CN108624027A - A kind of catalysis carbon-forming efficient halogen-free anti-inflaming PC/ABS mixtures and preparation method thereof - Google Patents
A kind of catalysis carbon-forming efficient halogen-free anti-inflaming PC/ABS mixtures and preparation method thereof Download PDFInfo
- Publication number
- CN108624027A CN108624027A CN201810535470.6A CN201810535470A CN108624027A CN 108624027 A CN108624027 A CN 108624027A CN 201810535470 A CN201810535470 A CN 201810535470A CN 108624027 A CN108624027 A CN 108624027A
- Authority
- CN
- China
- Prior art keywords
- abs
- inflaming
- carbon
- fibre reinforced
- carbon fiber
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/22—Halogen free composition
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a kind of catalysis carbon-forming efficient halogen-free anti-inflaming PC/ABS mixtures and preparation method thereof；Mixture is made of the raw material of following mass percent：PC resin 37~67%；ABS resin 14~37%；Compatilizer 0~5%；Antioxidant 0.1~0.5%；Chopped carbon fiber 5~15%；Organic phosphate fire retardant 3~5%；Phenoxy phosphazene 0.5~3%；Basic zirconium phosphate modifies the siliceous carbon forming agent of triazines 0~1%；Preparation method is：It will be sufficiently mixed in high-speed mixer after raw material drying in addition to chopped carbon fiber, be added in equidirectional parallel double-screw extruder barrel through main feeding bin, chopped carbon fiber is added by way of the feeding of side, melting extrusion is granulated.Object mixed by the present invention has both that intensity is high, flame retardant property is good and the advantages such as fire retardant additive amount is low, can be applied to ultra-thin notebook computer shell, high ferro interior trim, unmanned plane shell and other high-end appliance fields.
Description
Technical field
The present invention relates to the flame-retardant modified field of the enhancing of PC/ABS alloys, a kind of specifically catalysis carbon-forming efficient halogen-free
Fire-retardant fibre reinforced PC/ABS mixtures and preparation method thereof.
Background technology
Carbon fiber enhancing PC/ABS has many advantages, such as that proportion is small, specific strength is big, rigidity is high, and modulus is big, can meet ultra-thin pen
Remember rigors of the equipment such as this computer and unmanned plane to density and intensity.But there is also flame retardant properties by fibre reinforced PC/ABS
The defect of difference, there are larger fire hazards when use, it is necessary to be carried out to it flame-retardant modified.PC/ABS alloys commonly hinder at present
It is mainly phosphorus flame retardant, such as organic phosphate flame retardants, red phosphorus, ammonium polyphosphate to fire agent.But phosphorus flame retardant is in carbon fiber
In enhancing PC/ABS when being used alone, due to " the candle wick ignition in hydriding effect so that product carbon-forming performance is poor, flame retarding efficiency of carbon fiber
It is low, fire retardant additive amount is big, and fire retardant material mechanical performance and processing performance are deteriorated it is serious, it is difficult to meet fibre reinforced
The performance requirement of PC/ABS composite materials.Therefore there is high efficiency flame retardance fibre reinforced PC/ABS composite materials just to show for research
It obtains particularly urgent and important.
Chinese invention patent application CN104403295A discloses a kind of Halogen-free flame retardant highlight pool inorfil enhancing PC/
ABS material and preparation method thereof uses Sulfonates fire retardant to be compounded with phosphorus flame retardant fire-retardant to improve fiber reinforced PC/ABS
Performance inhibits the fire-retardant deteriorating effect of fiberfill to a certain extent；But its flame retarding efficiency is relatively low, needs larger additive amount (10
~12%) alloy can be just made to reach V-0 grades of flame retardant ratings of UL94 (3.2mm), and UL94 (1.6mm) is still HB grades.
Chinese invention patent application CN103756276A discloses a kind of fire-retardant fibre reinforced PC/ABS of high-environmental
Intermingling material and preparation method thereof, using pentaerythrite, phosphoric acid and urea compounding flame retardant, fire retardant total addition level is 5~
15%, vertical combustion grade (1.6mm) reaches V-0 grades；The system fire retardant additive amount is big, serious to matrix Effect on Mechanical Properties,
Such as bending modulus matrix mechanical property deterioration is apparent.
