CN103408915B - A kind of high rigidity polycarbonate composite material and preparation method thereof - Google Patents
A kind of high rigidity polycarbonate composite material and preparation method thereof Download PDFInfo
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- CN103408915B CN103408915B CN201310378604.5A CN201310378604A CN103408915B CN 103408915 B CN103408915 B CN 103408915B CN 201310378604 A CN201310378604 A CN 201310378604A CN 103408915 B CN103408915 B CN 103408915B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/12—Making granules characterised by structure or composition
- B29B9/14—Making granules characterised by structure or composition fibre-reinforced
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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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
- B29C48/78—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling
- B29C48/875—Thermal treatment of the extrusion moulding material or of preformed parts or layers, e.g. by heating or cooling for achieving a non-uniform temperature distribution, e.g. using barrels having both cooling and heating zones
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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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/42—Block-or graft-polymers containing polysiloxane sequences
- C08G77/445—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences
- C08G77/448—Block-or graft-polymers containing polysiloxane sequences containing polyester sequences containing polycarbonate sequences
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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
-
- 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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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
Abstract
The present invention relates to modified polycarbonate resin field, specifically disclose a kind of high rigidity polycarbonate composite material and preparation method thereof.This matrix material is prepared from proportion by following raw material, each raw materials quality portion rate such as under: polycarbonate 40 ~ 70; Glass fibre 30 ~ 60; Antioxidant 0.08 ~ 0.6; Anti-dripping agent 0.1 ~ 1; Lubricant 0.5 ~ 5; Fire retardant 0.08 ~ 5; Phase solvent 1 ~ 5.The preparation method of this matrix material is that (1) takes above-mentioned polycarbonate, antioxidant, anti-dripping agent, lubricant, fire retardant and phase solvent; (2) said components is fed in proportion in mixing tank and mixes 10 ~ 30 minutes; (3) raw material that step poly-(2) mixes is thrown in twin screw extruder, take above-mentioned glass fibre side and feed, melt extrude, granulation.Matrix material prepared by the method has high rigidity, high workability, ultra-tough, low warpage and halogen-free flameproof performance.
Description
Technical field
The present invention relates to modified polycarbonate resin field, particularly relate to a kind of high rigidity polycarbonate composite material and preparation method thereof.
Background technology
Polycarbonate, due to its good mechanical strength, is used widely in a lot of field now.At present, the polycarbonate strongthener of commercial type, mainly adds glass fibre and fine two kinds of carbon.The polycarbonate adding the fine modification of carbon causes being restricted in application due to the price of its costliness.Application is add glass fibre modification strongthener widely.Because the intermiscibility of glass fibre and polycarbonate is bad, the easy emersion material surface of glass fibre; Content of glass fiber is higher, and Drawing abillity is poorer, and forming process difficulty, toughness of material is poor, and easily warpage occurs.
The modified polycarbonate of high firm super tough low warpage properties energy is mainly used in ultra-thin product field, the glass fiber material adopting nylon to add high-content can meet the rigid requirements of ultra-thin materials, but this material spraying difficulty, and buckling deformation is larger, be difficult to the demand meeting this field, in this field, the magnesium-aluminium alloy material of many employings premium properties substitutes, but this material price is expensive, processing difficulties, make the comprehensive cost of product very high, so develop a kind of material with high firm super tough low warpage properties energy, be used for substituting magnesium-aluminium alloy material in ultra-thin product field and there is huge using value.
Polycarbonate adds glass fiber material good spraying effect, and stability is high, the internal stress that the adding of glass fibre can reduce polycarbonate and improve rigidity of material and fatigue resistance.But polycarbonate is non-crystalline material, and melt viscosity is high, particularly filled glass fiber makes the processing of polycarbonate glass fibre composite more difficult; And simple glass fiber imports in general bisphenol-a polycarbonate, the resistance to impact shock of polycarbonate is sharply declined, and particularly high-content glass fibre makes the viscosity of whole compound system higher, poor fluidity, processing difficulties, makes large-size ultra-thin product and hardly may.
Chinese Patent Application No.: 200910197243.8, disclose a kind of low warping high surface gloss glass glass fiber reinforced polyester matrix material and preparation method, this patent reduces system viscosity by importing PBT in polycarbonate, imports kaolin simultaneously, in order to reduce warpage.But importing PBT can make the processing temperature scope of material narrow, and make complicated, formula material is many, in earlier stage complex process; Kaolinic importing, can make mechanics of materials strength degradation, and surface gloss reduces, and selects common toughner in system, and the resistance to elevated temperatures of material is declined.
