CN101735585A - Halogen-free fire-retarding PC/ABS alloy and preparation method thereof - Google Patents
Halogen-free fire-retarding PC/ABS alloy and preparation method thereof Download PDFInfo
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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
- B29C48/36—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
- B29C48/92—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
- B29C2948/9258—Velocity
- B29C2948/9259—Angular velocity
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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
- B29C2948/9258—Velocity
- B29C2948/926—Flow or feed rate
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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
- B29C2948/92828—Raw material handling or dosing, e.g. active hopper or feeding device
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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
- B29C2948/92866—Inlet shaft or slot, e.g. passive hopper; Injector, e.g. injector nozzle on barrel
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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
- B29C2948/92885—Screw or gear
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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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- 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
- B29C2948/92904—Die; Nozzle zone
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Abstract
The invention discloses a halogen-free fire-retarding PC/ABS alloy. The raw materials comprise two kinds of polycarbonate of different melt index specifications, an ABS resin, phosphate flame fire retardants, an antioxidant, a mould release agent and polytetrafluoroethylene powder. In the PC/ABS alloy of the invention, the fire-retardant level of is no lower than UL-94 V0(1.6mm), the tensile strength is no less than 49MPa, the bending strength is no less than 90MPa, the impact strength of a cantilever notch is no less than 550J/m, the heat distortion temperature is no less than 80 DEG C(3.2MM, 1.82MPa), and the mold shrinkage is no more than 0.7 percent. The halogen-free fire-retarding PC/ABS alloy is halogen-free and environmentally-friendly and has comprehensive performance which is as good as or better than that of the PC/ABS resin materials reported at home and aboard. The halogen-free fire-retarding PC/ABS alloy contains a small amount of assistant and has a low cost. The preparation method of the halogen-free fire-retarding PC/ABS alloy of the invention is simple in process, easy to implement and low in energy consumption and is particularly suitable to be used for large-scale production of the halogen-free fire-retarding PC/ABS alloy.
Description
Technical field
The present invention relates to fire retardation PC/ABS alloy material and preparation method thereof, particularly a kind of halogen-free flame retardant PC/ABS Alloy And Preparation Method.
Background technology
That polycarbonate (PC) has is nontoxic, heat-resisting, transparent, water-intake rate is low, shock strength height, creep-resistant property and dimensional stability are good, advantages such as dielectric properties are good, but exist processing fluidity poor, easily stress cracking, to the breach sensitivity, shortcoming such as easily wear out, wear no resistance.Can overcome the deficiency of PC with thermoplastics acrylonitrile-butadiene-styrene copolymer (ABS) blend, improve its over-all properties.Fire retardation PC/ABS alloy is widely used in aspects such as automobile, machinery, household electrical appliances, computer, Communication Equipment, office equipment.
The flame retardant resistance of polycarbonate itself can reach UL94 V-2 level, but practical application often requires higher flame retardant properties, and the affiliation that adds of ABS causes the flame retardant resistance of PC itself to reduce.Addition is few although halogen containing flame-retardant has, the flame retarding efficiency advantages of higher, relevant its fire-retardant research to PC and PC/ABS alloy also has a lot of reports, but because halogen containing flame-retardant amount of being fuming in combustion processes is big, and discharge poisonous, corrosive gas, etching apparatus, in case catch fire, bring difficulty can for personnel escape and rescue operation.Halogen-free flame retardants has good flame retardation effect, pollutes characteristics such as little.
The mechanical property of PC/ABS alloy and flame retardant resistance height depend on the proportioning of PC/ABS and the kind and the consumption of fire retardant to a great extent.PC content is higher, PC/ABS alloy good flame resistance, but indexs such as toughness, ageing resistance and processing fluidity are then relatively poor relatively.
A kind of novel halogen-free flame-retardant PC/ABS alloy need be provided, not only good flame retardation effect, fire-retardant lasting, and good, the easy processing of mechanical property, good toughness, be difficult for aging and notch sensitivity low, simultaneously with low cost.
Summary of the invention
In view of this, one of purpose of the present invention provides a kind of halogen-free flame retardant PC/ABS alloy, not only good flame retardation effect, fire-retardant lasting, and good, the easy processing of mechanical property, good toughness, be difficult for aging and notch sensitivity low, simultaneously with low cost.
