CN107189393A - A kind of halogen-free flameproof enhancing PC/AES alloys and preparation method thereof - Google Patents

A kind of halogen-free flameproof enhancing PC/AES alloys and preparation method thereof Download PDF

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CN107189393A
CN107189393A CN201710375320.9A CN201710375320A CN107189393A CN 107189393 A CN107189393 A CN 107189393A CN 201710375320 A CN201710375320 A CN 201710375320A CN 107189393 A CN107189393 A CN 107189393A
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halogen
temperature
area
parts
aes
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高山俊
易娟
刘俊威
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/02Flame or fire retardant/resistant
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00Properties
    • C08L2201/22Halogen free composition
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/03Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C08L2205/035Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend

Abstract

The present invention relates to a kind of halogen-free flameproof enhancing PC/AES alloys and preparation method thereof, the alloy is made up of the raw material of following mass parts:10 25 parts of 55 65 parts of PC, AES, 4 12 parts of compatilizer, 16 20 parts of Halogen compound flame retardant, 0.5 1 parts of anti-dripping agent, 0.1 0.5 parts of lubricant, 0.1 0.5 parts of antioxidant;The Halogen compound flame retardant is by bisphenol-A double (diphenyl phosphates) and quaternary ammonium salt built up silane couple modified montmorillonoid in mass ratio 39:1 is mixed to get.Halogen-free flameproof that the present invention is provided enhancing PC/AES alloys have good comprehensive mechanical property and fire resistance, and carbon left is high after burning and will not produce a large amount of smog, is environmentally friendly practical alloy material.

Description

A kind of halogen-free flameproof enhancing PC/AES alloys and preparation method thereof
Technical field
The present invention relates to polymeric material field, PC/AES alloys and its preparation are strengthened more particularly, to a kind of halogen-free flameproof Method.
Background technology
Makrolon (PC) is a kind of engineering plastics of excellent performance, because it has excellent mechanical performance, heat-resisting quantity Can and be widely used in every field, however, on the other hand, makrolon there is also poor fluidity, notch sensitive, easily production The shortcomings of raw internal stress ftractures.AES resins are the terpolymer of the ethylene propylene diene rubber of one acrylonitrile of styrene one, AES resins Middle EPDM (ethylene propylene diene rubber) strand double bond content is few, therefore it is better than ABS resin in terms of weatherability, impact strength, PC/AES alloys can realize the mutual supplement with each other's advantages of two kinds of resins, obtain the excellent and easily processed into type alloy of comprehensive mechanical property Material.
The anti-flammability of PC/AES alloys is also the focus of people's Recent study, with increasingly carrying for people's living standard Height, society requires also stricter for the combustibility of material.AES resins and PC fire-retardant rank are UL94-HB, and itself is simultaneously Do not possess good fire resistance, the fire-retardant rank of its alloy is not also high, can improve PC/AES using different flame-retardant systems closes The flame-retarding characteristic of gold.The harm that traditional halogen system inhibiting tape comes has attracted increasing attention, as used bromide fire retardant fire-retardant PC/AES alloys generate more corrosive gas and smog when burning.Research direction both domestic and external was mainly Halogen in the last few years Flame-retardant system.For PC/AES alloys, halogen-free flame-retardant system mainly has phosphorus flame retardant (triphenyl phosphate, bisphenol-A bis phosphoric acid two Phenyl ester etc.), silicon-series five-retardant (methyl phenyl siloxane, inorganic silicate etc.), Intumscent Flame Retardant System etc..Current halogen-free flameproof The subject matter that PC/AES alloys are present is relatively low for the comprehensive mechanical property of flame-retardant alloy, and particularly shock resistance declines bright Aobvious, flame-retardant alloy produces a large amount of smog and molten drop when burning, and flame retarding efficiency is low.