Chinese invention patent application CN107189394A discloses a kind of fire-retardant plating PC/ of the automobile of fibre reinforced
ABS alloy material and preparation method select DOPO grafting silicon-based mesoporous materials and phosphorus flame retardant to compound, and the total dosage of fire retardant is
10~15%, vertical combustion grade (1.6mm) reaches V-0 grades；It is relatively low that the flame-retardant system equally exists flame retarding efficiency, fire retardant addition
Measure big defect.
In summary, the candle wick that existing flame-retarded technology is difficult to that carbon fiber filler is overcome to bring ignites effect, therefore, develops high
Imitating halogen-free flameproof carbon fiber enhancing PC/ABS mixtures has important social effect and huge economic benefit.
Invention content
The purpose of the present invention is being directed to the market demand and the shortcomings of the prior art, it is efficient to provide a kind of catalysis carbon-forming
Halogen-free flameproof fibre reinforced PC/ABS mixtures and preparation method thereof, which can be used for preparing highly effective flame-retardant electric appliance and vapour
Vehicle product can be applied to the fields such as ultra-thin notebook computer shell, high ferro interior trim, unmanned plane shell and other high-end electric appliances.
Catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS alloys prepared by the present invention, it is fire-retardant using organic phosphorus
Agent, phenoxy phosphazene, basic zirconium phosphate modify the siliceous carbon forming agent compounding flame retardant of triazines, are managed, are made by efficient catalytic charcoal forming machine
The layer of charcoal that must burn is combined closely with carbon fiber, effectively overcomes " the candle wick ignition in hydriding effect of fibre reinforced plastics.Organic phosphate is made
For fire retardant, PC/ABS flame retardant properties are improved, and low-alloyed melting viscosity can be dropped, improves material processing performance；Basic zirconium phosphate is repaiied
The siliceous carbon forming agent of triazines is adornd with phenoxy phosphazene as synergistic fire retardant, there is radical-scavenging, lamella barrier and strengthening material
The functions such as intensity are expected, with organic phosphate organic coupling, catalysis carbon-forming so that the layer of charcoal and carbon that polymer is formed in combustion process
Fiber is tightly combined, and layer of charcoal is more fine and close, realizes efficient halogen-free anti-inflaming.Flame-retardant system is polyarylate, with PC/ABS
With excellent compatibility and dispersibility, fire retardant additive amount is small, small to matrix Effect on Mechanical Properties.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS alloys, it by following mass fraction raw material group
At：
PC resin 37~67%
ABS resin 14~37%
Compatilizer 0~5%
Chopped carbon fiber 5~15%
Antioxidant 0.1%-0.5%
Organic phosphate fire retardant 3~5%
Phenoxy phosphazene 0.5~3%
Basic zirconium phosphate modifies the siliceous carbon forming agent of triazines 0~1%
The organic phosphate fire retardant be tricresyl phosphate (TCP), phenyl-phosphonic acid lanthanum, phenyl-phosphonic acid cerium, to benzene
The organic phosphates such as bis- (diphenyl) phosphates (HDP) of diphenol, isophthalic bis-phenol bis- (diphenyl phosphoesters) (RDP) and PX-200
It is one or more in fire retardant.
The phenoxy phosphazene is the benzene such as five phosphonitrile of six phenoxy groups, three phosphonitrile, eight phenoxy group rings, four phosphonitrile and ten phenoxy groups
It is one or more in oxygroup phosphonitrile class.
To further realize the object of the invention, it is preferable that the PC resin melt index is 5~25g/10min (300
DEG C/1.2kg), number-average molecular weight is 20000~50000.
Preferably, the ABS resin melt index is 3~10g/10min (200 DEG C/5kg), and number-average molecular weight is
10000~30000.
Preferably, the antioxidant is in N- alkoxy hindered amines kind antioxidant (NORs) such as Si-NOR or NOR116
It is one or more.
Preferably, the compatilizer is that organic-silicon-modified ethylene-vinyl acetate copolymer, makrolon organosilicon are embedding
It is one or more in section copolymer and maleic anhydride grafted polystyrene.
