CN101942174B - Halogen-free flame-retardant ABS/PA6 alloy material and preparation method thereof - Google Patents
Halogen-free flame-retardant ABS/PA6 alloy material and preparation method thereof Download PDFInfo
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 122
- 239000000956 alloy Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims abstract description 80
- 229920005989 resin Polymers 0.000 claims abstract description 40
- 239000011347 resin Substances 0.000 claims abstract description 40
- 239000002270 dispersing agent Substances 0.000 claims abstract description 36
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002156 mixing Methods 0.000 claims abstract description 16
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 7
- 150000002367 halogens Chemical class 0.000 claims abstract description 7
- 239000012745 toughening agent Substances 0.000 claims description 35
- 239000003112 inhibitor Substances 0.000 claims description 34
- 238000005461 lubrication Methods 0.000 claims description 34
- DXZMANYCMVCPIM-UHFFFAOYSA-L zinc;diethylphosphinate Chemical compound [Zn+2].CCP([O-])(=O)CC.CCP([O-])(=O)CC DXZMANYCMVCPIM-UHFFFAOYSA-L 0.000 claims description 32
- 230000003647 oxidation Effects 0.000 claims description 30
- 238000007254 oxidation reaction Methods 0.000 claims description 30
- 239000000203 mixture Substances 0.000 claims description 29
- 238000005303 weighing Methods 0.000 claims description 29
- -1 fatty acid acyl compounds Chemical class 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 13
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 12
- 239000000194 fatty acid Substances 0.000 claims description 12
- 229930195729 fatty acid Natural products 0.000 claims description 12
- XZTOTRSSGPPNTB-UHFFFAOYSA-N phosphono dihydrogen phosphate;1,3,5-triazine-2,4,6-triamine Chemical compound NC1=NC(N)=NC(N)=N1.OP(O)(=O)OP(O)(O)=O XZTOTRSSGPPNTB-UHFFFAOYSA-N 0.000 claims description 11
- AZAXDEGLWYZTDO-UHFFFAOYSA-N 3-(benzenesulfonyl)benzenesulfonic acid;potassium Chemical group [K].OS(=O)(=O)C1=CC=CC(S(=O)(=O)C=2C=CC=CC=2)=C1 AZAXDEGLWYZTDO-UHFFFAOYSA-N 0.000 claims description 10
- 239000002131 composite material Substances 0.000 claims description 10
- UVAUHTUDFIJIDS-UHFFFAOYSA-N FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F Chemical compound FC(C(C(C(F)(F)F)(F)F)(F)F)([K])F UVAUHTUDFIJIDS-UHFFFAOYSA-N 0.000 claims description 9
- 229920000877 Melamine resin Polymers 0.000 claims description 9
- 229920000388 Polyphosphate Polymers 0.000 claims description 9
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000003016 phosphoric acids Chemical class 0.000 claims description 9
- 239000001205 polyphosphate Substances 0.000 claims description 9
- 235000011176 polyphosphates Nutrition 0.000 claims description 9
- AFTLIIOXEHXDOZ-UHFFFAOYSA-N buta-1,3-diene;furan-2,5-dione;styrene Chemical compound C=CC=C.O=C1OC(=O)C=C1.C=CC1=CC=CC=C1 AFTLIIOXEHXDOZ-UHFFFAOYSA-N 0.000 claims description 8
- 229920001577 copolymer Polymers 0.000 claims description 8
- 239000000314 lubricant Substances 0.000 claims description 8
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims description 7
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 7
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 3
- 238000005469 granulation Methods 0.000 claims description 3
- 230000003179 granulation Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 abstract description 10
- 239000004033 plastic Substances 0.000 abstract description 10
- 229910045601 alloy Inorganic materials 0.000 abstract description 7
- 239000003963 antioxidant agent Substances 0.000 abstract 2
- 230000003078 antioxidant effect Effects 0.000 abstract 2
- 230000001050 lubricating effect Effects 0.000 abstract 2
- 229910019142 PO4 Inorganic materials 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 abstract 1
- 239000010452 phosphate Substances 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 7
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- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000012757 flame retardant agent Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 206010010071 Coma Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical group OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004500 asepsis Methods 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
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- 231100000419 toxicity Toxicity 0.000 description 1
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Classifications
-
- B29C47/92—
Abstract
The invention discloses a halogen-free flame-retardant ABS/PA6 alloy material and a preparation method thereof. The alloy material is a blended system consisting of a plastic alloy which is formed by blending ABS resin and PA6 resin and additives which are blended in the plastic alloy, wherein the additives comprise flame retardants, a compatible flexibilizer, a lubricating dispersant and an antioxidant; the flame retardants are melamine cyanurate, phosphate and sulfonate; and the alloy material comprises the following components in part by weight: 50 to 80 parts of ABS resin, 20 to 50 parts of PA6 resin, 5 to 25 parts of three flame retardants in total, 5 to 20 parts of compatible flexibilizer, 0.5 to 2.0 parts of lubricating dispersant, and 0.1 to 0.6 part of antioxidant. The alloy material in the invention does not contain any halogen and is harmless to environment; and the plastic alloy cannot be darkened and keeps the original color, so that the application field of the alloy plastic cannot be limited.