The content of the invention
The technical problems to be solved by the invention are to be hindered for above shortcomings in the prior art there is provided a kind of Halogen Combustion enhancing PC/AES alloys and preparation method thereof, bisphenol-A-bis- is cooperateed with using quaternary ammonium salt built up silane couple modified montmorillonoid (diphenyl phosphate) (BDP) carries out fire-retardant enhancing to PC/AES alloys, and it is carried out while compatilizer, lubricant etc. is respectively adopted Capacity increasing modifying, gained PC/AES alloys flame retarding efficiency is high, and comprehensive mechanical property is good, and can prevent a large amount of molten drops from generating.
In order to solve the above technical problems, the technical scheme that the present invention is provided is:
A kind of halogen-free flameproof enhancing PC/AES alloys are provided, the alloy is made up of the raw material of following mass parts:PC 55-65 Part, 10-25 parts of AES, 4-12 parts of compatilizer, 16-20 parts of Halogen compound flame retardant, 0.5-1 parts of anti-dripping agent, lubricant 0.1- 0.5 part, 0.1-0.5 parts of antioxidant;
The Halogen compound flame retardant is changed by bisphenol-A-bis- (diphenyl phosphates) (BDP) with quaternary ammonium salt built up silane couple Property montmorillonite 3-9 in mass ratio:1 is mixed to get;
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is:
1) sodium-based montmorillonite is scattered in deionized water, the removal of impurity is gone in centrifugation, adjusts pH=6 with HCl solution, finally use Deionized water rinsing is to without Cl-In the presence of being subsequently added the Cetyltrimethylammonium bromide of 1.1 times of cation exchange contents to sodium Base montmorillonite carries out cation exchange, and then the vigorous reaction 4h under the conditions of 60-80 DEG C washs through filtering, deionized water, dries Processing obtains quaternary ammonium salt modified montmorillonoid;
2) by step 1) gained quaternary ammonium salt modified montmorillonoid be dispersed in water, adjust pH=4, be subsequently added 1.1 times of sun from The silane coupler of sub- exchange capacity vigorous reaction 4h under the conditions of 60-80 DEG C, is washed, then be through drying through filtering, deionized water Obtain quaternary ammonium salt built up silane couple modified montmorillonoid.
The phosphorus content of the BDP is 8.9%, is light yellow transparent liquid, relative density 1.26g/cm3(20 DEG C), viscosity For 13000mPas (25 DEG C);
Preferably, the silane coupler is KH108 (3- piperazinopropyls methyl dimethoxysilane).KH108 is Colourless transparent liquid, molecular weight is 232g/mol, nitrogen content 12.10%.Cetyltrimethylammonium bromide molecular weight is 392.5g/mol。
Preferably, the cation exchange capacity of the sodium-based montmorillonite is 100mmol/100g.
Organic phosphorus flame retardant BDP has good compatibility with PC/AES alloy systems, while the double (di(2-ethylhexyl)phosphates of bisphenol-A Phenyl ester) BDP be liquid phase fire retardant, there is good plasticization for alloy, the processing characteristics of alloy can be improved.By right Flame-retardant alloy thermogravimetic analysis (TGA) is obtained, and the dominant mechanism of the fire-retardant enhancing alloys of BDP has gas phase fire-retardant with condensed phase simultaneously, can be with The thermal degradation temperature of alloy second stage PC phases is improved, while remaining carbon increase at 800 DEG C.BDP is heated to produce PO free radicals, It can capture H and HO free radicals, so as to suppress the progress of combustion reaction, reach the fire-retardant purpose of gas phase.Sodium-based montmorillonite Strengthen after organically-modified with high polymer alloy matrix compatibility, between matrix insertion cheating engaging layer, strand can be suppressed Warm-up movement, strengthens the heat endurance of alloy;Montmorillonite simultaneously is heated to form the surface that SI-O or SI-C keys are coated on alloy, hinder The only release of heat and the entrance of oxygen.The present invention utilizes the fire-retardant enhancing PC/AES alloys of organic phosphorus flame retardant BDP gas phases, together When promote the formation of organic layer of charcoal, utilize inorganic nano silicic acid organic modification montmonrillonite to suppress the warm-up movement of strand, promote table The stabilization of face layer of charcoal, prepares phosphorus-silicon efficient halogen-free anti-inflaming PC/AES alloys.