Preferably, the described basic zirconium phosphate modification siliceous carbon forming agent degree of polymerization of triazines is 5~10, molecular weight is 2000~
6000, structure is as follows：
Preferably, the chopped carbon fiber bulk density is 300~700g/L, length is 3~15mm, a diameter of 4~
10μm。
A kind of preparation method of catalysis carbon-forming efficient halogen-free anti-inflaming PC/ABS mixtures, it is characterised in that including following step
Suddenly：
1) PC resin, ABS resin and chopped carbon fiber are weighed by above-mentioned weight percent, is placed in 80~90 DEG C of convection ovens
Middle drying 4~6 hours；
2) it is siliceous at charcoal that compatilizer, antioxidant, organic phosphate, phenoxy phosphazene and basic zirconium phosphate modification triazines are weighed
Agent is placed in 60~80 DEG C of vacuum drying ovens and is dried in vacuo 4~6 hours；
3) thoroughly after drying, the raw material in addition to chopped carbon fiber is mixed into 10~15min through high-speed mixer；
4) main feeding bin of the mixed raw material through the combined double screw extruder of cocurrent and parallel is added to extruder material
In cylinder, feed screw rotating speed is 20~40rpm；
5) chopped carbon fiber is added by side spout in barrel, side feed screw rotating speed is 15~25rpm；
6) each section of processing temperature in barrel, exports from charge door to head and is followed successively by：180~200 DEG C, 190~210
DEG C, 200~220 DEG C, 205~225 DEG C, 225~240 DEG C, 230~250 DEG C, engine speed be 300~400rpm, by melting
The PC/ABS mixtures are obtained after squeezing out, be granulated and being dried.
Preferably, barrel vacuum pressure should control within 0.04MPa in twin screw extrusion process；In combination melt blending
When screw-rod structure, each component should be made fully to merge before side feeding there are enough Strong shears plasticizing structure space；In outlet
Mouthful and vacuumize equal aperture positions and should avoid left-hand thread structure, to prevent raw material to be ejected；After screw rod is added in carbon fiber, should also it stay
There is certain Strong shear plasticizing structure space.
The organic phosphate based flame retardant plays the effect of fire-retardant plasticising in system, and fire retardant mechanism is in organophosphor
Promote PC catabolites (hydroxy compounds) heat absorption to be dehydrated into carbon in hydrochlorate decomposable process, layer of charcoal is formed in material surface；- OP bases
Group is heated to be generated free radicals, and is combined with the living radical in polymer degradation processes, polymeric matrix is delayed further to decompose；
On the one hand the vapor that dehydration generates can dilute the concentration of fuel gas in gas phase, on the other hand can reduce polymer
Surface temperature plays good fire retardation.
The fire retardation mechanism of the basic zirconium phosphate modification siliceous carbon forming agent of triazines is mainly in fire retardation PC/ABS burnings
When, Zr4+Rare earth element can capture the H free radicals and OH free radicals of polymer degradation generation, to effectively inhibit
The progress of free chain reaction in gas phase plays highly effective flame-retardant effect；Basic zirconium phosphate is dispersed in poly- with the structure of monolithic layer
It closes in object, gives full play of its lamella blocking effect and solid acid catalysis effect, improve layer of charcoal intensity, air-tightness and thermostabilization
Property, block the heat and mass transport process between gas phase and condensed phase；The siliceous carbon forming agent of triazines and PC/ABS compatibilities are good, heat
Decomposition product generates nitrogen, the micro-nano space clustering of product char formation is degraded into basic zirconium phosphate, carbon fiber and PC, when aggregate amount reaches
Micro-nano Char Residues Structure will be broken through after to the space upper limit, the effect of putting out occurs, by fray-out of flame；And by phosphorus nitrogen silicon synergistic effect,
Promote the effect of organic phosphate fire retardant, catalysis carbon-forming halogen-free flameproof.
The fire retardant mechanism of the phenoxy phosphazene mainly in fire retardation PC/ABS, promotes PC drops by phosphorus nitrogen synergistic effect
Fries rearrangement reactions are carried out in solution preocess, PC is promoted to be cross-linked into charcoal, reduce hydroxy radical content in degradation process, and it is disconnected to alleviate PC main chains
It splits, improves PC/ABS thermal stability.More benzene oxide structures of more phenoxy groups have good compatibility with PC/ABS simultaneously, improve carbon
The mechanical property of fiber reinforced PC/ABS mixtures.
The N- alkoxy hindered amines kind antioxidant (NORs) also has promote at high temperature in addition to antioxidant effect
Into the function at charcoal.Its mechanism is to form NO free radical at high temperature, and the free radical that can generate polymerization without matrix degradation is sudden
It goes out, to effectively inhibit the progress of radical chain decomposition reaction, assists fire-retardant.