Description
Technical field
The present invention relates to a kind of polymer composite and preparation method thereof, be specifically related to a kind of halogen-free flame retardant ABS/PA6 alloy material and preparation method thereof.
Background technology
China is maximum in the world ABS resin country of consumption, and present year consumption is near the summation of the U.S. with Japan.Product mainly concentrates on electronics, the electrical accessorie.Wherein electricrefrigerator, televisor, phone, modern handle official bussiness articles for use and other small household appliances etc. account for about 80% of ABS resin aggregate consumption, and toy and auto parts machinery then respectively account for about 10% of ABS resin aggregate consumption.ABS resin itself belongs to inflammable, combustible matl, and oxygen index is 18.8%～20.2%, and HRR is high when burning; Calorific value is big; Flame propagation speed is difficult for extinguishing, and also produces thick smoke sometimes and toxic gas; This not only can cause serious property damage, brings very big threat also can for human life security and living environment.
And; Along with people's is to the pay attention to day by day of health, environment and ecological protection; Flame retardant of plastic standard and environmental protection standard be increasingly stringent also; Material Burning Effluents Toxicity and smoking property problem more and more come into one's own, and require plastic material or goods both to have good flame retardancy, lowly again poison and hang down being fuming.Like the TCO-99 of Sweden and the requirement of the Ecolable-9 in Northern Europe (white swan) environmental mark, the computingmachine material can not adopt PVC RESINS and brominated flame-retardant.The blue sky of Germany makes sign (BlueAngel) also require stamping machine and duplicating machine sheating material not halogen-containing.The EbobelEU-99 in Europe requires not contain halogenated flame retardant in the case of computer plastics.The particularly WEEE instruction of each member states's announcement of European Union in 2003 and RoHS instruction.
Chinese patent document CN101092501A (application number is 200710074687.3) discloses a kind of PA6/ABS alloy material and preparation method thereof; This alloy material comprises 20%～65% PA6; 10%～70% ABS, 0.1%～20% compatilizer, 5%～30% composite flame-retardant agent; 0.1%～0.6% lubricant, 0.1%～1.2% oxidation inhibitor.Wherein composite flame-retardant agent is by brominated flame-retardant with Antimony Trioxide: 99.5Min is composite forms, and lubricant is the ultra-high molecular weight ZGK 5.The deficiency of this alloy material just is: owing to used brominated flame-retardant; The plastic components that causes adopting this alloy material to produce produces bromize hydrogen gas poisonous and excitatory in combustion processes; Be prone to cause secondary disaster (promptly cause the victim to suffocate and go into a coma even death), this type of brominated alloy fire retardant material is forbidden by many countries.
Summary of the invention
One of the object of the invention is to solve the problems of the technologies described above, and a kind of halogen-free flame retardant ABS/PA6 alloy material is provided.The comprehensive mechanical strength height of this halogen-free fire retardant alloy material, good flame resistance, fluidity of molten is good, production cost is low, environment-protecting asepsis.
Another object of the present invention then provides the preparation method of above-mentioned alloy material.
The technical scheme that realizes first kind of purpose of the present invention is: a kind of halogen-free flame retardant ABS/PA6 alloy material, its state are particulate state; ABS resin and the polyblend of PA6 resin and the co-mixing system that the additive of blend in this polyblend formed that this particulate state halogen-free flame retardant ABS/PA6 alloy material is formed by blend; Described additive comprises fire retardant, compatible toughening agents, lubrication dispersing agent and oxidation inhibitor; Above-mentioned fire retardant has three kinds, and first kind of fire retardant is that melamine cyanurate, second kind of fire retardant are phosphoric acid salt, and the third fire retardant is a sulphonate, and three kinds of fire retardants form the Halogen composite flame retardant system in co-mixing system; Above-mentioned each composition content by weight is following: 50～80 parts of ABS resins, 20～50 parts of PA6 resins, all 5～25 parts of three kinds of fire retardants, 5～20 parts of compatible toughening agents, 0.5～2.0 part of lubrication dispersing agent, 0.1～0.6 part in oxidation inhibitor.The weight ratio of said first kind of fire retardant, second kind of fire retardant and the third fire retardant is (40～60): (40～60): (0.2～0.6).