By such scheme, the compatilizer be phenylethylene-maleic anhydride graft copolymer (SMA) or ethylene propylene diene rubber- Maleic anhydride graft copolymer (MAH-g-EPDM).The grafting rate of maleic anhydride is 18% in wherein SMA, and mean molecule quantity is 1.2-1.8 ten thousand, heat decomposition temperature is higher than 320 DEG C, and density is 1.06-1.12g/cm3.Maleic groups in SMA can be with PC terminal hydroxy group reacts, and reduces the interfacial tension of two-phase, refines dispersed phase particles in PC/AES alloys, reaches increase-volume Effect.MAH-g-EPDM is pale yellow coloured particles, and maleic anhydride grafting ratio is more than 0.8%.MAH-g-EPDM and AES have ternary second Third rubber components, and maleic anhydride can equally play compatibilization.
By such scheme, the anti-dripping agent is polytetrafluoroethylene (PTFE) (PTFE).
By such scheme, the lubricant is the double stearic amides of vinyl or ethylene bis stearamide.
By such scheme, the antioxidant is 4,4 '-thiobis (the 6- tert-butyl group -3- methylphenols) or double (2,4- bis- uncles Butyl phenyl) pentaerythritol diphosphites.
The present invention, which also provides above-mentioned halogen-free flameproof, strengthens the preparation method of PC/AES alloys, is specially:Original is weighed by proportioning Material, double screw extruder dog-house is put into after being well mixed by raw material, and the rotating speed for controlling double screw extruder is 100-200r/ Min is extruded and granulated, and prepares halogen-free flameproof enhancing PC/AES alloys.
By such scheme, the temperature in each area of double screw extruder is:One area's temperature is 220-230 DEG C, two area's temperature For 220-230 DEG C, three area's temperature are 230-240 DEG C, and four area's temperature are 230-240 DEG C, and five area's temperature are 235-245 DEG C, 6th area Temperature is 235-245 DEG C, and seven area's temperature are 235-245 DEG C.
The beneficial effects of the present invention are:
1) present invention uses organic phosphorus flame retardant BDP complex quaternary ammonium salts built up silane couple modified montmorillonoids, with reference to Gas phase and condensed phase fire retardant mechanism, prepare efficient halogen-free anti-inflaming enhancing PC/AES alloys, and gained PC/AES alloys have height The fire resistance of effect, limited oxygen index can reach 30.7-35.5%, and vertical combustion grade reaches V-0 ranks, in 800 DEG C of high temperature Lower remaining carbon is high, up to 15.62-17.77%, and maximum heat weightless temperature is improved, and flame retarding efficiency is high.
2) phosphorus flame retardant BDP has good plasticization for PC/AES alloy systems in the present invention, can be obvious Processing temperature is reduced, improves alloy processing characteristics, is easy to large-scale production, the PC/AES alloy moltens added after compound flame retardant Index is 7.2-9.9g/10min (test temperature is 245 DEG C, and counterbalance mass is 3.8Kg).
3) the modified PC/AES alloys of present invention Halogen compound flame retardant have good mechanical property, tensile strength Up to 64.32-67.03MPa, bending strength-reach 91.23-97.87MPa, impact strength reaches 46.36-49.28KJ/m2
Embodiment
To make those skilled in the art more fully understand technical scheme, the present invention is made with reference to embodiment It is described in further detail.