The present invention adds carbon fiber and a small amount of fire retardant by reasonable selection flame retardant and every raw material, high reaching
While intensity, fire-retardant (UL94 standards reach V-0 grades, thickness 1.6mm) performance, maintenance material is with certain impact intensity and rationally
Melt flow rate (MFR), realize that different component is fully plasticized and improves its blended characteristic in various ingredients system, it is proposed that crowded
Go out the parameters such as temperature, screw rod revolution, evacuated pressure, finally obtains a kind of efficient halogen-free anti-inflaming fibre reinforced PC/ABS conjunctions
Gold.
It can be seen from the above technical proposal that the present invention has the following advantages：
1, the PC/ABS mixtures prepared by the present invention have the advantages that efficient catalytic into charcoal halogen-free flameproof.Pass through organophosphor
A variety of synergistic effects catalysis PC/ABS that hydrochlorate, phenoxy phosphazene, basic zirconium phosphate modify the siliceous carbon forming agent of triazines is degraded into charcoal, ingeniously
Wonderfully by raising burning layer of charcoal and carbon fiber combination degree, " candle wick is lighted " effect is overcome, promote layer of charcoal density and quality；This
Invention plays fire-retardant phosphorus, nitrogen, silicon synergistic, lamella blocking effect and radical-scavenging effect, greatly promotes matrix flame retardant property,
Realize the efficient halogen-free anti-inflaming of fibre reinforced PC/ABS alloys.
2, the advantages of PC/ABS mixtures prepared by the present invention have fire retardant additive amount small, good mechanical performance.It is logical
Too small molecule phosphate flame retardants improve the mobility of PC/ABS mixtures, improve carbon fiber dispersion and are orientated；Pass through the carbon that is chopped
Fiber, compatilizer and toughener etc. are to PC/ABS activeness and quietness, and due to phenoxy phosphazene, organic phosphorus flame retardant and basic zirconium phosphate
Modify that the siliceous carbon forming agent of triazines and PC/ABS compatibilities are good, additive amount is small, flame-retardant system to matrix Effect on Mechanical Properties compared with
Power that is small, making carbon fiber reinforcement non-bittern flame-proof PC/ABS meet the products such as high-end electronic electric equipment products and automotive trim to material
The requirement with flame retardant property is learned, the ultra-thin product of lightweight high-intensity is can be made into.
Specific implementation mode
In order to facilitate further understanding of the present invention, with reference to specific embodiment, the present invention is described in detail, but this hair
Bright embodiment is without being limited thereto.
Properties of product test method is as follows in the embodiment of the present invention：
Tensile property is tested：According to 1040 standard testings of GB/T, test rate 50mm/min.
Bending property is tested：According to 9341 standard testings of GB/T, test rate 20mm/min.
Impact property is tested：According to GB/T1843 standard testings, test bars thickness is 4mm.
Vertical combustion grade：Standard testing is burnt according to 2408 direct combustions of GB/T, test bars size is 80*10*4mm3。
Limit oxygen index is tested：According to 2406.1 standard testings of GB/T, test bars size is 150*10*4mm3。
Melt index is tested：By 3682 standards of GB/T, 250 DEG C of test temperature, load 2.16kg.
Embodiment 1
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (59%), ABS resin (14.7%), chopped carbon fiber (15%), EMA (5%), RDP (5%), benzene
Oxygroup phosphonitrile (0.5%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (0.5%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 25rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 30rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 2
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (67%), ABS resin (16.7%), chopped carbon fiber (5%), EMA (5%), RDP (5%), benzene
Oxygroup phosphonitrile (0.5%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (0.5%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 25rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 30rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 3
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (37%), ABS resin (37%), chopped carbon fiber (15%), EMA (5%), RDP (5%), benzene oxygen
Base phosphonitrile (0.5%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (0.5%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 25rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 30rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 4
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (56.7%), ABS resin (14%), chopped carbon fiber (15%), EMA (5%), RDP (5%), benzene
Oxygroup phosphonitrile (3%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (1%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 40rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 25rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 5
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (59%), ABS resin (14.2%), chopped carbon fiber (15%), EMA (5%), RDP (5%), benzene
Oxygroup phosphonitrile (0.5%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (1%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 40rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 25rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 6
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (57%), ABS resin (14.2%), chopped carbon fiber (15%), EMA (5%), RDP (5%), benzene
Oxygroup phosphonitrile (3%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (0.5%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 40rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 25rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 7
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (58%), ABS resin (14.7%), chopped carbon fiber (15%), EMA (5%), RDP (3%), benzene
Oxygroup phosphonitrile (3%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (1%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 40rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 25rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Embodiment 8
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (60%), ABS resin (14.2%), chopped carbon fiber (15%), EMA (5%), RDP (5%), benzene
Oxygroup phosphonitrile (0.5%), NOR116 (0.3%).