Halogen-free flame retardant PC of the present invention/ABS alloy, raw material comprises following composition by weight:
Molten refer to for polycarbonate 35-60 part of 21-23,
Molten refer to for polycarbonate 15-30 part of 4-6,
Acrylonitrile-butadiene-styrene copolymer 11-19 part,
Phosphoric acid ester fire retardant 15-25 part,
Polytetrafluoroethylene powder 0.2-0.7 part,
Oxidation inhibitor 0.1-0.5 part,
With
Releasing agent 0.1-0.5 part.
Further, described raw material comprises by weight:
Molten refer to for polycarbonate 40-50 part of 21-23,
Molten refer to for polycarbonate 20-25 part of 4-6,
Acrylonitrile-butadiene-styrene copolymer 14-17 part,
Phosphoric acid ester fire retardant 18-22 part,
Polytetrafluoroethylene powder 0.4-0.6 part,
Oxidation inhibitor 0.2-0.4 part,
With
Releasing agent 0.2-0.4 part;
Further, the molten finger of first kind of polycarbonate is that the molten finger of 22, the second kinds of polycarbonate is 5;
Further, described phosphoric acid ester fire retardant is a diphenyl phosphoester;
Further, described raw material comprises by weight: molten finger is that 22 45 parts of polycarbonate, the molten finger are 0.38 part of 5 0.3 part in 0.5 part of 20 parts of 16 parts of 22 parts of polycarbonate, acrylonitrile-butadiene-styrene copolymers, diphenyl phosphoesters, polytetrafluoroethylene powder, oxidation inhibitor and releasing agent;
Further, described oxidation inhibitor is Hinered phenols antioxidant and phosphite ester kind antioxidant, and described releasing agent is the stearic acid releasing agent.
Two of purpose of the present invention provides the method for preparation described halogen-free flame retardant PC/ABS alloy, comprises the steps:
A. according to described ratio raw material was mixed in high-speed mixer 3-5 minute, get mixture;
B. the gained mixture melt extrudes postcooling through parallel double-screw extruder, described parallel double-screw extruder is provided with nine sections temperature controlled region, and the processing parameter that blend is extruded is respectively 1 district 195-205 ℃, 2 district 230-250 ℃, 3 district 240-260 ℃, 4 district 240-260 ℃, 5 district 240-260 ℃, 6 district 240-260 ℃, 7 district 240-260 ℃, 8 district 240-260 ℃, 9 district 255-265 ℃ and head 255-265 ℃;
C. the cooled material to step b gained carries out drying, promptly gets required halogen-free flame retardant PC/ABS alloy product.
Further, the processing parameter that described parallel double-screw extruder blend is extruded is: 260 ℃ of 200 ℃ in 1 district, 240 ℃ in 2 districts, 250 ℃ in 3 districts, 250 ℃ in 4 districts, 250 ℃ in 5 districts, 250 ℃ in 6 districts, 250 ℃ in 7 districts, 250 ℃ in 8 districts, 260 ℃ in 9 districts and heads, feed rate is 40KG/H, and engine speed is 400R/M.
The invention has the beneficial effects as follows:
Halogen-free flame retardant PC of the present invention/ABS alloy is arranged in pairs or groups the molten polycarbonate and the ABS resin of specification of referring to of two kinds of differences according to specified proportion, extrude and get with amount of retardant, antioxidant, releasing agent and four kinds of auxiliary agent melt blendings of polytetrafluoroethylene powder again; Fire retardation PC of the present invention/fire-retardant rank of ABS alloy is not less than UL-94V0 (1.6mm) level, tensile strength (ASTM D638,50mm/min) be not less than 49MPa, flexural strength (ASTMD790,1.3mm/min) being not less than 90MPa, socle girder notched Izod impact strength (ASTM D256,23 ℃) is not less than 550J/m, heat-drawn wire (ASTM D648,3.2mm, 1.82Mpa) be not less than 80 ℃, molding shrinkage (ASTM D955, thickness 3.2mm) is not more than 0.7%, and not halogen-containing, environmentally friendly, over-all properties is not second to the domestic and international fire retardation PC of reporting/ABS resin material property, auxiliary dosage of the present invention is little, and cost is cheaper.
The method of the described halogen-free flame retardant PC of preparation of the present invention/ABS alloy, its technology is simple, implements easily, and energy consumption is low, is suitable for very much the large-scale production of described halogen-free flame retardant PC/ABS alloy.
