CN108299814A - A kind of low bromine high-efficiency environment friendly fire-retardant polycarbonate - Google Patents
A kind of low bromine high-efficiency environment friendly fire-retardant polycarbonate Download PDFInfo
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- CN108299814A CN108299814A CN201710025488.7A CN201710025488A CN108299814A CN 108299814 A CN108299814 A CN 108299814A CN 201710025488 A CN201710025488 A CN 201710025488A CN 108299814 A CN108299814 A CN 108299814A
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- Prior art keywords
- retardant
- environment friendly
- efficiency environment
- fire
- sulfonate
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 63
- 229920000515 polycarbonate Polymers 0.000 title claims abstract description 47
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052794 bromium Inorganic materials 0.000 title claims abstract description 30
- 239000004417 polycarbonate Substances 0.000 title claims abstract description 30
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 27
- 239000004425 Makrolon Substances 0.000 claims abstract description 20
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims abstract description 19
- 150000008054 sulfonate salts Chemical class 0.000 claims abstract description 16
- 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 abstract description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 14
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical group C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011591 potassium Substances 0.000 claims abstract description 14
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 14
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 150000002148 esters Chemical class 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003086 colorant Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000012745 toughening agent Substances 0.000 claims description 4
- VEORPZCZECFIRK-UHFFFAOYSA-N 3,3',5,5'-tetrabromobisphenol A Chemical compound C=1C(Br)=C(O)C(Br)=CC=1C(C)(C)C1=CC(Br)=C(O)C(Br)=C1 VEORPZCZECFIRK-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000001125 extrusion Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- XDPAMDIXXGVQLF-UHFFFAOYSA-N FC(F)(F)C(F)(F)C(F)(F)C(F)(F)[S] Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)(F)[S] XDPAMDIXXGVQLF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 239000003205 fragrance Substances 0.000 claims 2
- 125000001246 bromo group Chemical group Br* 0.000 claims 1
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims 1
- 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 abstract description 16
- 239000000654 additive Substances 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000000979 retarding effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 6
- 238000013329 compounding Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- -1 acids salt Chemical class 0.000 description 5
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 3
- LVTHXRLARFLXNR-UHFFFAOYSA-M potassium;1,1,2,2,3,3,4,4,4-nonafluorobutane-1-sulfonate Chemical compound [K+].[O-]S(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F LVTHXRLARFLXNR-UHFFFAOYSA-M 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- TXQVDVNAKHFQPP-UHFFFAOYSA-N [3-hydroxy-2,2-bis(hydroxymethyl)propyl] octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(CO)(CO)CO TXQVDVNAKHFQPP-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 235000019260 propionic acid Nutrition 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- BZQKBFHEWDPQHD-UHFFFAOYSA-N 1,2,3,4,5-pentabromo-6-[2-(2,3,4,5,6-pentabromophenyl)ethyl]benzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1CCC1=C(Br)C(Br)=C(Br)C(Br)=C1Br BZQKBFHEWDPQHD-UHFFFAOYSA-N 0.000 description 1
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 1
- 229920009204 Methacrylate-butadiene-styrene Polymers 0.000 description 1
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical group CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 description 1
- 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 group 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 description 1
- 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 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- IRERQBUNZFJFGC-UHFFFAOYSA-L azure blue Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Na+].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[S-]S[S-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-].[O-][Si]([O-])([O-])[O-] IRERQBUNZFJFGC-UHFFFAOYSA-L 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 150000004651 carbonic acid esters Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- GLDOVTGHNKAZLK-UHFFFAOYSA-N n-octadecyl alcohol Natural products CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical group CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000008301 phosphite esters Chemical class 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Fireproofing Substances (AREA)
Abstract
The present invention provides a kind of low bromine high-efficiency environment friendly fire-retardant polycarbonates and preparation method thereof.The fire-retardant polycarbonate is grouped as by the following following group calculated by weight：A, 93~98 parts of makrolon, b, 0.2~0.5 part of sulfonate salt flame, c, 0.05~0.2 part of bromide fire retardant, d, 0.1~0.5 part of anti-dripping agent, e, 0~6 part of auxiliary agent, wherein the sum of parts by weight of five kinds of components of a, b, c, d, e are 100 parts；The sulfonate salt flame is the compound of perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate, and the weight ratio of the perfluorobutyl potassium sulfonate, diphenyl sulfuryl potassium sulfonate and bromide fire retardant is weight ratio 1:1~6:0.5~2.The compound that the present invention is compounded using perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate is acted on bromide fire retardant cooperative flame retardant, greatly reduce fire retardant additive amount, flame retarding efficiency is high, it is little to makrolon mechanical property, Effect of Thermal Performance, finally obtained makrolon meets ROSH and halogen-free environmental requirement, bromine content control is in 900ppm hereinafter, flame retardant rating reaches 1.6mm UL94 V0.