Summary of the invention
The object of the invention is for deficiency of the prior art, provide a kind of high rigidity polycarbonate composite material, it has the feature of high rigidity, high workability, low warpage, high tenacity and halogen-free flameproof.
Another object of the present invention is, provide a kind of preparation method of high rigidity polycarbonate composite material, it has working condition and easily manipulates, and material compatible is effective, effectively enhances productivity and reduces the feature of production cost.
Object of the present invention is achieved through the following technical solutions:
A kind of high rigidity polycarbonate composite material, is made up of the raw material of following weight part:
Polycarbonate 40 ~ 70;
Glass fibre 30 ~ 60;
Antioxidant 0.08 ~ 0.6;
Anti-dripping agent 0.1 ~ 1;
Lubricant 0.5 ~ 5;
Fire retardant 0.08 ~ 5;
Phase solvent 1 ~ 5.
Preferably, be made up of the raw material of following weight part:
Polycarbonate 55-65;
Glass fibre 35-45;
Antioxidant 0.2-0.4;
Anti-dripping agent 0.4-0.7;
Lubricant 0.5-3;
Fire retardant 0.1-4;
Phase solvent 2-3.
Further preferred, be made up of the raw material of following weight part:
Polycarbonate 60;
Glass fibre 40;
Antioxidant 0.4;
Anti-dripping agent 0.7;
Lubricant 1.5;
Fire retardant 3;
Phase solvent 2.5.
Wherein, described polycarbonate is organosilicon Copolycarbonate, and molecular-weight average is 17000, and this organosilicon polycarbonate makes material have good mobility and injection moulding performance, also makes material have good toughness simultaneously; Described glass fibre is cross section is flat or the non-conventional glass fiber of silkworm chrysalis type, the short glass fiber of this abnormity has good associativity compared to traditional regular cylindrical glass fibre and polycarbonate, also can play the effect of that resist warping and raising material flowability simultaneously.
Wherein, described anti-dripping agent is any one in tetrafluoroethylene, MMA coating modification PTFE or AS coating modification PTFE, and tetrafluoroethylene, English abbreviation is the full name of PTFE, MMA is methyl methacrylate, and the full name of AS is acrylonitritrile-styrene resin.Do not have the flame-retardant anti-dropping effect of coated tetrafluoroethylene better, but it is poor with polycarbonate consistency, can affect the mechanical property of material to a certain extent, but the present invention carries out reasonable compatibility by adding suitable non-conventional glass fiber, can make up the loss of material mechanical performance; The tetrafluoroethylene that MMA is coated or AS is coated, its flame-retardant anti-dropping effect a little almost, but the present invention is by coordinating with the optimization of polycarbonate, improves the consistency of integral material, ensure that the excellent properties of material property.
Wherein, described lubricant is the mixture of one or more in pentaerythritol stearate class, ethylene waxes or silicone oil, pentaerythritol stearate class belongs to internal lubricant for polycarbonate, it plays the effect of the interaction force weakened between molecular chain, intermolecular slip and rotation can be caused, lower intermolecular frictional force, avoid too much shearing force generation thermal conductance to cause material and degrade, the mobility of material can be improved simultaneously; Ethylene waxes or silicone oil belong to external lubricant for polycarbonate, and it can be attached to the surface of melt or processor, mould, form lubrication interface, reduce the frictional force of melt and processor, also can play the easy demoulding simultaneously and improve the effect of floating fibre.
Wherein, described antioxidant is antioxidant 168 and the mixture of any one or two kinds in antioxidant 1076 or fire-resistant oxidation resistant agent 412s, irgasfos 168 is as auxiliary antioxidant, antioxidant 1076 and 412S are as main anti-oxidant, and any one or two kinds in auxiliary antioxidant and main anti-oxidant are used in combination.Antioxidant 1076 is that Zi You Ji temper goes out agent, is the key of terminating chain degraded; The decomposition temperature of fire-resistant oxidation resistant agent 412s is higher, and thermotolerance is better.A large amount of shear heat can be produced owing to adding glass fiber material; Antioxidant 168 is peroxide decomposers, and can be stable non-free radical peroxide conversion, the preferred proportion of their consumption be; Antioxidant 1076: antioxidant 412s: antioxidant 168=1:1:1 ~ 2.