Other advantages of the present invention, target and feature will be set forth to a certain extent in the following description, and to a certain extent, based on being conspicuous to those skilled in the art, perhaps can obtain instruction from the practice of the present invention to investigating hereinafter.
Embodiment
Below will be described in detail the preferred embodiments of the present invention.Should be appreciated that preferred embodiment only for the present invention is described, rather than in order to limit protection scope of the present invention.
Embodiment 1
Be that 21 polycarbonate, 15 parts molten finger is that 4 polycarbonate, 11 parts of acrylonitrile-butadiene-styrene copolymers, 15 parts of phosphoric acid ester fire retardants, 0.2 part of polytetrafluoroethylene powder, 0.1 part of oxidation inhibitor and 0.1 part of releasing agent mix in high-speed mixer and melt extrude by parallel double-screw extruder after 5 minutes with 35 parts of molten fingers by weight, be required halogen-free flame retardant PC/ABS alloy behind the material cooling drying of extruding.In the present embodiment, described fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester), and oxidation inhibitor is Hinered phenols antioxidant 1076, and described releasing agent is stearic acid releasing agent PETS.In the present embodiment, the processing parameter that described parallel double-screw extruder blend is extruded is: 255 ℃ of 195 ℃ in 1 district, 230 ℃ in 2 districts, 240 ℃ in 3 districts, 240 ℃ in 4 districts, 250 ℃ in 5 districts, 250 ℃ in 6 districts, 250 ℃ in 7 districts, 250 ℃ in 8 districts, 255 ℃ in 9 districts and heads, engine speed 400r/min, feed rate is 40KG/H.
Through researchist's experiment confirm of the present invention, in the present embodiment, add the phosphoric acid ester fire retardant (as: dihydroxyphenyl propane two (diphenyl phosphoester) of 15-25 part weight, the cumyl phenyl phosphate ester, resorcin phosphate etc.) all can realize purpose of the present invention, when adopting diphenyl phosphoester, can bring into play fire retardation simultaneously in gas phase and condensed phase, comprise inhibition flame, molten stream heat dissipation, the surface barrier that phosphoric acid forms, acid catalysis becomes carbon, heat insulation and the oxygen barrier of carbon-coating etc., these influencing factors to fire-retardant Relative Contribution with relevant with the fire condition by the classification of fire-retardant superpolymer, but the multiple binding mode that all relates under many circumstances, phosphorus fire retardant.At condensed phase, phosphorus generates phosphoric acid in when burning, generates metaphosphoric acid under higher temperature, and phosphoric acid and metaphosphoric acid all are dewatering agents, makes the polymkeric substance carbonization of directly dewatering, and avoids inflammable gas to generate; Form coke layer on the combustionmaterial surface simultaneously, it can intercept contacting of combustion gases and flame front on the one hand, again air and heat are separated from the combustionmaterial surface on the other hand, thereby stop burning away of object, therefore the phosphoric acid ester fire retardant is used for the PC/ABS alloy material and has good effect, double fire-retardant, plasticization effect is an one, simultaneously additive-based easy to manufacture, the low price, easy to use of phosphoric acid ester fire retardant.
The oxidation inhibitor of present embodiment adopts Hinered phenols antioxidant or phosphite ester kind antioxidant, and polymer materials is in high temperature process or use, because the attack of Sauerstoffatom can make it that oxidative degradation takes place.Find through years of researches, the A dynamic oxidation process of polymkeric substance is that a series of A are by the radical reaction process, the primary product of initial reaction stage is to resolve into living radical under proper condition by hydroperoxide, this free radical generates new free radical with macromole hydrocarbon or oxygen reaction again, circulation makes oxidizing reaction be undertaken by free radical chain type course so again and again.
In polymkeric substance, add oxidation inhibitor,, make them unlikelyly cause the chain reaction that destruction is arranged exactly in order to catch free radical R and the ROO that the chain reaction stage forms; Oxidation inhibitor can also hydroperoxide decomposition ROOH, makes it generate stable nonactive product.By the mechanism of action, oxidation inhibitor can be divided into primary antioxidant and auxiliary antioxidant.Primary antioxidant can react with free radical R, ROO, interrupts the growth of living chain, and auxiliary antioxidant can suppress, delay the generation of free radical in the elicitation procedure, hydroperoxide decomposition, and passivation remains in the metal ion in the polymkeric substance.
