogen-free flame enhancing PC/ASA alloys.The alloy material of the present invention has good comprehensive mechanical property and anti-flammability, and HRR is slow and will not produce a large amount of molten drops and smog, is the practical alloy material of highly effective flame-retardant environment-protective.
Description
Technical field
The present invention relates to polymeric material field, more particularly, to a kind of high-toughness halogen-free flame strengthen PC/ASA alloys and
Its preparation method.
Background technology
Makrolon (PC) is a kind of engineering plastics of excellent performance, because it has excellent mechanical performance, heat-resisting quantity
Can and be widely used in every field, however, makrolon there is also poor fluidity, notch sensitive, be also easy to produce internal stress
The shortcomings of cracking.ASA resin is the terpolymer of styrene-acrylonitrile-butyl acrylate, in mobility, weatherability,
Color etc. is better than ABS resin, and PC/ASA alloys can realize the mutual supplement with each other's advantages of two kinds of resins, it is excellent to obtain comprehensive mechanical property
Different and easily processed into type extensive use type alloy.
With the increasingly raising of people's living standard, combustibility requirement of the society for material is also more strict, PC/
The anti-flammability of ASA alloys is also the focus of people's Recent study.ASA resin and PC fire-retardant rank are UL94-HB, and itself is simultaneously
Do not possess good fire resistance, the fire-retardant rank of its alloy is not also high, and can improve PC/ASA using different flame-retardant systems closes
The flame-retarding characteristic of gold.The harm that traditional halogen system inhibiting tape comes is very big, is such as burnt with the fire-retardant PC/ASA alloys of bromide fire retardant
Corrosive gas and smog more Shi Shengcheng.Fire-retardant research direction both domestic and external in the last few years is mainly halogen-free flame-retardant system.
For PC/ASA alloys, halogen-free flame-retardant system mainly have phosphorus flame retardant (triphenyl phosphate, bisphenol-A bis phosphoric acid diphenyl ester etc.),
Silicon-series five-retardant (methyl phenyl siloxane, inorganic silicate etc.), sulfur-bearing fire retardant (two lauseto neu sulfonate) etc..Halogen at present
Fire retardation PC/subject matter existing for ASA alloys is big for the addition of fire retardant, and the comprehensive mechanical property of flame-retardant alloy is relatively low, special
It is not that shock resistance declines substantially, flame retarding efficiency is not high.
The content of the invention
The technical problems to be solved by the invention are for above shortcomings in the prior art, there is provided a kind of high tenacity
Halogen-free flameproof enhancing PC/ASA alloys and preparation method thereof, triphenyl phosphate is cooperateed with to PC/ASA using quaternary phosphonium salt modified montmorillonoid
Alloy carries out fire-retardant enhancing, while toughening modifying, gained PC/ASA alloy flame retarding efficiencies are carried out to it using preferable toughener
Height, smog burst size is few during burning, and comprehensive mechanical property is high, and can prevent a large amount of molten drops from generating.
In order to solve the above technical problems, technical scheme provided by the invention is：
A kind of high-toughness halogen-free flame enhancing PC/ASA alloys are provided, the alloy is made up of the raw material of following mass parts：
PC55-65 parts, ASA 10-20 parts, compatilizer 3-8 parts, toughener 4-7 parts, Halogen compound flame retardant 15-20 parts, anti-dripping agent
0.5-1 parts, lubricant 0.1-0.5 parts, antioxidant 0.1-0.5 parts；
The Halogen compound flame retardant is by triphenyl phosphate (TPP) and quaternary phosphonium salt modified montmorillonoid 2.5-5 in mass ratio：1
It is mixed to get；
The preparation method of the quaternary phosphonium salt modified montmorillonoid is：Sodium-based montmorillonite is scattered in the mixed of deionized water and ethanol
In bonding solvent, tributyl n-tetradecane base phosphonium chloride is then slowly added into, is stirred overnight at 60-80 DEG C, it is then filtered, go
Ion water washing, that is, obtain quaternary phosphonium salt modified montmorillonoid.