The siliceous carbon forming agent high speed of PC, ABS, EMA, RDP, NOR116, phenoxy phosphazene and basic zirconium phosphate modification triazines is mixed
The main feeding bin of double screw extruder is put into after conjunction 20min, main feed screw rotating speed is 40rpm, and chopped carbon fiber is placed in
The side feeding bin of double screw extruder, side feed screw rotating speed are 25rpm, are added in extruder main barrel through feed screw,
Engine speed 300rpm, main barrel each bringing-up section section control temperature (totally eight sections of outlet from charge door to head) is 200 DEG C, 220
DEG C, 220 DEG C, 230 DEG C, 235 DEG C, 245 DEG C, 245 DEG C, 250 DEG C, barrel vacuum pressure should control in twin screw extrusion process
Within 0.04MPa；Product is obtained after the processes such as melting extrusion, granulation, drying process.Standard sample is prepared with injection molding machine,
For stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Comparative example 1
Verify mechanical property enhance modified effect, using be not added with carbon fiber, compatilizer, fire retardant PC/ABS as pair
Than.
The blank PC/ABS mixtures of this comparative example are mainly made of the raw material of following weight percent：PC resin
(80%), ABS resin (19.7%), antioxidant 1010 (0.3%).
The main feeding bin of double screw extruder will be put into after PC and ABS mixed at high speed 20min, main feed screw rotating speed is
40rpm is added to through feed screw in extruder main barrel, engine speed 300rpm, each bringing-up section control temperature of main barrel (from
Charge door is exported to head) it is 220 DEG C, 240 DEG C, 240 DEG C, 250 DEG C, 255 DEG C, 255 DEG C, 265 DEG C, 270 DEG C, twin-screw extrusion
Barrel vacuum pressure should control within 0.04MPa in technique；It is obtained after the processes such as melting extrusion, granulation, drying process
Product.Standard sample is prepared with injection molding machine, for stretching, being bent, impact and the performance tests such as fire-retardant, the results are shown in Table 1.
Comparative example 2
Verify flame-retardant modified effect, using be only added to the PC/ABS of the common fire retardant organic phosphorus flame retardant in market as pair
Than.
The catalysis carbon-forming halogen-free flameproof fibre reinforced PC/ABS mixtures of the present embodiment are mainly by following weight percent
Raw material be made：PC resin (61%), ABS resin (14.7%), chopped carbon fiber (15%), RDP (9%), antioxidant 1010
(0.3%).
The main feeding bin of double screw extruder will be put into after PC, ABS and RDP mixed at high speed 20min, main feed screw turns
Speed is 40rpm, is added in extruder main barrel through feed screw, engine speed 300rpm, each bringing-up section control temperature of main barrel
Degree (being exported from charge door to head) is 220 DEG C, 240 DEG C, 240 DEG C, 250 DEG C, 255 DEG C, 255 DEG C, 265 DEG C, 270 DEG C, double spiral shells
Barrel vacuum pressure should control within 0.04MPa in bar expressing technique；By processes such as melting extrusion, granulation, drying process
After obtain product.Standard sample is prepared with injection molding machine, for stretching, being bent, impact and the performance tests such as fire-retardant, as a result such as table 1
It is shown.
Flame retardant property, mechanical property and the melt index of table 1PC/ABS mixtures
By Examples 1 to 8 in table 1 and comparative example 2 it is found that the PC/ABS that organic phosphate RDP is fire retardant is used alone
It is NR that mixture, which reaches its flame retardant rating, (see comparative example 2).But by organic phosphate and phenoxy phosphazene compositional flame-retardant, fire-retardant effect
Rate is effectively improved, and there is phenoxy phosphazene phosphorus phosphorus-nitrogen coordinated fire-retardant effect, enhancing PC degradations to be cross-linked into charcoal, promote layer of charcoal shape
At rate and quality；Basic zirconium phosphate modifies the siliceous carbon forming agent of triazines has lamella barrier and radical-scavenging as synergistic fire retardant
Etc. functions so that the foamed char for formation of burning is finer and close, and with anti-dropping effect while, combustion process is generated
Living radical captured, further promote flame retarding efficiency so that entire flame-retardant system organic coupling, highly effective flame-retardant.Such as
Embodiment 4 is added to the carbon fiber of RDP (5%), phenoxy phosphazene (3%) and the basic zirconium phosphate modification siliceous carbon forming agent of triazines (1%)
Dimension enhancing PC/ABS mixtures, limit oxygen index LOI, can be from compared with the PC/ABS blends for being only added to RDP (9%)
26.1% is promoted to 33.1%, and reaches V-0 grades of flame retardant ratings.Illustrate that fire retardation PC/ABS systems of the present invention have highly effective flame-retardant
Function.