As the Hinered phenols antioxidant of primary antioxidant be a class on phenyl ring hydroxyl (there is substituent compound～OH) one or both sides.Because an OH is subjected to spatial obstacle, the H atom splits away off from molecule easily, combine with peroxylradicals (ROO), alkoxy free group (RO), hydroxy radical qiao (OH) etc. and to make it to lose activity, thereby the chain reaction of thermo-oxidative ageing is stopped, this mechanism is chain termination donor mechanism.
In the polymkeric substance weathering process,, just can stop this oxidising process if can catch peroxylradicals effectively.But the speed of reaction that generates peroxylradicals is exceedingly fast, so under the condition that has oxygen to exist, radical scavenger just can lose efficacy.Under the situation that Hinered phenols antioxidant exists, 1 peroxylradicals (ROO) will be captured 1 proton from polymkeric substance (RH), interrupt this a series of free radical reactions, and this is the controlled step of autoxidation.When adding hindered phenol antioxygen, it promptly provides a more favourable reaction to form the phenol oxyradical than the easier proton that provides of those polymkeric substance, and this makes polymkeric substance relatively stable, oxidation can not take place further.
In addition, hindered phenol can also carry out some reactions of catching carbon radicals, can generate dipolymer, and this dipolymer can lose activity it with the peroxylradicals reaction, self then become stable quinone molecule, because each hindered phenol can be caught at least 2 free radicals, so its aging-resistant effect is better.So Hinered phenols antioxidant or phosphite ester kind antioxidant all are applicable to the present invention.
Releasing agent adopts the stearic acid releasing agent, from the mechanics angle analysis, after two components are mixed and are expelled in the die cavity, Zinic stearas will precipitate into a kind of jelly, and carry out along with solidified and move to the surface of parts, thereby formed the film of a floor height release property at the interface at die cavity, so the stearic acid releasing agent all is applicable to the present invention.
Embodiment 2
In the present embodiment, except the molten finger of first kind of polycarbonate is 23, the molten finger of second kind of polycarbonate is 6, acrylonitrile-butadiene-styrene copolymer is 19 especially, all the other conditions are all identical with embodiment 1.
Embodiment 3
Be that 21 polycarbonate, 30 parts molten finger is that 4 polycarbonate, 11 parts of acrylonitrile-butadiene-styrene copolymers, 15 parts of phosphoric acid ester fire retardants, 0.2 part of polytetrafluoroethylene powder, 0.1 part of oxidation inhibitor and 0.1 part of releasing agent mix in high-speed mixer and melt extrude by parallel double-screw extruder after 3 minutes with 60 parts of molten fingers by weight, be required halogen-free flame retardant PC/ABS alloy behind the material cooling drying of extruding; In the present embodiment, described phosphoric acid ester fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester), oxidation inhibitor is Hinered phenols antioxidant 1076, described stearic acid releasing agent PETS, the processing parameter that the parallel double-screw extruder blend is extruded is: 265 ℃ of 205 ℃ in 1 district, 250 ℃ in 2 districts, 260 ℃ in 3 districts, 260 ℃ in 4 districts, 260 ℃ in 5 districts, 260 ℃ in 6 districts, 260 ℃ in 7 districts, 260 ℃ in 8 districts, 265 ℃ in 9 districts and heads, engine speed 400r/min, feed rate is 40KG/H.
Embodiment 4
Be that 22 polycarbonate, 15 parts molten finger is that 5 polycarbonate, 19 parts of acrylonitrile-butadiene-styrene copolymers, 15 parts of diphenyl phosphoesters, 0.7 part of polytetrafluoroethylene powder, 0.5 part of oxidation inhibitor and 0.1 part of releasing agent mix in high-speed mixer and melt extrude by parallel double-screw extruder after 3 minutes with 35 parts of molten fingers by weight, be required halogen-free flame retardant PC/ABS alloy behind the material cooling drying of extruding.Described fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester), and oxidation inhibitor is Hinered phenols antioxidant 1076, and described releasing agent is stearic acid releasing agent PETS.The processing parameter that the parallel double-screw extruder blend is extruded is respectively 265 ℃ of 205 ℃ in 1 district, 250 ℃ in 2 districts, 260 ℃ in 3 districts, 260 ℃ in 4 districts, 260 ℃ in 5 districts, 260 ℃ in 6 districts, 260 ℃ in 7 districts, 260 ℃ in 8 districts, 265 ℃ in 9 districts and heads, engine speed 400r/min, feed rate is 40KG/H.