Described fire retardant be Phosphorus, sulfonate or silicone based in a kind of or several arbitrarily mixtures.Phosphorus flame retardant has into the gentle effect intercepted mutually of carbon, and Sulfonates and organosilicon play a part coagulation phase and intercept; Fine flame retardant effect can play in single use phosphorus system, but has certain loss to thermal distortion; Be used alone Sulfonates flame retardant effect general, because glass fibre stops form fine and close carbon-coating, and its consumption has certain limit, and continuing interpolation after exceeding certain value does not have flame retardant effect, and it is large to material property loss to continue interpolation; Organosilicon adds separately can accomplish good flame retardant effect, but large usage quantity; The present invention preferably uses by this three based flame retardants interworking, can play good flame retardant effect, and consumption is little, little on the impact of material property.Further, the ratio of above-mentioned three based flame retardants is Phosphorus: Sulfonates: silicone based=2 ~ 8:0.1 ~ 1:0.8 ~ 10.
Wherein, described phase solvent is any one of styrene-maleic anhydride copolymer, POE grafted maleic anhydride copolymer or PE grafted maleic anhydride copolymer.Copolymer-maleic anhydride can combine with the active group on glass fibre well, the bond properties of styrene-maleic anhydride copolymer, POE grafted maleic anhydride copolymer or PE grafted maleic anhydride copolymer and polycarbonate is better, reduce the interfacial thickness of glass fibre and polycarbonate, reduce interfacial energy, improve boundary strength, make the mechanical property of whole material higher.
The preparation method of above-mentioned a kind of high rigidity polycarbonate composite material, step is as follows:
(1) polycarbonate, antioxidant, anti-dripping agent, lubricant, fire retardant and phase solvent is taken by formula;
(2) above-mentioned each raw material is fed in mixing tank and mixes 10 ~ 30 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take glass fibre side by formula and feed, melt extrude, granulation;
Wherein twin screw extruder comprises ten temperature controlled region, be respectively: the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, the temperature in temperature control 3-4 district is 260-280 DEG C, the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
Wherein, described twin screw extruder has two to vacuumize place, and one of them place of vacuumizing is positioned at the end of material conveying section, the starting end of melt zone; Another place of vacuumizing is positioned at metering zone.Two vacuumize and can better the oxygen in forcing machine and small molecules be extracted out, avoid polycarbonate molecule to be oxidized and degraded, ensure the performance of material.
Beneficial effect of the present invention: the present invention is by the reasonable coordination to each component, obtained matrix material of the present invention has ultra-tough energy and good processing fluidity, and high rigidity can be given prominence to, and low warpage properties can be excellent, and safer environmental protection, is particularly suitable for the processed and applied of ultra-large type thin section part.
Another beneficial effect of the present invention: controlled by the condition of preparation method, produce high rigidity can and high workability, low warpage properties can polycarbonate composite material, its especially applicable suitability for industrialized production.
Embodiment
The invention will be further described with the following Examples.
embodiment 1
(1) 60 parts of polycarbonate are taken, 0.3 part of antioxidant 1076 and the 168 mixing antioxidants that mix of 1:1 by weight, 0.4 part of PTFE, 2 parts of pentaerythritol stearate series lubricant agents, 3 parts of phosphorus type flame retardants and 3 parts of styrene-maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 20 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 40 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature, the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, and the temperature in temperature control 3-4 district is 260-280 DEG C, and the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 2
(1) 40 parts of polycarbonate are taken, 0.6 part of antioxidant 412S and the 168 mixing antioxidants that mix of 1:1 by weight, 0.6 part of PTFE, 5 parts of ethylene waxes, 5 parts of silicone based flame retardants and 5 parts of styrene-maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 15 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 60 parts of glass fibre sides and feed, melt extrude, granulation.