It is total to comparative example 3 it is found that can effectively promote PC/ABS using organic phosphate flame-retardant system by Examples 1 to 8
The mobility of mixed object, substantially improves its processing performance.If embodiment 1 is compared with comparative example 3, melt index is carried from 4.4g/10min
18.0g/10min is risen to, the processing performance of ultra-thin product can be met.
By embodiment 4 and comparative example 1 it is found that the present invention is compared with common PC/ABS alloys, modified PC/ provided by the invention
ABS mixtures have both the advantages of high highly effective flame-retardant, intensity and good fluidity.Such as embodiment 4, it is added to RDP (5%), phenoxy group
Phosphonitrile (3%), basic zirconium phosphate modify the siliceous carbon forming agent of triazines (1%), and the PC/ABS mixtures of carbon fiber (15%) stretch strong
Degree, bending strength, melt index and flame retardant property are compared with comparative example 1 from 66MPa, 81MPa, 4.4g/10min and vertical combustion
Off grade is promoted to 75MPa, 120MPa, 22.7g/10min and V-0 grades of vertical combustion.Pass through organic phosphate, phenoxy group phosphorus
While the synergistic effect that nitrile, basic zirconium phosphate modify the siliceous carbon forming agent of triazines promotes flame retarding efficiency, small molecule phosphate improves
PC/ABS blend flows, efficiently solve excessive fibre reinforced PC/ABS melt viscosities, processing difficulties, can not be made it is super
The problem of thin product；By chopped carbon fiber and compatilizer to PC/ABS activeness and quietness, it is made that proportion is small, intensity is high to be catalyzed into
Charcoal halogen-free flameproof fibre reinforced PC/ABS alloys.
A kind of catalysis carbon-forming efficient halogen-free anti-inflaming carbon fiber PC/ABS mixtures obtained through the invention have unique
Fire-retardant compounding mechanism, efficient catalytic have excellent mechanical property at charcoal halogen-free flameproof, can be widely applied to ultra-thin notebook
In the products such as shell, high ferro interior trim and unmanned plane shell.
Claims (10)
1. a kind of catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures, it is characterised in that by following quality percentage
The raw material of ratio forms：
Polycarbonate resin 37~67%
Acrylonitrile-butadiene-styrene copolymer resin 14~37%
Compatilizer 0~5%
Chopped carbon fiber 5~15%
Antioxidant 0.1%-0.5%
Organic phosphate fire retardant 3~5%
Phenoxy phosphazene 0.5~3%
Basic zirconium phosphate modifies the siliceous carbon forming agent of triazines 0~1%
The organic phosphate fire retardant is tricresyl phosphate, phenyl-phosphonic acid lanthanum, phenyl-phosphonic acid cerium, hydroquinone bis- (two
Phenyl) it is one or more in phosphate or isophthalic bis-phenol bis- (diphenyl phosphoesters)；
The phenoxy phosphazene is the phenoxy groups such as five phosphonitrile of six phenoxy groups, three phosphonitrile, eight phenoxy group rings, four phosphonitrile or ten phenoxy groups
It is one or more in phosphonitrile class；
The antioxidant is N- alkoxy hindered amine kind antioxidants.
2. catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures described in claim 1, it is characterised in that：Institute
The melt index for the polycarbonate resin stated is 5~25g/10min；The number-average molecular weight of the polycarbonate resin is
20000~50000.
3. catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures described in claim 1, it is characterised in that：Institute
The melt index for the acrylonitrile-butadiene-styrene copolymer resin stated is 3~10g/10min；The acrylic nitrile-butadiene two
The number-average molecular weight of alkene-styrene copolymer resin is 10000~30000.
4. catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures described in claim 1, it is characterised in that：Institute
The bulk density for the chopped carbon fiber stated is 300~700g/L, length is 3~15mm, 4~10 μm a diameter of.
5. catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures described in claim 1, it is characterised in that：Institute
The N- alkoxy hindered amine kind antioxidants stated are one or more in Si-NOR or NOR116.
6. catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures described in claim 1, it is characterised in that：Institute
The degree of polymerization for the basic zirconium phosphate modification siliceous carbon forming agent of triazines stated is 5~10, and molecular weight is 2000~6000, and molecular structure is such as
Under：
7. catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures described in claim 1, it is characterised in that：Institute
The compatilizer stated is organic-silicon-modified ethylene-vinyl acetate copolymer, makrolon organic silicon block copolymer and maleic anhydride
It is one or more in grafted polystyrene.
8. the preparation of claim 1-7 any one of them catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures
Method, it is characterised in that include the following steps：
(1) PC resin, ABS resin and chopped carbon fiber are dried；
(2) compatilizer, antioxidant, organic phosphate, phenoxy phosphazene and basic zirconium phosphate the modification siliceous carbon forming agent of triazines are done
It is dry；
(3) raw material after will be dry in addition to chopped carbon fiber is uniformly mixed through high-speed mixer；
(4) main feeding bin of the mixed raw material through the combined double screw extruder of cocurrent and parallel is added to extruder barrel
Interior, control feed screw rotating speed is 20~40rpm；
(5) chopped carbon fiber is added by side spout in barrel, control side feed screw rotating speed is 15~25rpm；
(6) each section of processing temperature in barrel, exports from charge door to head and is followed successively by：180~200 DEG C, 190~210 DEG C,
200~220 DEG C, 205~225 DEG C, 225~240 DEG C, 230~250 DEG C, engine speed is 300~400rpm, is squeezed by melting
The PC/ABS mixtures are obtained after going out, be granulated and being dried.
9. the preparation side of catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures according to claim 8
Method, it is characterised in that：The drying of step (1) is placed in 80~90 DEG C of convection ovens 4~6 hours dry；The drying of step (2)
60~80 DEG C of vacuum drying ovens are placed in be dried in vacuo 4~6 hours.
10. the preparation side of catalysis carbon-forming efficient halogen-free anti-inflaming fibre reinforced PC/ABS mixtures according to claim 8
Method, it is characterised in that：The control of barrel vacuum pressure is within 0.04MPa in twin screw extrusion process；The time of step (3) mixing
For 10~15min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810535470.6A CN108624027B (en) | 2018-05-30 | 2018-05-30 | High-efficiency halogen-free flame-retardant PC/ABS mixture for catalytic carbonization and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810535470.6A CN108624027B (en) | 2018-05-30 | 2018-05-30 | High-efficiency halogen-free flame-retardant PC/ABS mixture for catalytic carbonization and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108624027A true CN108624027A (en) | 2018-10-09 |
| CN108624027B CN108624027B (en) | 2020-02-18 |
Family
ID=63690925
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810535470.6A Active CN108624027B (en) | 2018-05-30 | 2018-05-30 | High-efficiency halogen-free flame-retardant PC/ABS mixture for catalytic carbonization and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108624027B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627734A (en) * | 2018-12-26 | 2019-04-16 | 成都其其小数科技有限公司 | For the lightweight of pesticide spraying unmanned plane shell, corrosion-resistant plastic and preparation method |
| WO2023160148A1 (en) * | 2022-02-25 | 2023-08-31 | 金发科技股份有限公司 | Flame-retardant polycarbonate composition, preparation method therefor and application thereof |
| CN116875021A (en) * | 2023-08-04 | 2023-10-13 | 山东乐佳达新材料科技有限公司 | PC/ABS alloy material and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995602A (en) * | 2017-04-07 | 2017-08-01 | 广州科苑新型材料有限公司 | A kind of high-modulus height flowing halogen-free flame retardant PC/ABS alloy material and preparation method thereof |
| CN107474510A (en) * | 2017-08-29 | 2017-12-15 | 华南理工大学 | High fluidity high rigidity halogen-free flame retardant PC/ABS mixtures and preparation method thereof |
-
2018
- 2018-05-30 CN CN201810535470.6A patent/CN108624027B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106995602A (en) * | 2017-04-07 | 2017-08-01 | 广州科苑新型材料有限公司 | A kind of high-modulus height flowing halogen-free flame retardant PC/ABS alloy material and preparation method thereof |