Organic phosphorus flame retardant TPP has good compatibility, while triphenyl phosphate TPP with PC/ASA alloy systems
It is good plasticizer, the processing characteristics of alloy can be improved.It is 230 DEG C that TPP, which decomposes initial temperature, therefore processing temperature should not surpass
Cross 230 DEG C.By being obtained to flame-retardant alloy thermogravimetic analysis (TGA), the dominant mechanism of the fire-retardant enhancing alloys of TPP is that gas phase is fire-retardant, for
The remaining carbon of alloy influences little.TPP fire retardants are heated to produce PO free radicals, and it can capture H and HO free radicals, from
And suppress the progress of combustion reaction；The heated generation phosphoric acid promoted PC of TPP are burned into gas dilutions such as charcoal generation vapor simultaneously
The concentration of oxygen in journey.Sodium-based montmorillonite strengthens after organically-modified with high polymer alloy matrix compatibility, and matrix insertion is covered
Between de- soil layer, the warm-up movement of strand can be suppressed, strengthen the heat endurance of alloy.The present invention utilizes organic phosphorus flame retardant
The fire-retardant enhancing PC/ASA alloys of TPP gas phases, suppress the warm-up movement of strand using inorganic nano silicic acid quaternary phosphonium salt modified montmorillonoid,
Promote the stabilization of surface layer of charcoal simultaneously, prepare efficient high-toughness halogen-free flame PC/ASA alloys.
By such scheme, the PC weight average molecular weight is 3-5 ten thousand, density 1.18-1.20g/cm3.ASA resin (the trade mark
PW-978B ASA graft copolymers mass content is 60% in), and methyl styrene mass content is 40%, and surveyed in 50 DEG C/hr
Softening point under the conditions of examination is 115 DEG C.UL-94 vertical combustions grade is HB.
By such scheme, the compatilizer is phenylethylene-maleic anhydride graft copolymer (SMA).Maleic anhydride in SMA
Grafting rate is 18%, and mean molecule quantity is 1.2-1.8 ten thousand, and heat decomposition temperature is higher than 320 DEG C, density 1.06-1.12g/cm3。
Maleic groups therein can react with PC terminal hydroxy group, reduce the interfacial tension of two-phase, make in PC/ASA alloys
Dispersed phase particles refine, and reach the effect of increase-volume.
By such scheme, the toughener is that toughener is risen by the beautiful positive silicon systems toughener S-2001 of Mitsubishi or section of the U.S.
FG1901 (maleic anhydride-g-SBS block copolymer).S-2001 is core-shell type structure, and shell is methyl methacrylate, core
It is organosilicon and acrylate, the internal stress of resin matrix can be effectively reduced, increases the toughness of PC/ASA alloy materials.
FG1901 is the SEBS (hydrogenated styrene-butadiene block copolymer) being grafted through maleic anhydride, and wherein maleic anhydride is grafted
Rate is 1.7%, and styrene is 37 with rubber phase mass ratio：63.
By such scheme, the anti-dripping agent is polytetrafluoroethylene (PTFE) (PTFE).
By such scheme, the lubricant is the double stearic amides of vinyl or ethylene bis stearamide.
By such scheme, the antioxidant is 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols) or double (2,4- bis- uncles
Butyl phenyl) pentaerythritol diphosphites.
Present invention additionally comprises the preparation method of above-mentioned high-toughness halogen-free flame enhancing PC/ASA alloys, it is characterised in that step
It is rapid as follows：Raw material is weighed by proportioning, raw material is put into double screw extruder dog-house after being well mixed, double screw extruder is set
Rotating speed extruded and be granulated for 100-300r/min, obtain high-toughness halogen-free flame enhancing PC/ASA alloys.
By such scheme, the temperature in each area of double screw extruder is：One area's temperature is 200-210 DEG C, two area's temperature
For 210-220 DEG C, three area's temperature are 210-220 DEG C, and four area's temperature are 215-225 DEG C, and five area's temperature are 215-225 DEG C, 6th area
Temperature is 215-225 DEG C, and seven area's temperature are 220-230 DEG C.
The beneficial effects of the present invention are：
1) present invention compounds organic quaternary phosphonium salt modified montmorillonoid using organic phosphorus flame retardant TPP, with reference to gas phase and cohesion
Phase fire retardant mechanism, is prepared efficient halogen-free anti-inflaming enhancing PC/ASA alloys, and gained PC/ASA alloys have efficient anti-flammability
Can, limited oxygen index reaches 27.2-30.1%, and vertical combustion grade reaches V-0 ranks, and carbon left is high under 800 DEG C of high temperature, maximum
Thermal weight loss temperature improves, and amount of smoke is few and does not have a large amount of molten drop drippages, and flame retarding efficiency is high；
2) phosphorus flame retardant TPP has good plasticization for PC/ASA alloy systems in the present invention, can be obvious
Processing temperature is reduced, improves alloy processing characteristics, the PC/ASA alloy moltens index added after Halogen compound flame retardant is 18-
26g/10min (test temperature is 220 DEG C, counterbalance mass 2.16Kg).