Embodiment 5
In the present embodiment, raw material comprises that by weight 40 parts of molten fingers are that 22 polycarbonate, 20 parts of molten fingers are 5 polycarbonate, 14 parts of acrylonitrile-butadiene-styrene copolymers, 22 parts of diphenyl phosphoesters, 0.4 part of polytetrafluoroethylene powder, 0.2 part of oxidation inhibitor and 0.2 part of releasing agent, and all the other conditions of present embodiment are identical with embodiment 4.
Embodiment 6
Be that 22 polycarbonate, 25 parts molten finger is that 5 polycarbonate, 14 parts of acrylonitrile-butadiene-styrene copolymers, 18 parts of phosphoric acid ester fire retardants, 0.6 part of polytetrafluoroethylene powder, 0.4 part of oxidation inhibitor and 0.4 part of releasing agent mix in high-speed mixer and melt extrude by parallel double-screw extruder after 3 minutes with 50 parts of molten fingers by weight, be required halogen-free flame retardant PC/ABS alloy behind the material cooling drying of extruding.In the present embodiment, described fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester), and oxidation inhibitor is Hinered phenols antioxidant 1076, and described releasing agent is stearic acid releasing agent PETS.The processing parameter that the parallel double-screw extruder blend is extruded is respectively 255 ℃ of 195 ℃ in 1 district, 230 ℃ in 2 districts, 240 ℃ in 3 districts, 240 ℃ in 4 districts, 240 ℃ in 5 districts, 240 ℃ in 6 districts, 240 ℃ in 7 districts, 240 ℃ in 8 districts, 255 ℃ in 9 districts and heads, engine speed 400r/min, feed rate is 40KG/H.
Embodiment 7
In the present embodiment, raw material comprises that by weight 40 parts of molten fingers are that 22 polycarbonate, 20 parts of molten fingers are 5 polycarbonate, 17 parts of acrylonitrile-butadiene-styrene copolymers, 18 parts of diphenyl phosphoesters, 0.6 part of polytetrafluoroethylene powder, 0.4 part of oxidation inhibitor and 0.4 part of releasing agent, and all the other conditions are identical with embodiment 4.
Embodiment 8
Be that 22 polycarbonate, 22 parts molten finger is that 5 polycarbonate, 16 parts of acrylonitrile-butadiene-styrene copolymers, 20 parts of diphenyl phosphoesters, 0.5 part of polytetrafluoroethylene powder, 0.3 part of oxidation inhibitor and 0.38 part of releasing agent mix in high-speed mixer and melt extrude by parallel double-screw extruder after 3 minutes with 45 parts of molten fingers by weight, be required halogen-free flame retardant PC/ABS alloy behind the material cooling drying of extruding; In the present embodiment, described fire retardant is dihydroxyphenyl propane two (diphenyl phosphoester), and oxidation inhibitor is Hinered phenols antioxidant 1076, and described releasing agent is stearic acid releasing agent PETS.The processing parameter that the parallel double-screw extruder blend is extruded is respectively 260 ℃ of 200 ℃ in 1 district, 240 ℃ in 2 districts, 250 ℃ in 3 districts, 250 ℃ in 4 districts, 260 ℃ in 5 districts, 260 ℃ in 6 districts, 250 ℃ in 7 districts, 250 ℃ in 8 districts, 260 ℃ in 9 districts and heads, engine speed 400r/min, feed rate is 40KG/H.