Wherein twin screw extruder each temperature controlled region temperature, the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, and the temperature in temperature control 3-4 district is 260-280 DEG C, and the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 3
(1) 50 parts of polycarbonate are taken, 0.5 part of antioxidant 1076 and the 168 mixing antioxidants that mix of 1:2 by weight, 0.5 part of MMA coating modification PTFE, 4 parts of silicone oil, the mixing fire retardant of 4 parts of Phosphorus and silicone based arbitrary proportion mixing and 4 parts of POE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 10 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 50 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature, the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, and the temperature in temperature control 3-4 district is 260-280 DEG C, and the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 4
(1) 70 parts of polycarbonate are taken, 0.08 part of antioxidant 168 and 412s be the mixing antioxidant that mixes of 2:1 by weight, 0.1 part of MMA coating modification PTFE, the hybrid lubricant of 0.5 part of pentaerythritol stearate class and the mixing of ethylene waxes arbitrary proportion, Phosphorus, the sulphonic acids of 0.08 part of equivalent and the mixing fire retardant of silicone based mixing and 4 parts of PE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 25 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 30 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature, the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, and the temperature in temperature control 3-4 district is 260-280 DEG C, and the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 5
(1) 65 parts of polycarbonate are taken, 0.1 part of antioxidant 1076 with 168 by weight the mixing antioxidant mixed for 2:1,0.7 part of AS coating modification PTFE, the hybrid lubricant that 1 part of pentaerythritol stearate class and silicone oil mix in any proportion, 1 part of Phosphorus, sulphonic acids and the silicone based mixing oxidation inhibitor that mixes according to mass ratio 2:1:5 and 3.5 parts of POE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 30 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 35 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature is respectively: the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, the temperature in temperature control 3-4 district is 260-280 DEG C, the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, and the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 6
(1) 45 parts of polycarbonate are taken, 0.4 part of antioxidant 1076, antioxidant 168 and anti-oxidant 412s press the mixing antioxidant of balanced mix, 1 part of MMA coating modification PTFE, the hybrid lubricant that 3 parts of ethylene waxes and silicone oil mix in any proportion, the mixing fire retardant that 4 parts of Phosphorus, sulphonic acids and silicone based 8:0.5:4 in mass ratio mix and 4.5 parts of POE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 30 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 55 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature is respectively: the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, the temperature in temperature control 3-4 district is 260-280 DEG C, the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, and the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 7
(1) 55 parts of polycarbonate are taken, the mixing antioxidant that 0.2 part of antioxidant 1076, antioxidant 168 and anti-oxidant 412s mix by weight 1:2:1,0.3 part of AS coating modification PTFE, 1.5 parts of pentaerythritol stearate classes, the hybrid lubricant that ethylene waxes and silicone oil mix in any proportion, the mixing fire retardant that 0.1 part of Phosphorus, sulphonic acids and silicone based 2:0.1:10 in mass ratio mix and 2.5 parts of POE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 30 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 45 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature is respectively: the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, the temperature in temperature control 3-4 district is 260-280 DEG C, the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, and the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
embodiment 8
(1) 60 parts of polycarbonate are taken, the mixing antioxidant that 0.4 part of antioxidant 1076, antioxidant 168 and anti-oxidant 412s mix by weight 1:1:1,0.7 part of AS coating modification PTFE, the mixed lubrication that 1.5 parts of pentaerythritol stearate class, ethylene waxes and silicone oil mix in any proportion, the mixing fire retardant that 3 parts of Phosphorus, sulphonic acids and silicone based 2:0.5:5 in mass ratio mix and 2.5 parts of PE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 30 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 40 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature is respectively: the temperature in temperature control 1-2 district is 200 ~ 250 DEG C, the temperature in temperature control 3-4 district is 260-280 DEG C, the temperature in temperature control 5-6 district is 260 ~ 270 DEG C, and the temperature in temperature control 7-8 district is 240 ~ 260 DEG C, and the temperature in temperature control 9-10 district is 250 ~ 260 DEG C.
comparative example 1
(1) taking 60 parts of molecular-weight average is the bisphenol A-type PC of 17000, the mixing antioxidant of 0.6 part of antioxidant 1076 and 168,0.4 part of AS coating modification PTFE, 4 parts of pentaerythritol stearate classes, 5 parts of phosphorus flame retardants and 4 parts of ethylene waxes and silicone oil mixing compatilizer;
(2) said components is fed in proportion in mixing tank and mixes 20 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 40 parts of glass fibre sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature is respectively: the temperature in temperature control 1-2 district is 200 ~ 280 DEG C; The temperature in temperature control 3-4 district is 200 ~ 280 DEG C; The temperature in temperature control 5-6 district is 200 ~ 280 DEG C; The temperature in temperature control 7-8 district is 200 ~ 280 DEG C; The temperature in temperature control 9-10 district is 200 ~ 280 DEG C.