3) the modified PC/ASA alloys of the present invention have good mechanical property, can be alleviated using suitable toughener
Influence of the small molecule fire retardant to alloy impact property, alloy tensile intensity reach 56.3-63.4MPa, and bending strength reaches 86.5-
93.5MPa, impact strength reach 42.4-47.8KJ/m2。
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made with reference to embodiment
It is described in further detail.
Comparative example 1
A kind of PC/ASA alloys, it is following (mass parts) that it is formulated composition
PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA graft copolymers in ASA resin (trade mark PW-978B)
Mass content be 60%, the mass content of methyl styrene is 40%, and the softening point under 50 DEG C/hr test conditions is
115 DEG C, UL-94 vertical combustions grade is HB.Compatilizer is SMA (phenylethylene-maleic anhydride graft copolymer), and maleic anhydride connects
Branch rate is 18%, and number-average molecular weight is 1.2-1.8 ten thousand, and toughener is the beautiful positive silicon systems toughener S-2001 of Mitsubishi；Antioxidant
For 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE) (PTFE, 327 DEG C of fusing point)；Lubrication
Agent is the double stearic amides of vinyl.
PC/ASA alloy preparation technologies are as follows：Precise above each component raw material, it is after being well mixed that raw material input is double
Screw extruder dog-house, the temperature in each area of double screw extruder are：One area's temperature be 200 DEG C, two area's temperature be 210 DEG C, three
Area's temperature is 210 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are 220 DEG C, and seven area's temperature are 225
DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 100r/min, PC/ASA alloys are prepared.
Comparative example 2
A kind of PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is that toughener FG1901 (maleic anhydride-g-SBS block copolymer) rises in section of the U.S.,
Wherein maleic anhydride grafting ratio is 1.7%, and styrene is 37 with rubber phase mass ratio:63.The antioxidant is the (uncles of 2,4- bis-
Butyl phenyl) pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is ethylene bis stearamide.
Triphenyl phosphate (TPP) phosphorus content is 9.9%, and fusing point is 50.52 DEG C, and flash-point is 223 DEG C, is white crystals
Powder.
PC/ASA alloy preparation technologies are as follows：Precise above each component raw material, it is after being well mixed that raw material input is double
Screw extruder dog-house, the temperature in each area of double screw extruder are：One area's temperature be 200 DEG C, two area's temperature be 210 DEG C, three
Area's temperature is 215 DEG C, and four area's temperature are 215 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are 225 DEG C, and seven area's temperature are 225
DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 200r/min, PC/ASA alloys are prepared.
Comparative example 3
A kind of PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is the beautiful positive silicon systems toughener S-2001 of Mitsubishi.The antioxidant is 4,4 '-sulphur
Dai Shuan (the 6- tert-butyl group -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is the double stearic amides of vinyl.
The preparation method of the quaternary phosphonium salt modified montmorillonoid is：By the mixed of 5g Na-MMT and 300mL deionized water and ethanol
Bonding solvent (volume ratio 1:1) it is added in 500mL three-necked bottles, 2.44g (tributyl) n-tetradecane is slowly added to after stirring 1h
Base phosphonium chloride (presses 1.1 times of cation exchange capacities of sodium-based montmorillonite), is stirred overnight at 70 DEG C, suspension system is used after filtering
Deionized water washing is multiple, that is, obtains quaternary phosphonium salt modified montmorillonoid.
High-toughness halogen-free compositional flame-retardant enhancing PC/ASA alloy preparation technologies are as follows：Precise above each component raw material,
Raw material is put into double screw extruder dog-house after well mixed, the temperature in each area of double screw extruder is：One area's temperature is 210
DEG C, two area's temperature are 220 DEG C, and three area's temperature are 220 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are
225 DEG C, seven area's temperature are 230 DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 300r/min, are prepared
High-toughness halogen-free flame strengthens PC/ASA alloys.