The various embodiments described above are carried out performance test according to table 1 standard:
Table 1
| Performance | Testing standard | Test condition | International unit |
| Melt index | ??ASTM?D1238 | ??300℃/1.2Kg | ??g/10min |
| Proportion | ??ASTM?D792 | ??23℃ | ??g/cm 3 |
| Tensile strength | ??ASTM?D638 | ??50mm/min | ??Mpa |
| Elongation at break | ??ASTM?D638 | ??50mm/min | ??％ |
| Flexural strength | ??ASTM?D790 | ??1.3mm/min | ??Mpa |
| Modulus in flexure | ??ASTM?D790 | ??1.3mm/min | ??Mpa |
| The socle girder notched Izod impact strength | ??ASTM?D256 | ??23℃ | ??J/m |
| Heat-drawn wire | ??ASTM?D648 | ??3.2mm，1.82Mpa | ??℃ |
| Performance | Testing standard | Test condition | International unit |
| Molding shrinkage | ??ASTM?D955 | Thickness 3.2mm | ??％ |
| Flame retardant resistance | ??UL-94 | ??1.6mm |
And obtain the performance of described each embodiment product, as table 2:
Table 2
| Embodiment | Melt index | Proportion | Tensile strength | Elongation at break | The socle girder notched Izod impact strength | Flexural strength | Modulus in flexure | Heat-drawn wire | Molding shrinkage | Flame retardant resistance |
| ??1 | ??11 | ??1.19 | ??63.5 | ??50 | ??560 | ??95 | ??2240 | ??104 | ??0.7 | ??V-1 |
| ??2 | ??11 | ??1.17 | ??64.3 | ??69 | ??552 | ??93 | ??2214 | ??103 | ??0.7 | ??V-1 |
| ??3 | ??12 | ??1.17 | ??64.5 | ??53 | ??570 | ??93 | ??2216 | ??104 | ??0.7 | ??V-1 |
| ??4 | ??13 | ??1.15 | ??64.7 | ??68 | ??583 | ??94 | ??2318 | ??96 | ??0.7 | ??V-1 |
| ??5 | ??13 | ??1.15 | ??65.2 | ??54 | ??586 | ??96 | ??2619 | ??97 | ??0.6 | ??V-0 |
| ??6 | ??14 | ??1.14 | ??65.8 | ??52 | ??591 | ??99 | ??2319 | ??98 | ??0.6 | ??V-0 |
| ??7 | ??14 | ??1.13 | ??66.1 | ??60 | ??595 | ??99 | ??2321 | ??98 | ??0.6 | ??V-0 |
| ??8 | ??14 | ??1.12 | ??66.8 | ??66 | ??602 | ??101 | ??2525 | ??101 | ??0.5 | ??V-0 |
Explanation is at last, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although the present invention is had been described in detail with reference to preferred embodiment, those of ordinary skill in the art is to be understood that, can make amendment or be equal to replacement technical scheme of the present invention, and not breaking away from the aim and the scope of technical solution of the present invention, it all should be encompassed in the middle of the claim scope of the present invention.
Claims (8)
1. halogen-free flame retardant PC/ABS alloy, it is characterized in that: raw material comprises following composition by weight:
Molten finger is polycarbonate 35-60 part of 21-23
Molten finger is polycarbonate 15-30 part of 4-6
Acrylonitrile-butadiene-styrene copolymer 11-19 part
Phosphoric acid ester fire retardant 15-25 part
Polytetrafluoroethylene powder 0.2-0.7 part
Oxidation inhibitor 0.1-0.5 part
Releasing agent 0.1-0.5 part.
2. halogen-free flame retardant PC according to claim 1/ABS alloy is characterized in that: described raw material comprises by weight:
Molten finger is polycarbonate 40-50 part of 21-23
Molten finger is polycarbonate 20-25 part of 4-6
Acrylonitrile-butadiene-styrene copolymer 14-17 part
Phosphoric acid ester fire retardant 18-22 part
Polytetrafluoroethylene powder 0.4-0.6 part
Oxidation inhibitor 0.2-0.4 part
Releasing agent 0.2-0.4 part.
3. halogen-free flame retardant PC according to claim 1 and 2/ABS alloy is characterized in that: the molten finger of first kind of polycarbonate is that the molten finger of 22, the second kinds of polycarbonate is 5.
4. halogen-free flame retardant PC according to claim 3/ABS alloy is characterized in that: described phosphoric acid ester fire retardant is a diphenyl phosphoester.
5. halogen-free flame retardant PC according to claim 4/ABS alloy is characterized in that: described raw material comprises by weight: molten finger is that 22 45 parts of polycarbonate, the molten finger are 0.38 part of 5 0.3 part in 0.5 part of 20 parts of 16 parts of 22 parts of polycarbonate, acrylonitrile-butadiene-styrene copolymers, diphenyl phosphoesters, polytetrafluoroethylene powder, oxidation inhibitor and releasing agent.
6. halogen-free flame retardant PC according to claim 5/ABS alloy is characterized in that: described oxidation inhibitor is Hinered phenols antioxidant or phosphite ester kind antioxidant, and described releasing agent is the stearic acid releasing agent.