Described second kind of fire retardant phosphoric acid salt is melamine pyrophosphate salt or melamine polyphosphate; Described the third fire retardant sulphonate is 3-benzenesulfonyl Phenylsulfonic acid potassium or perfluoro butyl potassium sulfonate.
Described compatible toughening agents is styrene butadiene-maleic anhydride multiple copolymer.
Described lubrication dispersing agent is an ethylenebis fatty acid acyl compounds.
The commercial disignation that described ethylenebis fatty acid acyl compounds derives from the production of Suzhou Xingtai state photochemistry auxiliary agent ltd is the powdered bright lubricant of TAS-2A.
Described oxidation inhibitor chemistry four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester by name derives from the powdered antioxidant 1010.
The technical scheme that realizes second kind of purpose of the present invention is: the preparation method of a kind of halogen-free flame retardant ABS/PA6 alloy material; Have following steps: 1. with particulate state ABS resin and particulate state PA6 resin respectively under 80 ℃～90 ℃ temperature in convection oven dry 3h～5h; Take by weighing 50～80 parts of ABS resins after the taking-up; And 20～50 parts of PA6 resins, for use.2. the proportioning according to following weight part takes by weighing first kind of fire retardant melamine cyanurate of powdery, second kind of fire retardant phosphoric acid salt of powdery, the third fire retardant sulphonate of powdery, particulate state compatible toughening agents, powdery lubrication dispersing agent and powdery oxidation inhibitor, and is for use; Described particulate state compatible toughening agents is particulate state styrene butadiene-maleic anhydride multiple copolymer; The powdery lubrication dispersing agent is a powdery ethylenebis fatty acid acyl compounds; Described powdery oxidation inhibitor is powdered four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester; Second kind of fire retardant phosphoric acid salt of described powdery is powdery melamine pyrophosphate salt or powdery melamine polyphosphate; The third fire retardant sulphonate of powdery is powdery 3-benzenesulfonyl Phenylsulfonic acid potassium or powdery perfluoro butyl potassium sulfonate; The weight part proportioning of each composition is: all 5～25 parts of three kinds of fire retardants, 5～20 parts of compatible toughening agents, 0.5～2.0 part of lubrication dispersing agent, 0.1～0.6 part in oxidation inhibitor; The weight ratio of first kind of fire retardant, second kind of fire retardant and the third fire retardant is (40～60): (40～60): (0.2～0.6).3. it is to mix in 800 rev/mins～1000 rev/mins the high-speed mixer that compatible toughening agents that 2. ABS resin that 1. step is taken by weighing and PA6 resin and step take by weighing and lubrication dispersing agent are poured rotating speed into; Make temperature of charge be increased to 80 ℃～90 ℃ until mixing the heat of friction that is produced, and make lubrication dispersing agent fusing when being dispersed in ABS resin, PA6 resin and compatible toughening agents surface adhere to ABS resin, PA6 resin and compatible toughening agents surface; It is to continue in 800 rev/mins～1000 rev/mins high-speed mixers to mix that the first kind of fire retardant that then 2. step is taken by weighing, second kind of fire retardant, the third fire retardant and oxidation inhibitor are poured rotating speed into; In the presence of lubrication dispersing agent; Make each fire retardant and oxidation inhibitor evenly adhere to ABS resin, PA6 resin and compatible toughening agents surface; Discharging after the heat of friction that mixing is produced makes material temperature reach 100 ℃～120 ℃ is sent into mixture then and under agitation is cooled to 30 ℃～50 ℃ in the cooling and stirring device.4. cooled mixture is sent in the twin screw extruder that is heated to design temperature; Mixture is in the process process of twin screw extruder; Be heated on the one hand and soften and become molten state gradually; The further uniform mixing of various at the volley on the other hand compositions is extruded as billot by die head at last, and the extrusion die temperature that sets is 225 ℃ to 235 ℃; The billot of being extruded gets into the dicing machine granulation through tank cooling, traction, promptly obtains granular halogen-free flame retardant ABS/PA6 alloy material.