PC used in comparative example and embodiment of the present invention is provided by Taiwan Qimei Industry Co., Ltd., and the trade mark is PC- 110, molding shrinkage is 0.6%, and density is 1.2g/cm3, the melt index under conditions of 300 DEG C, counterbalance mass are 1.2kg For 10g/10min, UL-94 vertical combustions grade is HB.AES resins used are provided by Shanghai Kumbosunny Plastics CO.,LTD (trade mark HW600G), density is 1.04g/cm3, molding shrinkage is that 0.4%, UL-94 vertical combustions grade is HB.
Comparative example 1
A kind of PC/AES alloys, it is following (mass parts) that it is formulated composition
The compatilizer is SMA, and wherein maleic anhydride grafting ratio is 18%.The antioxidant is 4,4 '-thiobis (uncle 6- Butyl -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE) (PTFE, the production of Zhenjiang, Jiangsu Chun Huan fluorine Products Co., Ltd), profit Lubrication prescription is the double stearic amides of vinyl.
This comparative example PC/AES alloy preparation methods are as follows:Precise above each component raw material, by original after being well mixed Material puts into double screw extruder dog-house, and the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, and two area's temperature are 220 DEG C, three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature Spend for 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare PC/AES alloys.
Comparative example 2
A kind of PC/AES alloys, it is following (mass parts) that it is formulated composition:
The compatilizer is MAH-g-EPDM, and wherein maleic anhydride grafting ratio is more than 0.8%.The antioxidant be 4,4 '- Thiobis (the 6- tert-butyl group -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE), and the lubricant is ethylene bis stearamide.
This comparative example PC/AES alloy preparation methods are as follows:Precise above each component raw material, by original after being well mixed Material puts into double screw extruder dog-house, and the temperature in each area of double screw extruder is:One area's temperature is 230 DEG C, and two area's temperature are 230 DEG C, three area's temperature are 240 DEG C, and four area's temperature are 240 DEG C, and five area's temperature are 245 DEG C, and six area's temperature are 245 DEG C, seven area's temperature Spend for 245 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare PC/AES alloys.
Comparative example 3
A kind of PC/AES alloys, it is following (mass parts) that it is formulated composition:
The compatilizer is SMA, and wherein maleic anhydride grafting ratio is 18%.The antioxidant is 4,4 '-thiobis (uncle 6- Butyl -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE), and lubricant is the double stearic amides of vinyl.
The fire retardant is quaternary ammonium salt built up silane couple modified montmorillonoid, and its preparation method is:
1) sodium-based montmorillonite (cation exchange capacity is 100mmol/100g) is scattered in deionized water, centrifugation is removed Impurity, pH=6 is adjusted with HCl solution, is finally existed with deionized water rinsing to without Cl-, is subsequently added 1.1 times of cation exchanges The Cetyltrimethylammonium bromide of content carries out cation exchange, the vigorous reaction under the conditions of 60-80 DEG C to sodium-based montmorillonite 4h, then obtains quaternary ammonium salt modified montmorillonoid through filtering, deionized water washing, drying process;
2) by step 1) gained quaternary ammonium salt modified montmorillonoid be dispersed in water, adjust pH=4, be subsequently added 1.1 times of sun from The silane coupler KH108 of sub- exchange capacity vigorous reaction 4h under the conditions of 60-80 DEG C, are washed through filtering, deionized water, then through dry It is dry to obtain quaternary ammonium salt built up silane couple modified montmorillonoid.
This comparative example PC/AES alloy preparation methods are as follows:Precise above each component raw material, by original after being well mixed Material puts into double screw extruder dog-house, and the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, and two area's temperature are 220 DEG C, three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature Spend for 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare PC/AES alloys.
Embodiment 1
A kind of halogen-free flameproof strengthens PC/AES alloys, and it is following (mass parts) that it is formulated composition:
The compatilizer is MAH-g-EPDM, and maleic anhydride grafting ratio is more than 0.8%.The antioxidant be 4,4 '-it is thio Double (the 6- tert-butyl group -3- methylphenols), anti-dripping agent is polytetrafluoroethylene (PTFE).The lubricant is ethylene bis stearamide.