Description
Technical field
The present invention relates to technical field of polymer materials, more specifically to a kind of low bromine high-efficiency environment friendly anti-flaming polycarbonate
Ester.
Background technology
Makrolon is a kind of plastics with excellent comprehensive performance, and the phenyl ring on molecular backbone makes it have well
Mechanical property, heat resistance, and ehter bond makes its strand have certain compliance, is a kind of rigid and tough engineering plastics.It is poly-
Carbonic ester itself has certain anti-flammability, can reach UL94V2 grades, but still be difficult to meet certain application fields to high fire-retardance
The requirement of performance, it is therefore desirable to it be carried out flame-retardant modified.Mainly there are following a few classes for the flame-retardant modified of makrolon at present
Fire retardant：Bromide fire retardant, phosphorus flame retardant, silicon-series five-retardant, sulfonate salt flame.
In recent years, bromide fire retardant is due to the raising of various countries' environmental requirement, and additive amount is big, is used alone increasingly
It is few；Phosphorus flame retardant hydrolytic stability is poor, and makrolon heat distortion temperature can be caused to be decreased obviously；Silicon-series five-retardant performance
It is superior, but additive amount is more, it is of high cost generally 4% or so；Sulfonate salt flame flame retarding efficiency is high, and additive amount is small, and heat is steady
It is qualitative excellent, but cannot be satisfied thin wall parts（Less than 2mm）Requirement.There is certain defect in view of each based flame retardant,
In use, several based flame retardants would generally be selected to be compounded.As 103788610 A of patent CN disclose the low temperature resistant punching of high transparency
Fire-retardant polycarbonate composite material and preparation method is hit, the fire retardant which uses is decabromodiphenylethane, poly- bromo carbon
One or more of acid esters, perfluorobutyl potassium sulfonate or diphenyl sulfone sulfonate mix, and add percentage 1 ~ 4%.But its bromine system
The additive amount of fire retardant is on the high side, exceeds the limitation of 900ppm.Patent CN102164991A discloses a kind of flame-proofed thermoplastic combination
Object, with aromatic sulfonesulfonic acids salt, aromatic sulphonate and bromination carbonate resin come modified polycarbonate.Obtained flame retardant combination
The final brominated amount of object is the 0.25% ~ 2.5% of total weight, seriously has exceeded the limitation of 900ppm.
Invention content
The purpose of the invention is to overcome the deficiencies of the prior art and provide a kind of low bromine high-efficiency environment friendly anti-flaming polycarbonate
Ester.
It is another object of the present invention to provide the preparation methods of the low bromine high-efficiency environment friendly anti-flaming polycarbonate.
Above-mentioned purpose of the present invention is achieved by following technical solution：
A kind of low bromine high-efficiency environment friendly fire-retardant polycarbonate, is grouped as by the group calculated by weight as follows：
A, 93~98 parts of makrolon,
B, 0.2~0.5 part of sulfonate salt flame,
C, 0.05~0.2 part of bromide fire retardant,
D, 0.1~0.5 part of anti-dripping agent,
E, 0~6 part of other auxiliary agent,
Wherein, the sum of parts by weight of five kinds of components of a, b, c, d, e are 100 parts；
The sulfonate salt flame is the compound of perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate, the perfluoro butyl sulphur
The weight ratio of sour potassium, diphenyl sulfuryl potassium sulfonate and bromide fire retardant is weight ratio 1:1~6:0.5~2.
Inventors be surprised to learn that when perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate compounding using aforementioned proportion,
By the addition of a small amount of bromide fire retardant, in the case of fire retardant total amount of adding very little can be made, reach 1.6mm UL94 V0's
Flame retardant rating.Due in the case of compounding, the additive amount very little of bromide fire retardant, therefore bromine content can control in finished product
Within 900ppm, meet ROSH and halogen-free environmental requirement.
Preferably, in the sulfonate salt flame, consider in conjunction with cost and performance, the parts by weight of perfluorobutyl potassium sulfonate
To be not more than 0.1 part.That is, 0.2~0.5 part of sulfonate salt flame by be not more than 0.1 part of perfluorobutyl potassium sulfonate with it is remaining
Amount is diphenyl sulfuryl potassium sulfonate compounding composition.