comparative example 2
(1) take 60 parts of polycarbonate, 0.3 part of 412s with 168 mix antioxidant, 0.4 part of tetrafluoroethylene, 2 parts of pentaerythritol stearate classes, 3 parts of silicone based flame retardant agent and 3 parts of POE grafted maleic anhydride copolymers;
(2) said components is fed in proportion in mixing tank and mixes 20 minutes;
(3) raw material that step (2) mixes is thrown in twin screw extruder, take 40 parts of glass fibre 995 sides and feed, melt extrude, granulation;
Wherein twin screw extruder each temperature controlled region temperature, the temperature in temperature control 1-2 district is 200 ~ 280 DEG C; The temperature in temperature control 3-4 district is 200 ~ 280 DEG C; The temperature in temperature control 5-6 district is 200 ~ 280 DEG C; The temperature in temperature control 7-8 district is 200 ~ 280 DEG C; The temperature in temperature control 9-10 district is 200 ~ 280 DEG C.
table 1: the performance test results of each embodiment
| Example 1 | Example 2 | Example 3 | Example 4 | Example 5 | Example 6 | Example 7 | Example 8 | Comparison example 1 | Comparison example 2 | |
| Modulus in flexure Kgf/cm2 ASTM D790 | 123340 | 145136 | 134023 | 82874 | 93057 | 140100 | 133807 | 123405 | 103678 | 90106 |
| Flexural strength Kgf/cm2 ASTM D790 | 2030 | 1833 | 2084 | 1906 | 1987 | 2035 | 2100 | 2210 | 1600 | 1850 |
| Tensile strength Kgf/cm2 ASTM D638 | 1610 | 1280 | 1350 | 1580 | 1760 | 1530 | 1570 | 1750 | 940 | 1120 |
| Shock strength 1/8 ' ' kgf cm/cm | 16.4 | 12.8 | 14.6 | 17.6 | 17.23 | 15.76 | 16.84 | 18 | 6.4 | 10.8 |
| Melting index g/10min ASTM D1238 | 22.7 | 21.6 | 23.4 | 26.1 | 25.2 | 22.3 | 23.7 | 24.2 | 10.2 | 18.7 |
| Fire-retardant UL vertical checkout | V0 | V0 | V0 | V0 | V0 | V0 | V1 | V0 | V0 | V0 |
| Angularity | 0.23 | 0.09 | 0.12 | 0.27 | 0.22 | 0.17 | 0.19 | 0.11 | 0.35 | 0.51 |
| Heat-drawn wire 1.82MP/3.2mm | 130 | 142 | 134 | 135 | 138 | 137 | 140 | 138 | 136 | 134 |
| Elongation at break % | 4 | 2.1 | 3 | 4.9 | 4.2 | 3.2 | 3.9 | 4.5 | 0.3 | 1.5 |
Note: Elongation test condition is 50mm/min, crooked test condition is 2.8mm/min, and melting index test condition is 300 DEG C of * 1.2kg.
As shown in Table 1, the modulus in flexure in the present invention, flexural strength and tensile strength numerical value are overall higher than comparative example, then illustrate that the polycarbonate composite material of preparation has good high rigidity energy; Shock strength and elongation at break are comparatively large, then illustrate that the polycarbonate composite material of preparation has ultra-tough energy; The warpage performance of angularity energy reactor product, angularity is lower, then illustrate that the buckling deformation of product is less, that resist warping performance is better, the glass fibre selected is the flat or short glass fiber of pupa shape in cross section and the reasonable compatibility of other components, makes the polycarbonate composite material of preparation have low warpage properties energy; Melting index is high, illustrates that product has high mobility, makes processing characteristics excellent; Fire retardant is halogen-free flameproof, and the most high energy of flame retardant properties reaches UL94 V0 level.In sum, polycarbonate composite material of the present invention has the performance of high rigidity, high workability and low warpage, and toughness is fine, is especially suitable for ultra-thin product field.
Finally should be noted that; above embodiment is only in order to illustrate technical scheme of the present invention; but not limiting the scope of the invention; although done to explain to the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (4)
1. a high rigidity polycarbonate composite material, is characterized in that: be made up of the raw material of following weight part:
Polycarbonate 40 ~ 70;
Glass fibre 30 ~ 60;
Antioxidant 0.08 ~ 0.6;
Anti-dripping agent 0.1 ~ 0.6;
Lubricant 0.5 ~ 5;
Fire retardant 0.08 ~ 5;
Phase solvent 1 ~ 5, described polycarbonate is organosilicon Copolycarbonate, described glass fibre is cross section is short glass fiber that is flat or silkworm chrysalis type, described anti-dripping agent is tetrafluoroethylene, described fire retardant is silicone based, and described phase solvent is any one in styrene-maleic anhydride copolymer, POE grafted maleic anhydride copolymer or PE grafted maleic anhydride copolymer.