Comparative example 4
A kind of PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is that toughener FG1901 (maleic anhydride-g-SBS block copolymer) rises in section of the U.S.,
Wherein maleic anhydride grafting ratio is 1.7%, and styrene is 37 with rubber phase mass ratio:63.The antioxidant is the (uncles of 2,4- bis-
Butyl phenyl) pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is ethylene bis stearamide.
The Halogen compound flame retardant is mixed to get by triphenyl phosphate and quaternary phosphonium salt modified montmorillonoid compounding, wherein TPP
10 parts, 2 parts of quaternary phosphonium salt modified montmorillonoid.
The quaternary phosphonium salt modified montmorillonoid preparation method is：By the mixing of 5g Na-MMT and 300mL deionized water and ethanol
Solvent (volume ratio 1:1) it is added in 500mL three-necked bottles, 2.44g (tributyl) n-tetradecane base is slowly added to after stirring 1h
Phosphonium chloride (Aladdin reagent Co., Ltd), is stirred overnight, suspension system is washed with deionized more after filtering at 70 DEG C
It is secondary, that is, obtain quaternary phosphonium salt modified montmorillonoid.
The present embodiment PC/ASA alloy preparation technologies are as follows：Precise above each component raw material, by original after being well mixed
Material input double screw extruder dog-house, the temperature in each area of double screw extruder are：One area's temperature is 210 DEG C, and two area's temperature are
210 DEG C, three area's temperature are 220 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 225 DEG C, and six area's temperature are 225 DEG C, seven area's temperature
Spend and for 225 DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 100r/min, be prepared
PC/ASA alloys.
Embodiment 1
A kind of silicon-phosphorus cooperative flame retardant enhancing PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is the beautiful positive silicon systems toughener S-2001 of Mitsubishi.The antioxidant is 4,4 '-sulphur
Dai Shuan (the 6- tert-butyl group -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is the double stearic amides of vinyl.
The Halogen compound flame retardant is mixed to get by triphenyl phosphate and quaternary phosphonium salt modified montmorillonoid compounding, wherein TPP
12 parts, 3 parts of quaternary phosphonium salt modified montmorillonoid.
The quaternary phosphonium salt modified montmorillonoid preparation method is：By the mixing of 5g Na-MMT and 300mL deionized water and ethanol
(deionized water is 1 with ethanol volume ratio to solvent:1) it is added in 500mL three-necked bottles, 2.44g (three fourths is slowly added to after stirring 1h
Base) n-tetradecane base phosphonium chloride, it is stirred overnight at 70 DEG C, suspension system is washed with deionized repeatedly after filtering, produces
To quaternary phosphonium salt modified montmorillonoid.
High-toughness halogen-free compositional flame-retardant enhancing PC/ASA alloy preparation technologies are as follows：Precise above each component raw material,
Raw material is put into double screw extruder dog-house after well mixed, the temperature in each area of double screw extruder is：One area's temperature is 210
DEG C, two area's temperature are 210 DEG C, and three area's temperature are 215 DEG C, and four area's temperature are 215 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are
220 DEG C, seven area's temperature are 225 DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 200r/min, are prepared
High-toughness halogen-free flame strengthens PC/ASA alloys.
Embodiment 2
A kind of silicon-phosphorus cooperative flame retardant enhancing PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is that toughener FG1901 (maleic anhydride-g-SBS block copolymer) rises in section of the U.S.,
Wherein maleic anhydride grafting ratio is 1.7%, and styrene is 37 with rubber phase mass ratio:63.The antioxidant is the (uncles of 2,4- bis-
Butyl phenyl) pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is ethylene bis stearamide.
The Halogen compound flame retardant is mixed to get by triphenyl phosphate and quaternary phosphonium salt modified montmorillonoid compounding, wherein TPP
11 parts, 4 parts of quaternary phosphonium salt modified montmorillonoid.
The quaternary phosphonium salt modified montmorillonoid preparation method is：By the mixing of 5g Na-MMT and 300mL deionized water and ethanol
Solvent is added in 500mL three-necked bottles, 2.44g (tributyl) n-tetradecane base phosphonium chloride is slowly added to after stirring 1h, in 70 DEG C
Under be stirred overnight, suspension system is washed with deionized repeatedly after filtering, that is, obtains quaternary phosphonium salt modified montmorillonoid.