Preferably, the perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate are by weight 1:2~1:3 compoundings.At this
In range, flame retardant property is good in the case of bromine additive amount can not only be kept few, while reaching cost optimization and having excellent
Mechanical property.
Preferably, the makrolon is preferably aromatic copolycarbonate.
The aromatic carbonate can be made of a kind of aromatic carbonate, can also be by several melt index difference
Aromatic carbonate mixing constitute.Preferably, if it is a kind of independent aromatic carbonate is used, then preferred molten index is excellent
It is selected as 6 ~ 20 g/10min；It is mixed if it is a variety of aromatic carbonates, then preferably mixed aromatic copolycarbonate melting
Index is preferably 6 ~ 20 g/10min.
Preferably, the bromide fire retardant is preferably one kind or several in brominated polycarbonates oligomer or tetrabromobisphenol-A
Kind.Brominated polycarbonates oligomer can be the trades mark such as BC-52, BC-58.
Preferably, the anti-dripping agent is polytetrafluoroethylene (PTFE) or Kynoar.Anti-dripping agent can also play auxiliary and improve
The effect of anti-flammability, but if not adding perfluorobutyl potassium sulfonate, flame retardant property is unable to reach ideal level.
Preferably, the dosage of the anti-dripping agent is 0.2 ~ 0.5 part.
Other described auxiliary agents are usual auxiliaries in plastic processes, it is preferable that other described auxiliary agents are toughener, antioxygen
Agent, lubricant and/or colorant.Specifically, the toughener can be methyl methacrylate-butadiene-organosilicon copolymerization
Object（MBSi）, nucleocapsid structure Methyl Methacrylate-Butadiene-Styrene Copolymer（MBS）, ethylene-acrylate
（EMA）One or more of；The antioxidant can be three (2,4- di-tert-butyl-phenyls) phosphite esters（That is antioxidant
168）, four [β-（3,5- di-tert-butyl-hydroxy phenyls）Propionic acid] pentaerythritol ester（That is antioxidant 1010）Or β-（Bis- uncles of 3,5-
Butyl -4- hydroxy phenyls）Propionic acid n-octadecyl alcohol ester（That is antioxidant 1076）One or more of；The lubricant can be
Pentaerythritol stearate (PETS) or N, N- ethylene bis stearic acid amide（EBS）One or more of；The colorant choosing
From titanium dioxide, carbon black, phthalocyanine, ultramarine, azo, Naphtocyclinon etc. be inorganic and one or more of toner.
The preparation method of the low bromine high-efficiency environment friendly fire-retardant polycarbonate, includes the following steps：
S1. by makrolon drying for standby；
S2. it is equal that makrolon, sulfonate salt flame, bromide fire retardant, anti-dripping agent and auxiliary agent mixing are weighed by weight percentage
It is even, obtain mixed material；
S3. the mixed material described in step S2 is put into double screw extruder, melting extrusion is granulated.
Preferably, it is 260~280 DEG C that each section of extruder temperature of double screw extruder is controlled in the step S3., screw speed
At 300~400 revs/min.
Compared with prior art, the present invention has following advantageous effects：
Low bromine high-efficiency environment friendly fire-retardant polycarbonate prepared by the present invention, utilizes perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate
The compound of compounding is acted on bromide fire retardant cooperative flame retardant, greatly reduces fire retardant additive amount, flame retarding efficiency is high, to poly- carbonic acid
Ester mechanical property, Effect of Thermal Performance are little, and finally obtained makrolon meets ROSH and halogen-free environmental requirement, bromine content control
System is in 900ppm hereinafter, flame retardant rating reaches 1.6mm UL94 V0, and thermal stability is high, and excellent in mechanical performance can extensive use
In fields such as automobile, electronic apparatus.
Specific implementation mode
With reference to specific embodiment and comparative example, the present invention is described in further detail, but the present invention is not limited to
Following embodiments.
In embodiment, it is conventional commercial commodity not have the raw material of special instruction.
Makrolon A, aromatic copolycarbonate, 10 g/10min of melt index（PC 1300-10NP LG chemistry）；
Makrolon B, aromatic copolycarbonate, 15 g/10min of melt index；It is 10 g/10min by melt index（PC
1300-10NP LG chemistry）With 22 g/10min of melt index（PC 1300-22NP LG chemistry）Two kinds of compoundings obtain；
Perfluorobutyl potassium sulfonate（PPFBS）, it is purchased from 3M companies；
Diphenyl sulfuryl potassium sulfonate（KSS）, it is purchased from India Metro；
Brominated polycarbonates BC-58 is purchased from U.S. big lake；
Tetrabromobisphenol-A is purchased from the Israel Dead Sea.