2. the high rigidity polycarbonate composite material of one according to claim 1, is characterized in that: be made up of the raw material of following weight part:
Polycarbonate 55-65;
Glass fibre 35-45;
Antioxidant 0.2-0.4;
Anti-dripping agent 0.4-0.6;
Lubricant 0.5-3;
Fire retardant 0.1-4;
Phase solvent 2-3.
3. the high rigidity polycarbonate composite material of one according to claim 1, is characterized in that: described lubricant is the mixture of one or more in pentaerythritol stearate class, ethylene waxes or silicone oil.
4. the high rigidity polycarbonate composite material of one according to claim 1, is characterized in that: described antioxidant is antioxidant 168 and the mixture of any one or two kinds in antioxidant 1076.
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| CN103013088A (en) * | 2012-12-29 | 2013-04-03 | 东莞市奥能工程塑料有限公司 | High-rigidity polycarbonate composite material and preparation method thereof |
| CN103333477A (en) * | 2013-06-24 | 2013-10-02 | 吴江市物华五金制品有限公司 | Halogen-free flame-retardant PC/PBT (Poly Carbonate/Polybutylene Terephthalate) composite material |
| CN103435997A (en) * | 2013-08-23 | 2013-12-11 | 北京化工大学常州先进材料研究院 | Continuous long-fiber enhanced halogen-free flame-retardant polycarbonate composite material and preparation method thereof |
| CN103740072A (en) * | 2013-11-20 | 2014-04-23 | 青岛佰众化工技术有限公司 | Polycarbonate compound |
| CN104693772A (en) * | 2015-03-04 | 2015-06-10 | 安徽科聚新材料有限公司 | Glass fiber-mica mixed enhanced polycarbonate material and preparation method thereof |
| CN105331075A (en) * | 2015-11-03 | 2016-02-17 | 五行材料科技（江苏）有限公司 | Halogen-free flame-retardant polycarbonate composite material used for plate products and preparation method |
| CN105694414B (en) * | 2016-04-12 | 2017-12-15 | 东莞市奥能工程塑料有限公司 | A kind of high content fiber glass reinforced halogen-free flame retardant PC composites and preparation method thereof |
| CN106118007A (en) * | 2016-06-30 | 2016-11-16 | 河南鼎力杆塔股份有限公司 | Pc product information identification system |
| CN106633778A (en) * | 2016-12-30 | 2017-05-10 | 东莞市奥能工程塑料有限公司 | High-content glass fiber reinforced antistatic PC composite material and preparation method thereof |
| CN108047677A (en) * | 2017-12-13 | 2018-05-18 | 四川大学 | A kind of high-wear-resistancehigh-strength high-strength polycarbonate composite material and preparation method thereof |
| CN109206875A (en) * | 2018-07-25 | 2019-01-15 | 天津金发新材料有限公司 | A kind of polycarbonate compositions and preparation method thereof |
| CN109280135A (en) * | 2018-08-30 | 2019-01-29 | 铨盛聚碳科技股份有限公司 | A kind of anti-dripping agent and preparation method thereof with superior compatibility |
| CN110157174A (en) * | 2019-05-30 | 2019-08-23 | 深圳华力兴新材料股份有限公司 | A kind of the fire-retardant polycarbonate composite material and preparation method and application of glass fiber reinforcement |
| CN112430388A (en) * | 2019-08-26 | 2021-03-02 | 汉达精密电子(昆山)有限公司 | High-performance halogen-free flame-retardant PC/GF composite material and product thereof |
| CN114075382A (en) * | 2020-08-21 | 2022-02-22 | 汉达精密电子(昆山)有限公司 | High-performance glass fiber reinforced PC material and product thereof |
| CN111926278B (en) * | 2020-09-24 | 2021-01-08 | 华中科技大学 | Three-phase electromagnetic wiping device for strip-shaped workpiece and hot dip coating system |
| CN114736499B (en) * | 2022-03-07 | 2023-05-23 | 金发科技股份有限公司 | PC composite material and preparation method and application thereof |
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