The Halogen compound flame retardant is changed by bisphenol-A-bis- (diphenyl phosphates) (BDP) with quaternary ammonium salt built up silane couple Property montmorillonite is mixed to get, wherein 12 parts of BDP, 4 parts of quaternary ammonium salt built up silane couple modified montmorillonoid.
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is identical with comparative example 3.
The present embodiment halogen-free flameproof enhancing PC/AES alloy preparation methods are as follows:Precise above each component raw material, is mixed Raw material is put into double screw extruder dog-house after closing uniformly, the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, two area's temperature are 220 DEG C, and three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature are 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare Phosphorus-silicon collaboration halogen-free flameproof enhancing PC/AES alloys.
Embodiment 2
A kind of halogen-free flameproof strengthens PC/AES alloys, and it is following (mass parts) that it is formulated composition:
The compatilizer is SMA, and maleic anhydride grafting ratio is 18%.The antioxidant is double (2,4- di-tert-butyl-phenyls) Pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE), and lubricant is the double stearic amides of vinyl.
The Halogen compound flame retardant is changed by bisphenol-A-bis- (diphenyl phosphates) (BDP) with quaternary ammonium salt built up silane couple Property montmorillonite is mixed to get, wherein 16 parts of BDP, 2 parts of quaternary ammonium salt built up silane couple modified montmorillonoid.
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is identical with comparative example 3.
The present embodiment halogen-free flameproof enhancing PC/AES alloy preparation methods are as follows:Precise above each component raw material, is mixed Raw material is put into double screw extruder dog-house after closing uniformly, the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, two area's temperature are 220 DEG C, and three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature are 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare Phosphorus-silicon collaboration halogen-free flameproof enhancing PC/AES alloys.
Embodiment 3
A kind of halogen-free flameproof strengthens PC/AES alloys, and it is following (mass parts) that it is formulated composition:
The compatilizer is MAH-g-EPDM, and maleic anhydride grafting ratio is more than 0.8%.The antioxidant is double (2,4- bis- Tert-butyl-phenyl) pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE), and the lubricant is ethylene stearic bicine diester Amine.
The Halogen compound flame retardant is changed by bisphenol-A-bis- (diphenyl phosphates) (BDP) with quaternary ammonium salt built up silane couple Property montmorillonite is mixed to get, wherein 14 parts of BDP, 4 parts of quaternary ammonium salt built up silane couple modified montmorillonoid.
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is identical with comparative example 3.
The present embodiment halogen-free flameproof enhancing PC/AES alloy preparation technologies are as follows:Precise above each component raw material, is mixed Raw material is put into double screw extruder dog-house after closing uniformly, the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, two area's temperature are 220 DEG C, and three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature are 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare Phosphorus-silicon collaboration halogen-free flameproof enhancing PC/AES alloys.
Embodiment 4
A kind of halogen-free flameproof strengthens PC/AES alloys, and it is following (mass parts) that it is formulated composition:
The compatilizer is SMA, and maleic anhydride grafting ratio is 18%.The antioxidant is double (2,4- di-tert-butyl-phenyls) Pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE), and lubricant is the double stearic amides of vinyl.
The Halogen compound flame retardant is changed by bisphenol-A-bis- (diphenyl phosphates) (BDP) with quaternary ammonium salt built up silane couple Property montmorillonite is mixed to get, wherein 18 parts of BDP, 2 parts of quaternary ammonium salt built up silane couple modified montmorillonoid.
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is identical with comparative example 3.
The present embodiment halogen-free flameproof enhancing PC/AES alloy preparation technologies are as follows:Precise above each component raw material, is mixed Raw material is put into double screw extruder dog-house after closing uniformly, the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, two area's temperature are 220 DEG C, and three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature are 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare Phosphorus-silicon collaboration halogen-free flameproof enhancing PC/AES alloys.