7. the described halogen-free flame retardant PC of preparation claim 1/ABS alloy is characterized in that: comprise the steps:
A. according to described ratio raw material was mixed in high-speed mixer 3-5 minute, get mixture;
B. the gained mixture melt extrudes postcooling through parallel double-screw extruder, described parallel double-screw extruder is provided with nine sections temperature controlled region, and the processing parameter that blend is extruded is respectively 1 district 195-205 ℃, 2 district 230-250 ℃, 3 district 240-260 ℃, 4 district 240-260 ℃, 5 district 240-260 ℃, 6 district 240-260 ℃, 7 district 240-260 ℃, 8 district 240-260 ℃, 9 district 255-265 ℃ and head 255-265 ℃;
C. the cooled material to step b gained carries out drying, promptly gets required halogen-free flame retardant PC/ABS alloy product.
8. the method for preparing halogen-free flame retardant PC/ABS alloy according to claim 7, it is characterized in that: the processing parameter that described parallel double-screw extruder blend is extruded is: 260 ℃ of 200 ℃ in 1 district, 240 ℃ in 2 districts, 250 ℃ in 3 districts, 250 ℃ in 4 districts, 250 ℃ in 5 districts, 250 ℃ in 6 districts, 250 ℃ in 7 districts, 250 ℃ in 8 districts, 260 ℃ in 9 districts and heads, feed rate is 40KG/H, and engine speed is 400R/M.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464876A (en) * | 2010-11-15 | 2012-05-23 | 苏州汉扬精密电子有限公司 | PC/ABS defective material modified recovery formula |
| CN103374214A (en) * | 2012-04-25 | 2013-10-30 | 黑龙江鑫达企业集团有限公司 | High-impact environment-friendly flame-retardant PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation technology thereof |
| CN103890093A (en) * | 2012-10-18 | 2014-06-25 | Lg化学株式会社 | Glass fiber reinforced polycarbonate flame retardant resin composition |
| CN106147188A (en) * | 2016-08-05 | 2016-11-23 | 江苏金发科技新材料有限公司 | A kind of high fluidity polycarbonate alloy and preparation method thereof |
| CN111073242A (en) * | 2019-11-25 | 2020-04-28 | 上海锦湖日丽塑料有限公司 | High-melt-strength halogen-free flame-retardant blow-molded PC/ABS alloy and preparation method thereof |
| WO2022081000A1 (en) * | 2020-10-12 | 2022-04-21 | Toray Industries, Inc. | Flame-retardant rubber-reinforced polycarbonate resin composition and molded article thereof |
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2009
- 2009-12-15 CN CN200910191931A patent/CN101735585A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102464876A (en) * | 2010-11-15 | 2012-05-23 | 苏州汉扬精密电子有限公司 | PC/ABS defective material modified recovery formula |
| CN103374214A (en) * | 2012-04-25 | 2013-10-30 | 黑龙江鑫达企业集团有限公司 | High-impact environment-friendly flame-retardant PC (Polycarbonate)/ABS (Acrylonitrile Butadiene Styrene) alloy material and preparation technology thereof |
| CN103890093A (en) * | 2012-10-18 | 2014-06-25 | Lg化学株式会社 | Glass fiber reinforced polycarbonate flame retardant resin composition |
| CN103890093B (en) * | 2012-10-18 | 2015-11-25 | Lg化学株式会社 | The Polycarbonate flame retardant resin combination of glass fiber reinforcement |
| CN106147188A (en) * | 2016-08-05 | 2016-11-23 | 江苏金发科技新材料有限公司 | A kind of high fluidity polycarbonate alloy and preparation method thereof |
| CN106147188B (en) * | 2016-08-05 | 2019-01-15 | 江苏金发科技新材料有限公司 | A kind of high fluidity polycarbonate alloy and preparation method thereof |
| CN111073242A (en) * | 2019-11-25 | 2020-04-28 | 上海锦湖日丽塑料有限公司 | High-melt-strength halogen-free flame-retardant blow-molded PC/ABS alloy and preparation method thereof |
| WO2022081000A1 (en) * | 2020-10-12 | 2022-04-21 | Toray Industries, Inc. | Flame-retardant rubber-reinforced polycarbonate resin composition and molded article thereof |
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