High-toughness halogen-free compositional flame-retardant enhancing PC/ASA alloy preparation technologies are as follows：Precise above each component raw material,
Raw material is put into double screw extruder dog-house after well mixed, the temperature in each area of double screw extruder is：One area's temperature is 200
DEG C, two area's temperature are 210 DEG C, and three area's temperature are 210 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are
220 DEG C, seven area's temperature are 230 DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 100r/min, are prepared
High-toughness halogen-free flame strengthens PC/ASA alloys.
Embodiment 3
A kind of silicon-phosphorus cooperative flame retardant enhancing PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is the beautiful positive silicon systems toughener S-2001 of Mitsubishi.The antioxidant is 4,4 '-sulphur
Dai Shuan (the 6- tert-butyl group -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is the double stearic amides of vinyl.Institute
State Halogen compound flame retardant by triphenyl phosphate and quaternary phosphonium salt modified montmorillonoid compounding be mixed to get, wherein 15 parts of TPP, season phosphine
3 parts of salt modified montmorillonoid.
The quaternary phosphonium salt modified montmorillonoid preparation method is：By the mixing of 5g Na-MMT and 300mL deionized water and ethanol
Solvent is added in 500mL three-necked bottles, 2.44g (tributyl) n-tetradecane base phosphonium chloride is slowly added to after stirring 1h, in 70 DEG C
Under be stirred overnight, suspension system is washed with deionized repeatedly after filtering, that is, obtains quaternary phosphonium salt modified montmorillonoid.
High-toughness halogen-free compositional flame-retardant enhancing PC/ASA alloy preparation technologies are as follows：Precise above each component raw material,
Raw material is put into double screw extruder dog-house after well mixed, the temperature in each area of double screw extruder is：One area's temperature is 210
DEG C, two area's temperature are 210 DEG C, and three area's temperature are 210 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are
220 DEG C, seven area's temperature are 225 DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 100r/min, are prepared
High-toughness halogen-free flame strengthens PC/ASA alloys.
Embodiment 4
A kind of silicon-phosphorus cooperative flame retardant enhancing PC/ASA alloys, it is following (mass parts) that it is formulated composition：
The PC weight average molecular weight is 40,000, density 1.18g/cm3, ASA connects in the ASA resin (trade mark PW-978B)
The mass content of graft copolymer is 60%, and the mass content of methyl styrene is 40%, and soft under 50 DEG C/hr test conditions
It is 115 DEG C to change point, and UL-94 vertical combustions grade is HB.The compatilizer is SMA, and maleic anhydride grafting ratio 18% is several to divide equally
Son amount is 1.2-1.8 ten thousand, and the toughener is that toughener FG1901 (maleic anhydride-g-SBS block copolymer) rises in section of the U.S.,
Wherein maleic anhydride grafting ratio is 1.7%, and styrene is 37 with rubber phase mass ratio:63.The antioxidant is the (uncles of 2,4- bis-
Butyl phenyl) pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE)；Lubricant is ethylene bis stearamide.
The Halogen compound flame retardant is mixed to get by triphenyl phosphate and quaternary phosphonium salt modified montmorillonoid compounding, wherein TPP
16 parts, 4 parts of quaternary phosphonium salt modified montmorillonoid.
The quaternary phosphonium salt modified montmorillonoid preparation method is：By the mixing of 5g Na-MMT and 300mL deionized water and ethanol
Solvent is added in 500mL three-necked bottles, 2.44g (tributyl) n-tetradecane base phosphonium chloride is slowly added to after stirring 1h, in 70 DEG C
Under be stirred overnight, suspension system is washed with deionized repeatedly after filtering, that is, obtains quaternary phosphonium salt modified montmorillonoid.
High-toughness halogen-free compositional flame-retardant enhancing PC/ASA alloy preparation technologies are as follows：Precise above each component raw material,
Raw material is put into double screw extruder dog-house after well mixed, the temperature in each area of double screw extruder is：One area's temperature is 200
DEG C, two area's temperature are 210 DEG C, and three area's temperature are 210 DEG C, and four area's temperature are 220 DEG C, and five area's temperature are 220 DEG C, and six area's temperature are
220 DEG C, seven area's temperature are 225 DEG C, control the rotating speed of double screw extruder to be extruded and be granulated for 100r/min, are prepared
High-toughness halogen-free flame strengthens PC/ASA alloys.