Embodiment 5
A kind of halogen-free flameproof strengthens PC/AES alloys, and it is following (mass parts) that it is formulated composition:
The compatilizer is MAH-g-EPDM, and maleic anhydride grafting ratio is more than 0.8%.The antioxidant is double (2,4- bis- Tert-butyl-phenyl) pentaerythritol diphosphites, anti-dripping agent is polytetrafluoroethylene (PTFE), and the lubricant is ethylene stearic bicine diester Amine.
The Halogen compound flame retardant is changed by bisphenol-A-bis- (diphenyl phosphates) (BDP) with quaternary ammonium salt built up silane couple Property montmorillonite is mixed to get, wherein 16 parts of BDP, 4 parts of quaternary ammonium salt built up silane couple modified montmorillonoid.
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is identical with comparative example 3.
The present embodiment halogen-free flameproof enhancing PC/AES alloy preparation technologies are as follows:Precise above each component raw material, is mixed Raw material is put into double screw extruder dog-house after closing uniformly, the temperature in each area of double screw extruder is:One area's temperature is 220 DEG C, two area's temperature are 220 DEG C, and three area's temperature are 230 DEG C, and four area's temperature are 230 DEG C, and five area's temperature are 235 DEG C, and six area's temperature are 240 DEG C, seven area's temperature are 240 DEG C, control the rotating speed of double screw extruder to be extruded and granulated for 100r/min, prepare Phosphorus-silicon collaboration halogen-free flameproof enhancing PC/AES alloys.
Embodiment 6
The performance of halogen-free flameproof enhancing PC/AES alloys obtained by comparative example 1-3 and embodiment 1-5 is tested, tested As a result it is as shown in table 1:
Table 1
As it can be seen from table 1 with the increase of flame retardant agent content, the limited oxygen index of gained PC/AES alloys gradually rises (and when the addition of compound flame retardant is 18 parts, wherein BDP is 14 with organic quaternary ammonium salt modified montmorillonoid quality parts ratio:4 When, flame retardant effect is best), fire-retardant rank is reached more than the V-0 levels of UL94 standards, and carbon left is obviously improved.The present invention Tensile strength, bending strength, impact strength etc. of halogen-free flameproof enhancing PC/AES alloy materials reach PC/AES alloys Use requirement, with very high practical value.
Obviously, above-described embodiment is used for the purpose of clearly illustrating made example, and the not limitation to embodiment. For those of ordinary skill in the field, other various forms of changes can also be made on the basis of the above description Or change.There is no need and unable to all embodiments and with exhaustion.And the obvious change therefore amplified or Change within still in the protection domain of the invention.

Claims (8)

1. a kind of halogen-free flameproof strengthens PC/AES alloys, it is characterised in that the alloy is made up of the raw material of following mass parts:PC 55-65 parts, 10-25 parts of AES, 4-12 parts of compatilizer, 16-20 parts of Halogen compound flame retardant, 0.5-1 parts of anti-dripping agent, lubricant 0.1-0.5 parts, 0.1-0.5 parts of antioxidant;
The Halogen compound flame retardant is by bisphenol-A-bis- (diphenyl phosphates) and quaternary ammonium salt built up silane couple modified montmorillonoid 3-9 in mass ratio:1 is mixed to get;
The preparation method of the quaternary ammonium salt built up silane couple modified montmorillonoid is:
1) sodium-based montmorillonite is scattered in deionized water, centrifugation go the removal of impurity, with HCl solution adjust pH=6, finally spend from Sub- water is rinsed to without Cl-In the presence of the Cetyltrimethylammonium bromide for being subsequently added 1.1 times of cation exchange contents is covered to sodium base De- soil carries out cation exchange, the vigorous reaction 4h under the conditions of 60-80 DEG C, then through filtering, deionized water washing, drying process Obtain quaternary ammonium salt modified montmorillonoid;
2) by step 1) gained quaternary ammonium salt modified montmorillonoid is dispersed in water, adjusts pH=4, be subsequently added the friendship of 1.1 times of cations The silane coupler for the amount of changing vigorous reaction 4h under the conditions of 60-80 DEG C, washs through filtering, deionized water, is drying to obtain Quaternary ammonium salt built up silane couple modified montmorillonoid.