The powdery oxidation inhibitor of above-mentioned steps in 2. is the powdered antioxidant 1010.
The powdery ethylenebis fatty acid acyl compounds of above-mentioned steps in 2. is that the powdered commercial disignation that Suzhou Xingtai state photochemistry auxiliary agent ltd produces is the bright lubricant of TAS-2A.
Above-mentioned steps 4. in, twin screw extruder is divided into 4 heating zone and extrusion die according to the precedence of material process, the Heating temperature of each heating zone that sets is followed successively by: T
1=160 ℃～170 ℃, T
2=200 ℃～210 ℃, T
3=220 ℃～235 ℃, T
4=235 ℃.
The positively effect that the present invention has: (1) halogen-free flame retardant ABS of the present invention/PA6 alloy material is when forming co-mixing system; Make melamine cyanurate, phosphoric acid salt and sulphonate form the Halogen composite flame retardant system therein simultaneously; Make alloy material not halogen-containing on the one hand, environmental sound; Can not make darkening of alloy material on the other hand, still be true qualities, can not limit the Application Areas of alloy material.(2) preparation method of alloy material of the present invention earlier carries out forced air drying with ABS resin and PA6 resin, can avoid like this ABS resin and PA6 resin with moisture the preparation and the application of alloy material caused detrimentally affect.(3) lubrication dispersing agent of the present invention's selection is preferably ethylenebis fatty acid acyl compounds (specifically can select the TAS-2A bright lubricant); It can effectively reduce the melt flow resistance of ABS/PA6 polyblend; Reduce the processor moment of torsion; Help Halogenless composite fire retardant and be dispersed in the ABS/PA6 polyblend, improve the flame retardant resistance and the material mechanical performance of this alloy plastic, can also effectively improve surface gloss.And when preparation mixes lubrication dispersing agent earlier with the pellet of ABS resin and PA6 resin; Lubrication dispersing agent is melted be dispersed in resin surface; Thereby help Halogenless composite fire retardant and evenly adhere to the resin granular material surface; Thereby when ABS resin and PA6 resin granular material heating and melting, each component is uniformly dispersed each other, helps the alloy material overall performance homogeneous of final gained.(4) the present invention uses styrene butadiene-maleic anhydride multiple copolymer to make the compatible toughening agents of ABS/PA6 alloy, can improve the consistency between the ABS/PA6 interface effectively, improves the comprehensive mechanical property of halogen-free flame retardant ABS/PA6 alloy material.
Embodiment
(embodiment 1)
The halogen-free flame retardant ABS of present embodiment/PA6 alloy material is a particulate state.ABS resin and the polyblend of PA6 resin and the co-mixing system that the additive of blend in this polyblend formed that this particulate state halogen-free flame retardant ABS/PA6 alloy material is formed by blend.Described additive comprises fire retardant, compatible toughening agents, lubrication dispersing agent and oxidation inhibitor.Above-mentioned fire retardant has three kinds, and first kind of fire retardant is melamine cyanurate, and second kind of fire retardant is phosphoric acid salt, and the third fire retardant is a sulphonate, and these three kinds of fire retardants form the Halogen composite flame retardant system in co-mixing system.
Above-mentioned second kind of fire retardant phosphoric acid salt is the melamine pyrophosphate salt; The third fire retardant sulphonate is 3-benzenesulfonyl Phenylsulfonic acid potassium; Compatible toughening agents is styrene butadiene-maleic anhydride multiple copolymer; Lubrication dispersing agent is an ethylenebis fatty acid acyl compounds; Oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester.
In particulate state halogen-free flame retardant ABS/PA6 alloy material of 100kg, the content of above-mentioned each composition is following:
ABS resin 55kg; PA6 resin 20kg; Melamine cyanurate 7.47kg, melamine pyrophosphate salt (also claiming melamine pyrophosphate) 7.47kg, 3-benzenesulfonyl Phenylsulfonic acid potassium 0.06kg, styrene butadiene-maleic anhydride multiple copolymer 8kg; Ethylenebis fatty acid acyl compounds 1.5kg, four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester 0.5kg.
The preparation method of above-mentioned particulate state halogen-free flame retardant ABS/PA6 alloy material is following:
1. take by weighing 110kg particulate state ABS resin and 40kg particulate state PA6 resin respectively under 85 ℃ temperature in convection oven dry 4h, take out the ABS resin that takes by weighing 55kg more respectively, and the PA6 resin of 20kg, for use.