Embodiment 5
High-toughness halogen-free flame enhancing PC/ASA obtained by comparative example 1-4 (being designated as D1, D2, D3, D4) and embodiment 1-4 is closed
The performance of gold is tested, and test result is as shown in table 1：
Table 1
As it can be seen from table 1 with the increase of flame retardant agent content, the limited oxygen index of gained PC/ASA alloys gradually rises
(and when the addition of Halogen compound flame retardant is 20 parts, wherein TPP is 4 with quaternary phosphonium salt modified montmorillonoid quality parts ratio:When 1,
Flame retardant effect is best), fire-retardant rank reaches more than the V-0 levels of UL94 standards, and carbon left is obviously improved.The nothing of the present invention
The tensile strengths of the fire-retardant enhancing PC/ASA alloy materials of halogen, bending strength, impact strength etc. reach the use of PC/ASA alloys
It is required that there is very high practical value.
Obviously, above-described embodiment is just for the sake of the made example of clearly explanation, and is not the limitation to embodiment.
For those of ordinary skill in the field, other various forms of changes can also be made on the basis of the above description
Or change.There is no need and unable to all embodiments and with exhaustion.And the obvious change therefore amplified or
Change within still in the protection domain of the invention.
Claims (9)
1. a kind of high-toughness halogen-free flame strengthens PC/ASA alloys, it is characterised in that the alloy by following mass parts raw material group
Into：PC 55-65 parts, ASA 10-20 parts, compatilizer 3-8 parts, toughener 4-7 parts, Halogen compound flame retardant 15-20 parts, anti-drop
Fall agent 0.5-1 parts, lubricant 0.1-0.5 parts, antioxidant 0.1-0.5 parts；
The Halogen compound flame retardant is by triphenyl phosphate and quaternary phosphonium salt modified montmorillonoid 2.5-5 in mass ratio：1 is mixed to get；
The preparation method of the quaternary phosphonium salt modified montmorillonoid is：The mixing that sodium-based montmorillonite is scattered in deionized water and ethanol is molten
In agent, tributyl n-tetradecane base phosphonium chloride is then slowly added into, is stirred overnight at 60-80 DEG C, then filtered, deionization
Water washing, that is, obtain quaternary phosphonium salt modified montmorillonoid.
2. high-toughness halogen-free flame according to claim 1 strengthens PC/ASA alloys, it is characterised in that the PC divides equally again
Son amount is 3-5 ten thousand, density 1.18-1.20g/cm3。
3. high-toughness halogen-free flame according to claim 1 strengthens PC/ASA alloys, it is characterised in that the compatilizer is
Phenylethylene-maleic anhydride graft copolymer.
4. high-toughness halogen-free flame according to claim 1 strengthens PC/ASA alloys, it is characterised in that the toughener is
Toughener FG1901 rises in the beautiful positive silicon systems toughener S-2001 of Mitsubishi or section of the U.S..
5. high-toughness halogen-free flame according to claim 1 strengthens PC/ASA alloys, it is characterised in that the anti-dripping agent
For polytetrafluoroethylene (PTFE).
6. high-toughness halogen-free flame according to claim 1 strengthens PC/ASA alloys, it is characterised in that the lubricant is
The double stearic amides of vinyl or ethylene bis stearamide.
7. high-toughness halogen-free flame according to claim 1 strengthens PC/ASA alloys, it is characterised in that the antioxidant is
4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols) or double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
8. a kind of preparation method of any described high-toughness halogen-free flame enhancing PC/ASA alloys of claim 1-7, its feature
It is, step is as follows：Raw material is weighed by proportioning, raw material is put into double screw extruder dog-house after being well mixed, double spiral shells are set
The rotating speed of bar extruder is that 100-300r/min is extruded and is granulated, and obtains high-toughness halogen-free flame enhancing PC/ASA alloys.
9. preparation method according to claim 8, it is characterised in that the temperature in each area of double screw extruder is：One
Area's temperature is 200-210 DEG C, and two area's temperature are 210-220 DEG C, and three area's temperature are 210-220 DEG C, and four area's temperature are 215-225
DEG C, five area's temperature are 215-225 DEG C, and six area's temperature are 215-225 DEG C, and seven area's temperature are 220-230 DEG C.
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Application publication date: 20171201 |