2. halogen-free flameproof according to claim 1 strengthens PC/AES alloys, it is characterised in that the compatilizer is benzene second Alkene-maleic anhydride graft copolymer or ethylene propylene diene rubber-maleic anhydride graft copolymer.
3. halogen-free flameproof according to claim 1 strengthens PC/AES alloys, it is characterised in that the anti-dripping agent is poly- four PVF.
4. halogen-free flameproof according to claim 1 strengthens PC/AES alloys, it is characterised in that the lubricant is vinyl Double stearic amides or ethylene bis stearamide.
5. halogen-free flameproof according to claim 1 strengthens PC/AES alloys, it is characterised in that the antioxidant is 4,4 '- Thiobis (the 6- tert-butyl group -3- methylphenols) or double (2,4- di-tert-butyl-phenyls) pentaerythritol diphosphites.
6. halogen-free flameproof according to claim 1 strengthens PC/AES alloys, it is characterised in that the silane coupler is KH108, the cation exchange capacity of the sodium-based montmorillonite is 100mmol/100g.
7. a kind of strengthen the preparation method of PC/AES alloys according to any described halogen-free flameproofs of claim 1-6, its feature exists In:Raw material is weighed by proportioning, raw material is put into double screw extruder dog-house, turn of control double screw extruder after being well mixed Speed is extruded and granulated for 100-200r/min, prepares halogen-free flameproof enhancing PC/AES alloys.
8. preparation method according to claim 7, it is characterised in that the temperature in each area of double screw extruder is:One area Temperature is 220-230 DEG C, and two area's temperature are 220-230 DEG C, and three area's temperature are 230-240 DEG C, and four area's temperature are 230-240 DEG C, Five area's temperature are 235-245 DEG C, and six area's temperature are 235-245 DEG C, and seven area's temperature are 235-245 DEG C.
CN201710375320.9A 2017-05-24 2017-05-24 A kind of halogen-free flameproof enhancing PC/AES alloys and preparation method thereof Pending CN107189393A (en)

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CN110408154A (en) * 2019-08-19 2019-11-05 南京天诗实验微粉有限公司 A kind of modified ptfe anti-dripping agent and preparation method thereof
CN110484123A (en) * 2019-09-16 2019-11-22 巩义市弘盛管道设备有限公司 A kind of antibacterial mould-proof-type monocomponent polyurethane building water-proof paint and preparation method thereof

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CN103740084A (en) * 2013-12-27 2014-04-23 安徽科聚新材料有限公司 PC (polycarbonate)/AES (sodium alcohol ether sulphate) alloy material and preparation method thereof
CN106009581A (en) * 2016-05-24 2016-10-12 武汉理工大学 Intumescent flame retardant enhanced ASA/PC (acrylonitrile styrene acrylate/poly carbonate) alloy and preparation method thereof

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CN103740084A (en) * 2013-12-27 2014-04-23 安徽科聚新材料有限公司 PC (polycarbonate)/AES (sodium alcohol ether sulphate) alloy material and preparation method thereof
CN106009581A (en) * 2016-05-24 2016-10-12 武汉理工大学 Intumescent flame retardant enhanced ASA/PC (acrylonitrile styrene acrylate/poly carbonate) alloy and preparation method thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110408154A (en) * 2019-08-19 2019-11-05 南京天诗实验微粉有限公司 A kind of modified ptfe anti-dripping agent and preparation method thereof
CN110484123A (en) * 2019-09-16 2019-11-22 巩义市弘盛管道设备有限公司 A kind of antibacterial mould-proof-type monocomponent polyurethane building water-proof paint and preparation method thereof

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