Above-mentioned ABS resin is that the strange beautiful commercial disignation of producing in Taiwan is 747 ABS resin; Above-mentioned PA6 resin is that the silent commercial disignation of producing in German road is 28 PA6 resin.2. take by weighing powdery melamine cyanurate 7.47kg, powdery melamine pyrophosphate salt 7.47kg, powdery 3-benzenesulfonyl Phenylsulfonic acid potassium 0.06 kg, particulate state compatible toughening agents 8kg, powdery lubrication dispersing agent 1.5kg and powdery oxidation inhibitor 0.5kg, for use.
The weight ratio of above-mentioned three kinds of powdery combustion inhibitors is 49.8: 49.8: 0.4.First kind of fire retardant powdery melamine cyanurate derives from Shenzhen Hong Taiji Industrial Co., Ltd.; Second kind of fire retardant powdery melamine pyrophosphate salt derives from the Jinan rising sun in morning chemical industry ltd, and the third fire retardant 3-benzenesulfonyl Phenylsulfonic acid potassium derives from Dow corning company.
Above-mentioned powdery compatible toughening agents is styrene butadiene-maleic anhydride multiple copolymer, and the commercial disignation that derives from the chemical ltd of the liter production of Shanghai day is the particulate state compatible toughening agents of MPC 1545R.
Above-mentioned powdery lubrication dispersing agent is an ethylenebis fatty acid acyl compounds, and the powdered commercial disignation that derives from the production of Suzhou Xingtai state photochemistry auxiliary agent ltd is the bright lubricant of TAS-2A.
Powdery oxidation inhibitor is four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester, derives from the powdered antioxidant 1010 that Switzerland's vapour crust is produced.
3. it is to mix in 900 rev/mins the high-speed mixer that compatible toughening agents that 2. ABS resin that takes by weighing that earlier 1. step is taken by weighing and PA6 resin and step take by weighing and lubrication dispersing agent TAS-2A pour rotating speed into; Make temperature of charge be increased to 80 ℃ until mixing the heat of friction produced, and make lubrication dispersing agent melt and be dispersed in ABS resin particle, PA6 resin particle and compatible toughening agents particle surface.It is to continue in 900 rev/mins the high-speed mixer to mix that the fire retardant melamine cyanurate that then 2. step is taken by weighing, fire retardant phosphoric acid salt, fire retardant sulphonate and antioxidant 1010 are poured rotating speed into; In the presence of lubrication dispersing agent; Make each fire retardant and oxidation inhibitor evenly adhere to ABS resin particle, PA6 resin particle and compatible toughening agents particle surface; Make until the heat of friction that is produced and mixture to be sent to just discharging after material temperature reaches 110 ℃ under agitation to be cooled to 50 ℃ in the cooling and stirring device then.
4. cooled mixture is sent in the twin screw extruder that is heated to design temperature; Mixture is in the process process of twin screw extruder; Be heated on the one hand and soften and become molten state gradually; The further uniform mixing of various at the volley on the other hand compositions is extruded as billot by die head at last, the extrusion die temperature T that sets
Mould=230 ℃; The billot of being extruded gets into the dicing machine granulation through tank cooling, traction, and (particle diameter is about 2mm～3mm), promptly obtain the pellet of halogen-free flame retardant ABS/PA6 alloy material.
Twin screw extruder is divided into 4 heating zone and extrusion die according to the precedence of material process, and the Heating temperature of each heating zone that sets is followed successively by: with the depanning heating zone, the temperature in each district is followed successively by: the first Heating Zone Temperature T
1=160 ℃～170 ℃, the second Heating Zone Temperature T
2=200 ℃～210 ℃, the 3rd Heating Zone Temperature T
3=220 ℃～235 ℃, the 4th Heating Zone Temperature T
4=235 ℃.
(embodiment 2)
The rest part of present embodiment is identical with embodiment 1, and difference is: in halogen-free flame retardant ABS/PA6 alloy material of 100kg, each composition and corresponding content are following:
ABS resin 50kg, PA6 resin 24kg, first kind of fire retardant melamine cyanurate 7.952kg; Second kind of fire retardant melamine pyrophosphate salt 7.952kg, the third fire retardant powdery perfluoro butyl potassium sulfonate 0.096kg, compatible toughening agents 8kg; Lubrication dispersing agent 1.5kg, oxidation inhibitor 0.5kg.
The weight ratio of above-mentioned three kinds of powdery combustion inhibitors is 49.7: 49.7: 0.6.The third fire retardant powdery perfluoro butyl potassium sulfonate derives from Weifang Yucheng Chemical Co., Ltd..
Corresponding, when preparation above-mentioned halogen-free flame retardant ABS/PA6 alloy material, step 1. in, the ABS resin that dry back is taken by weighing is 50kg, the PA6 resin that is taken by weighing is 24kg.
Step 2. in; The weight of the various raw materials that taken by weighing is corresponding with the content of above-mentioned each composition; Also promptly take by weighing the melamine cyanurate of 7.952kg, the melamine pyrophosphate salt of 7.952kg, the perfluoro butyl potassium sulfonate of 0.096kg, the compatible toughening agents of 8kg, the lubrication dispersing agent of 1.5kg and the oxidation inhibitor of 0.5kg, for use.
(embodiment 3)
The rest part of present embodiment is identical with embodiment 1, and difference is: in halogen-free flame retardant ABS/PA6 alloy material of 100kg, each composition and corresponding content are following:
ABS resin 52kg; First kind of fire retardant melamine cyanurate of PA6 resin 21kg 7.485kg; Second kind of fire retardant melamine polyphosphate 7.485kg, the third fire retardant 3-benzenesulfonyl Phenylsulfonic acid potassium 0.03kg, compatible toughening agents 10kg lubrication dispersing agent 1.5kg oxidation inhibitor 0.5kg.
The weight ratio of above-mentioned three kinds of powdery combustion inhibitors is 49.9: 49.9: 0.2.Second kind of fire retardant melamine polyphosphate derives from Shanghai Mei Laipo chemical materials Science and Technology Ltd..
Corresponding, when preparation above-mentioned halogen-free flame retardant ABS/PA6 alloy material, step 1. in, the ABS resin that dry back is taken by weighing is 52kg, the PA6 resin that is taken by weighing is 21kg.
Step 2. in; The weight of the various raw materials that taken by weighing is corresponding with the content of above-mentioned each composition; Also promptly take by weighing the melamine cyanurate of 7.485kg, the melamine polyphosphate of 7.485kg, the 3-benzenesulfonyl Phenylsulfonic acid potassium of 0.03kg, the compatible toughening agents of 10kg, the lubrication dispersing agent of 1.5kg and the oxidation inhibitor of 0.5kg, for use.
(embodiment 4)
The rest part of present embodiment is identical with embodiment 1, and difference is: in halogen-free flame retardant ABS/PA6 alloy material of 100kg, each composition and corresponding content are following:
ABS resin 51kg, PA6 resin 22kg, wherein first kind of fire retardant melamine cyanurate 8.964kg; Second kind of fire retardant melamine polyphosphate 8.964kg, the third fire retardant perfluoro butyl potassium sulfonate 0.072kg, compatible toughening agents 7kg; Lubrication dispersing agent 1.5kg, oxidation inhibitor 0.5kg.
The weight ratio of above-mentioned three kinds of powdery combustion inhibitors is 49.8: 49.8: 0.4.
Corresponding, when preparation above-mentioned halogen-free flame retardant ABS/PA6 alloy material, step 1. in, the ABS resin that dry back is taken by weighing is 51kg, the PA6 resin that is taken by weighing is 22kg.
Step 2. in; The weight of the various raw materials that taken by weighing is corresponding with the content of above-mentioned each composition; Also promptly take by weighing the melamine cyanurate of 8.964kg, the melamine polyphosphate of 8.964kg, the perfluoro butyl potassium sulfonate of 0.072kg, the compatible toughening agents of 7kg, the lubrication dispersing agent of 1.5kg and the oxidation inhibitor of 0.5kg, for use.
(application examples)
Particulate state halogen-free flame retardant ABS/PA6 alloy material that embodiment 1～embodiment 4 is made joins connector and the injection of plastic standard test specimen of producing electronic apparatus in the injection moulding machine respectively; And by national standard to this standard test specimen make an experiment the test its thermal property, mechanical property and flame retardant resistance, test result is seen table 1.
Table 1
| Test performance | Performance index | Testing standard | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Non-notch resistance to impact shock/KJm -2 | ﹥7.0 | GB/T1043-93 | 7.8 | ?8.2 | 8.1 | 8.5 |
| Flexural strength/Mpa | ﹥60.0 | GB/T9341-2000 | 62.8 | 64.5 | 61.2 | 63.5 |
| Modulus in flexure/Mpa | ﹥2100 | GB/T9341-2000 | 2130 | 2230 | 2340 | 2310 |
| Tensile strength/Mpa | ﹥40.0 | GB/T1040-1992 | 42.8 | 43.9 | 42.6 | 42.5 |
| Heat-drawn wire/℃ | ﹥70.0 | GB/T1634.2-2004 | 72.1 | 71.5 | 72.1 | 72.9 |
| Melt flow rate(MFR)/g10min -1 | ﹥4.0 | GB／T3682-2000 | 4.8 | 5.2 | 5.8 | 5.5 |
| Oxygen index/% | ﹥25.0 | GB/T2406-1993 | 25.8 | 25.6 | 25.9 | 26.0 |
Claims (9)
1. halogen-free flame retardant ABS/PA6 alloy material, its state is a particulate state; It is characterized in that: ABS resin and the polyblend of PA6 resin and the co-mixing system that the additive of blend in this polyblend formed that this particulate state halogen-free flame retardant ABS/PA6 alloy material is formed by blend; Described additive comprises fire retardant, compatible toughening agents, lubrication dispersing agent and oxidation inhibitor; Above-mentioned fire retardant has three kinds; First kind of fire retardant is that melamine cyanurate, second kind of fire retardant are melamine pyrophosphate salt or melamine polyphosphate; The third fire retardant is 3-benzenesulfonyl Phenylsulfonic acid potassium or perfluoro butyl potassium sulfonate, and three kinds of fire retardants form the Halogen composite flame retardant system in co-mixing system; Above-mentioned each composition content by weight is following:
50～80 parts of ABS resins, 20～50 parts of PA6 resins, all 5～25 parts of three kinds of fire retardants, 5～20 parts of compatible toughening agents, 0.5～2.0 part of lubrication dispersing agent, 0.1～0.6 part in oxidation inhibitor;
The weight ratio of said first kind of fire retardant, second kind of fire retardant and the third fire retardant is (40～60): (40～60): (0.2～0.6).
2. halogen-free flame retardant ABS according to claim 1/PA6 alloy material is characterized in that: described compatible toughening agents is styrene butadiene-maleic anhydride multiple copolymer.
3. halogen-free flame retardant ABS according to claim 1/PA6 alloy material is characterized in that: described lubrication dispersing agent is an ethylenebis fatty acid acyl compounds.
4. halogen-free flame retardant ABS according to claim 3/PA6 alloy material is characterized in that: the commercial disignation that described ethylenebis fatty acid acyl compounds derives from the production of Suzhou Xingtai state photochemistry auxiliary agent ltd is the powdered bright lubricant of TAS-2A.
5. halogen-free flame retardant ABS according to claim 1/PA6 alloy material is characterized in that: described oxidation inhibitor chemistry four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester by name derives from the powdered antioxidant 1010.
6. the preparation method of the described halogen-free flame retardant ABS of claim 1/PA6 alloy material is characterized in that having following steps:
1. with particulate state ABS resin and particulate state PA6 resin respectively under 80 ℃～90 ℃ temperature in convection oven dry 3h～5h, take by weighing 50～80 parts of ABS resins after the taking-up, and 20～50 parts of PA6 resins, for use;
2. the proportioning according to following weight part takes by weighing first kind of fire retardant melamine cyanurate of powdery, second kind of fire retardant phosphoric acid salt of powdery, the third fire retardant sulphonate of powdery, particulate state compatible toughening agents, powdery lubrication dispersing agent and powdery oxidation inhibitor, and is for use;
Described particulate state compatible toughening agents is particulate state styrene butadiene-maleic anhydride multiple copolymer; The powdery lubrication dispersing agent is a powdery ethylenebis fatty acid acyl compounds; Described powdery oxidation inhibitor is powdered four [methyl-β-(3, the 5-di-tert-butyl-hydroxy phenyl) propionic ester] pentaerythritol ester; Second kind of fire retardant phosphoric acid salt of described powdery is powdery melamine pyrophosphate salt or powdery melamine polyphosphate; The third fire retardant sulphonate of powdery is powdery 3-benzenesulfonyl Phenylsulfonic acid potassium or powdery perfluoro butyl potassium sulfonate;
The weight part proportioning of each composition is: all 5～25 parts of three kinds of fire retardants, 5～20 parts of compatible toughening agents, 0.5～2.0 part of lubrication dispersing agent, 0.1～0.6 part in oxidation inhibitor; The weight ratio of first kind of fire retardant, second kind of fire retardant and the third fire retardant is (40～60): (40～60): (0.2～0.6);
3. it is to mix in 800 rev/mins～1000 rev/mins the high-speed mixer that compatible toughening agents that 2. ABS resin that 1. step is taken by weighing and PA6 resin and step take by weighing and lubrication dispersing agent are poured rotating speed into; Make temperature of charge be increased to 80 ℃～90 ℃ until mixing the heat of friction that is produced, and make lubrication dispersing agent fusing when being dispersed in ABS resin, PA6 resin and compatible toughening agents surface adhere to ABS resin, PA6 resin and compatible toughening agents surface; It is to continue in 800 rev/mins～1000 rev/mins high-speed mixers to mix that the first kind of fire retardant that then 2. step is taken by weighing, second kind of fire retardant, the third fire retardant and oxidation inhibitor are poured rotating speed into; In the presence of lubrication dispersing agent; Make each fire retardant and oxidation inhibitor evenly adhere to ABS resin, PA6 resin and compatible toughening agents surface; Discharging after the heat of friction that mixing is produced makes material temperature reach 100 ℃～120 ℃ is sent into mixture then and under agitation is cooled to 30 ℃～50 ℃ in the cooling and stirring device;
4. cooled mixture is sent in the twin screw extruder that is heated to design temperature; Mixture is in the process process of twin screw extruder; Be heated on the one hand and soften and become molten state gradually; The further uniform mixing of various at the volley on the other hand compositions is extruded as billot by die head at last, and the extrusion die temperature that sets is 225 ℃ to 235 ℃; The billot of being extruded gets into the dicing machine granulation through tank cooling, traction, promptly obtains granular halogen-free flame retardant ABS/PA6 alloy material.
7. the preparation method of halogen-free flame retardant ABS according to claim 6/PA6 alloy material is characterized in that: the powdery oxidation inhibitor of step in 2. is the powdered antioxidant 1010.
8. the preparation method of halogen-free flame retardant ABS according to claim 6/PA6 alloy material is characterized in that: the powdery ethylenebis fatty acid acyl compounds of step in 2. is that the powdered commercial disignation that Suzhou Xingtai state photochemistry auxiliary agent ltd produces is the bright lubricant of TAS-2A.
9. according to the preparation method of the described halogen-free flame retardant ABS of one of claim 6 to 8/PA6 alloy material; It is characterized in that: step 4. in; Twin screw extruder is divided into 4 heating zone and extrusion die according to the precedence of material process, and the Heating temperature of each heating zone that sets is followed successively by: T
1=160 ℃～170 ℃, T
2=200 ℃～210 ℃, T
3=220 ℃～235 ℃, T
4=235 ℃.
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| CN105885334A (en) * | 2016-05-10 | 2016-08-24 | 康晓霞 | Production method of high-efficiency flame-retardant and environmentally-friendly material |
| CN107186987A (en) * | 2017-05-12 | 2017-09-22 | 江阴市龙山合成材料有限公司 | The production method of high-strength halogen-free flame-retardant PA 66 particle |
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| US4298518A (en) * | 1976-09-06 | 1981-11-03 | Mitsubishi Chemical Industries, Ltd. | Polyamide resin composition |
| CN1990551A (en) * | 2005-12-28 | 2007-07-04 | 上海日之升新技术发展有限公司 | Preparation method of flame-proof nylon and ABS alloy material |
| CN101092501A (en) * | 2007-06-01 | 2007-12-26 | 深圳市科聚新材料有限公司 | PA6 / ABS alloy material, and preparation method |
| CN101311221A (en) * | 2007-05-25 | 2008-11-26 | 佛山市顺德区汉达精密电子科技有限公司 | Fiberglass reinforced fire retardant engineering plastics and preparation method |
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| JP5255169B2 (en) * | 2000-11-24 | 2013-08-07 | 株式会社ダイセル | Flame retardant resin composition |
| KR100569757B1 (en) * | 2003-10-30 | 2006-04-10 | 주식회사 엘지화학 | The thermoplast ic non-halogen resin composition with the flame resistance |
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| US4298518A (en) * | 1976-09-06 | 1981-11-03 | Mitsubishi Chemical Industries, Ltd. | Polyamide resin composition |
| CN1990551A (en) * | 2005-12-28 | 2007-07-04 | 上海日之升新技术发展有限公司 | Preparation method of flame-proof nylon and ABS alloy material |
| CN101311221A (en) * | 2007-05-25 | 2008-11-26 | 佛山市顺德区汉达精密电子科技有限公司 | Fiberglass reinforced fire retardant engineering plastics and preparation method |
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