The fire-retardant polycarbonate of each embodiment is formulated by table 1, and prepared by following method：
S1. the electric heating constant-temperature blowing drying box by makrolon at 100~110 DEG C dries 3~4h；
S2. makrolon, sulfonate salt flame, bromide fire retardant, anti-dripping agent, colorant, antioxygen are weighed according to parts by weight
Agent, toughener and lubricant are added sequentially in high mixer, stir 3~5min；
S3. by high-speed mixer and mixing material put into double screw extruder, control each section of extruder temperature of double screw extruder be 260~
280 DEG C, screw speed is granulated in 300~400 turns/min, melting extrusion；Up to the fire-retardant poly- carbon of low bromine high-efficiency environment friendly of the present invention
Acid esters.
Table 1
Continued 1
Comparative example 1 ~ 5 is prepared according to the formula of table 2 according to identical preparation method
Table 2
The flame retardant property, mechanical property, bromine content of the makrolon of embodiment and comparative example preparation are tested, as a result such as table
Shown in 3：
Table 3
By embodiment and comparative example comparison as can be seen that the present invention is coordinated a small amount of by the reasonably combined of PPFBS and KBS
Bromide fire retardant, anti-dripping agent in the case of bromine content can be made to reach ROSH and Halogen-free requirement, maintain ideal fire-retardant effect
Fruit.Such as embodiment 2 is added without bromide fire retardant, thin-walled with comparative example 1 as can be seen that working as in system（1.6mm）Anti-flammability
The level of UL94V0 can be reached, comparative example 3 cannot reach outstanding it can be seen that when not adding sulfonate salt flame in system
Thin-walled（1.6mm）Flame retardant property.When PPFBS too high levels in system, sulfonate salt flame too high levels, shock resistance
It is significantly affected.When bromine content is excessively high, although flame retardant property reaches requirement, bromine content and shock resistance are by apparent
Influence.
Claims (10)
1. a kind of low bromine high-efficiency environment friendly fire-retardant polycarbonate, is grouped as by the group calculated by weight as follows：
A, 93~98 parts of makrolon,
B, 0.2~0.5 part of sulfonate salt flame,
C, 0.05~0.2 part of bromide fire retardant,
D, 0.1~0.5 part of anti-dripping agent,
E, 0~6 part of other auxiliary agent,
Wherein, the sum of parts by weight of five kinds of components of a, b, c, d, e are 100 parts；
The sulfonate salt flame is the compound of perfluorobutyl potassium sulfonate and diphenyl sulfuryl potassium sulfonate, the perfluoro butyl sulphur
The weight ratio of sour potassium, diphenyl sulfuryl potassium sulfonate and bromide fire retardant is weight ratio 1:1~6:0.5~2.
2. low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 1, which is characterized in that the makrolon is fragrance
Adoption carbonic ester.
3. low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 2, which is characterized in that the aromatic copolycarbonate
Melt index is 6 ~ 20 g/10min.
4. according to low bromine high-efficiency environment friendly fire-retardant polycarbonate described in Claims 2 or 3, which is characterized in that the fragrance adoption carbon
Acid esters forms for one or more aromatic copolycarbonates.
5. low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 1, which is characterized in that the bromide fire retardant is bromine
For one or more of polycarbonate oligomer or tetrabromobisphenol-A.
6. low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 1, which is characterized in that the anti-dripping agent is poly- four
Vinyl fluoride or Kynoar.
7. low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 1, which is characterized in that other described auxiliary agents are toughening
Agent, antioxidant, lubricant and/or colorant.
8. low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 1, which is characterized in that the sulfonate salt flame
In, the parts by weight of perfluorobutyl potassium sulfonate are not more than 0.1 part.
9. the preparation method of any one of claim 1 to the 8 low bromine high-efficiency environment friendly fire-retardant polycarbonate, which is characterized in that packet
Include following steps：
S1. by makrolon drying for standby；
S2. makrolon, sulfonate salt flame, bromide fire retardant, anti-dripping agent and auxiliary agent are weighed by weight to be uniformly mixed, and are obtained
To mixed material；
S3. the mixed material described in step S2 is put into double screw extruder, melting extrusion is granulated.
10. the preparation method of low bromine high-efficiency environment friendly fire-retardant polycarbonate according to claim 9, which is characterized in that the step
Control each section of extruder temperature of double screw extruder is 260~280 DEG C in rapid S3., and screw speed is at 300~400 revs/min.
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