| CN107474510A (en) * | 2017-08-29 | 2017-12-15 | 华南理工大学 | High fluidity high rigidity halogen-free flame retardant PC/ABS mixtures and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XUEJUN LAI, ET AL.: "Synergistic Effect Between Silicone-Containing Macromolecular Charring Agent and Ammonium Polyphosphate in Flame Retardant Polypropylene", 《JOURNAL OF APPLIED POLYMER SCIENCE》 * |
| XUEJUN LAI,ET AL.: "Thermal degradation and combustion behavior of novel intumescent flame retardant polypropylene with N-alkoxy hindered amine", 《JOURNAL OF ANALYTICAL AND APPLIED PYROLYSIS》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109627734A (en) * | 2018-12-26 | 2019-04-16 | 成都其其小数科技有限公司 | For the lightweight of pesticide spraying unmanned plane shell, corrosion-resistant plastic and preparation method |
| WO2023160148A1 (en) * | 2022-02-25 | 2023-08-31 | 金发科技股份有限公司 | Flame-retardant polycarbonate composition, preparation method therefor and application thereof |
| CN116875021A (en) * | 2023-08-04 | 2023-10-13 | 山东乐佳达新材料科技有限公司 | PC/ABS alloy material and preparation method and application thereof |
| CN116875021B (en) * | 2023-08-04 | 2024-02-27 | 山东乐佳达新材料科技有限公司 | PC/ABS alloy material and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108624027B (en) | 2020-02-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102391608B (en) | Ultrahigh heat-resistant and flame-retardant ABS (acrylonitrile butadiene styrene) composition and preparation method thereof | |
| CN112250935B (en) | High-flame-retardant-grade low-smoke halogen-free material and preparation method and application thereof | |
| CN101280097A (en) | Nanometer flame-proof polyethylene glycol terephthalate engineering plastics and preparation thereof | |
| CN108117735B (en) | High-performance halogen-free flame-retardant polycarbonate material and preparation method thereof | |
| CN108624027A (en) | A kind of catalysis carbon-forming efficient halogen-free anti-inflaming PC/ABS mixtures and preparation method thereof | |
| CN103059346A (en) | Composite flame retardant, preparation method and application thereof | |
| CN110105738B (en) | Flame-retardant PC/ABS material and preparation method and application thereof | |
| CN106009585A (en) | Halogen-free flame retardation polycarbonate material and preparation method thereof | |
| CN112812435A (en) | Normal-temperature heat-conducting high-temperature flame-retardant polymer composite material and preparation method thereof | |
| CN105482349A (en) | High temperature resistant halogen-free flame retardant ABS composition | |
| CN104231575A (en) | Halogen-free and phosphorus-free PBT enhanced composite material and preparation method thereof | |
| CN110643165A (en) | High-performance ultraviolet-resistant environment-friendly flame-retardant PC/ABS composite material and preparation method thereof | |
| CN101062992A (en) | Halogen-free flame-proof highly anti-flush polyphenylacetylene composition and method of making the same | |
| CN109206739A (en) | Nitrogen phosphorus Si modification graphene Halogenless fire retarded polymer composite material and preparation method | |
| CN101851405B (en) | High-CTI high-GWIT environment-friendly flame-retardant reinforced PBT engineering plastic for unattended electric appliance and preparation method thereof | |
| CN111171542B (en) | High CTI flame-retardant polycarbonate alloy material and preparation method and application thereof | |
| CN105111729B (en) | Environmental protection flame retardant carbon fiber reinforced polyamide composite material and its preparation method and application | |
| CN101643576B (en) | Zero halogen flame resistance alloy composite and preparation method thereof | |
| CN112322020B (en) | Polyphenyl ether resin composition and preparation method thereof, and wire slot and preparation method thereof | |
| CN108003600A (en) | A kind of flame retardant automotive inside gadget material and preparation method thereof | |
| CN108570205A (en) | A kind of Flameproof styrenic composition and preparation method thereof | |
| CN1300238C (en) | Magnesium solt whisker rein forced fire-resisting polypropylene composition | |
| CN102604212A (en) | Aramid fiber pulp-enhanced expansion flame retardant polypropylene composite material and preparation method thereof | |
| CN109852050A (en) | A kind of glass fiber reinforcement low-smoke non-halogen flame-retardant PA66 material and preparation method thereof | |
| CN102391581A (en) | Halogen-free flame-retarding polypropylene nano composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |