CN112646343A - Low-smoke-density flame-retardant PC composition - Google Patents
Low-smoke-density flame-retardant PC composition Download PDFInfo
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- CN112646343A CN112646343A CN202011540247.4A CN202011540247A CN112646343A CN 112646343 A CN112646343 A CN 112646343A CN 202011540247 A CN202011540247 A CN 202011540247A CN 112646343 A CN112646343 A CN 112646343A
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- flame retardant
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- retardant
- smoke density
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 81
- 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 79
- 239000000779 smoke Substances 0.000 title claims abstract description 42
- 239000000203 mixture Substances 0.000 title claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000002086 nanomaterial Substances 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 10
- 229920005989 resin Polymers 0.000 claims abstract description 10
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims abstract description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 9
- 239000011574 phosphorus Substances 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000012763 reinforcing filler Substances 0.000 claims abstract description 4
- 239000004417 polycarbonate Substances 0.000 claims description 50
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- -1 6-methylphenyl Chemical group 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003365 glass fiber Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 4
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 4
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- 229920000402 bisphenol A polycarbonate polymer Polymers 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- OWICEWMBIBPFAH-UHFFFAOYSA-N (3-diphenoxyphosphoryloxyphenyl) diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=C(OP(=O)(OC=2C=CC=CC=2)OC=2C=CC=CC=2)C=CC=1)(=O)OC1=CC=CC=C1 OWICEWMBIBPFAH-UHFFFAOYSA-N 0.000 claims description 2
- VSIKJPJINIDELZ-UHFFFAOYSA-N 2,2,4,4,6,6,8,8-octakis-phenyl-1,3,5,7,2,4,6,8-tetraoxatetrasilocane Chemical compound O1[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si](C=2C=CC=CC=2)(C=2C=CC=CC=2)O[Si]1(C=1C=CC=CC=1)C1=CC=CC=C1 VSIKJPJINIDELZ-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- KCSVLWWBFNKRRA-UHFFFAOYSA-N OS(C1=CC=CC=C1)(=O)=O.O=[S-](C1=CC=CC=C1)=O.[K+] Chemical compound OS(C1=CC=CC=C1)(=O)=O.O=[S-](C1=CC=CC=C1)=O.[K+] KCSVLWWBFNKRRA-UHFFFAOYSA-N 0.000 claims description 2
- HAMULBACRNAYNL-UHFFFAOYSA-N P(O)(=O)(OP(=O)(O)O)OC1=CC(O)=C(C=C1C1=C(C=CC=C1C)C)C1=C(C=CC=C1C)C Chemical compound P(O)(=O)(OP(=O)(O)O)OC1=CC(O)=C(C=C1C1=C(C=CC=C1C)C)C1=C(C=CC=C1C)C HAMULBACRNAYNL-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- LAUIXFSZFKWUCT-UHFFFAOYSA-N [4-[2-(4-phosphonooxyphenyl)propan-2-yl]phenyl] dihydrogen phosphate Chemical compound C=1C=C(OP(O)(O)=O)C=CC=1C(C)(C)C1=CC=C(OP(O)(O)=O)C=C1 LAUIXFSZFKWUCT-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 claims description 2
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 claims description 2
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 claims description 2
- UBHZUDXTHNMNLD-UHFFFAOYSA-N dimethylsilane Chemical compound C[SiH2]C UBHZUDXTHNMNLD-UHFFFAOYSA-N 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- UQSHIDHNLKIYGN-UHFFFAOYSA-N diphenoxyphosphoryl diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OP(=O)(OC=1C=CC=CC=1)OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 UQSHIDHNLKIYGN-UHFFFAOYSA-N 0.000 claims description 2
- ASMQGLCHMVWBQR-UHFFFAOYSA-M diphenyl phosphate Chemical compound C=1C=CC=CC=1OP(=O)([O-])OC1=CC=CC=C1 ASMQGLCHMVWBQR-UHFFFAOYSA-M 0.000 claims description 2
- 238000009826 distribution Methods 0.000 claims description 2
- 229960001545 hydrotalcite Drugs 0.000 claims description 2
- 229910001701 hydrotalcite Inorganic materials 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- 239000005543 nano-size silicon particle Substances 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 235000012239 silicon dioxide Nutrition 0.000 claims description 2
- XZJUCCSDEMXAQU-UHFFFAOYSA-N sodium;1,2,4-trichlorobenzene Chemical compound [Na].ClC1=CC=C(Cl)C(Cl)=C1 XZJUCCSDEMXAQU-UHFFFAOYSA-N 0.000 claims description 2
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 2
- 239000010456 wollastonite Substances 0.000 claims description 2
- 229910052882 wollastonite Inorganic materials 0.000 claims description 2
- GQOUGABZQVSVHX-UHFFFAOYSA-N 3-hydroxy-2,4-dioxa-3lambda5-phosphabicyclo[3.3.1]nona-1(9),5,7-triene 3-oxide Chemical compound C1=CC(OP(O)(=O)O2)=CC2=C1 GQOUGABZQVSVHX-UHFFFAOYSA-N 0.000 claims 1
- 229920000734 polysilsesquioxane polymer Polymers 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 238000002485 combustion reaction Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 6
- 230000005855 radiation Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011159 matrix material Substances 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
- 239000000243 solution Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000003111 delayed effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- LAQFLZHBVPULPL-UHFFFAOYSA-N methyl(phenyl)silicon Chemical compound C[Si]C1=CC=CC=C1 LAQFLZHBVPULPL-UHFFFAOYSA-N 0.000 description 2
- 239000012994 photoredox catalyst Substances 0.000 description 2
- CTFKOMUXSHQLLL-UHFFFAOYSA-N 2,6-ditert-butyl-4-[[1-(hydroxymethyl)cyclopentyl]methyl]phenol Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CC2(CO)CCCC2)=C1 CTFKOMUXSHQLLL-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920007019 PC/ABS Polymers 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N phosphoric acid Substances OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000379 polypropylene carbonate Polymers 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002109 single walled nanotube Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012808 vapor phase 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
- C08K2201/011—Nanostructured additives
-
- 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
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)
Abstract
The invention discloses a low-smoke-density flame-retardant PC composition which is prepared from the following raw materials in parts by weight: 10-85 parts of PC resin, 5-50 parts of organosilicon PC, 0.1-2 parts of sulfonate flame retardant, 0-10 parts of phosphorus flame retardant, 0.3-5 parts of organosilicon flame retardant, 2-40 parts of reinforcing filler and 0.5-5 parts of nano material. According to the low-smoke-density flame-retardant PC composition, the flame retardant efficiency can be improved through a compounded flame-retardant system and the addition of the inorganic nano material due to the large nano specific surface, the release of combustible gas during the degradation of the material is slowed down and reduced, so that the smoke generation and combustion of the material are slowed down, the low-smoke-density flame-retardant effect is achieved while the addition amount of the flame retardant is low, and the low-smoke-density flame-retardant PC composition can be applied to the fields of rail transit, aerospace, buildings and the like with strict requirements on the material combustion smoke density.
Description
Technical Field
The invention belongs to the technical field of low-smoke density flame-retardant compositions, and particularly relates to a low-smoke density flame-retardant PC composition.
Background
The PC has high impact strength, is an engineering plastic with wide application, has high carbon content and self-extinguishing property when the thickness is higher, and is widely applied to the fields of electronic appliances, rail transit, buildings and the like with flame retardant requirements. The high carbon content of PC can generate more smoke during combustion, and particularly 50kW/m after the phosphorus flame retardant is added2The degradation or combustion of the PC and flame retardant results in a greater smoke density when tested at the heat flow of (a). The defects in the prior art patent are as follows: sabic US9266541B2 used a PC copolymerization scheme which was costly, not suitable for use in common raw material plants, and the material lost the properties of bisphenol a polycarbonate itself. Patent CN109777073A is to add more flame retardant to PC to achieve low smoke density. The product in patent CN106589784 is a PC/ABS alloy with low carbon content, but is only applicable to the fields of low-end vehicles, buildings and the like. The smoke suppressant molybdenum of patent 201210076335, in the pure PC formulation, causes degradation of pure PC, which is not suitable for the pure PC formulation, and thus the performance advantages of PC cannot be realized. In the prior art, the traditional scheme with low cost is that high-temperature-resistant and low-smoke-density raw materials such as PPC and PEI are added into PC, or more fillers are added to dilute resin, so that the performance of the material is changed.
Disclosure of Invention
The invention provides a low-smoke density flame-retardant PC composition in order to overcome the defects in the prior art.
The invention is realized by the following technical scheme: the invention discloses a low-smoke density flame-retardant PC composition which is prepared from the following raw materials in parts by weight: 10-85 parts of PC resin and 5-50 parts of organic silicon PC; 0.1-2 parts of a sulfonate flame retardant; 0-10 parts of a phosphorus flame retardant; 0.3-5 parts of organic silicon flame retardant, 2-40 parts of reinforcing filler and 0.5-5 parts of nano material.
The PC resin is bisphenol A polycarbonate, the weight average molecular weight of the PC resin is 25000-50000, and the molecular weight distribution of the PC resin is 1-2.
The organosilicon PC is prepared from dimethylsilane and unsaturated aliphatic monohydric phenol. In the block dialkyl siloxane PC, 50 to 90 Wt% of carbonate unit, 1 to 50 Wt% of silane group unit and 5 to 9 Wt% of silicon are used.
The phosphorus flame retardant is 1,3 phenylene phosphoric acid (2, 6-methylphenyl) tetraester, tetraphenyl bisphenol A diphosphate and derivative flame retardant (BDP), tetraphenyl resorcinol diphosphate and derivative flame Retardant (RDP), triphenyl phosphate (TPP) flame retardant, resorcinol bis [ di (2, 6-dimethylphenyl) phosphate ] (RDX), one or more of methylphenyl-bis (2, 6-dimethylphenyl) phosphate, di- (2, 6-dimethylphenyl) resorcinol diphosphate (DMP-RDP), hydroquinone bis (diphenylphosphate) (HDP), tetra- (2, 6-dimethylphenyl) hydroquinone diphosphate (DMP-HDP), p-biphenylene tetraphenyl diphosphate (DH-BDP), and diphenylene sulfone tetraphenyl diphosphate (BSPP). The phosphorus content of all the phosphorus flame retardants is between 7 and 15 Wt percent, wherein the effect of DMP-HDP on reducing smoke density is optimal.
The sulfonate fire retardant is one or more of benzenesulfonyl potassium benzenesulfonate (KSS) and its derivatives, perfluorobutyl potassium sulfonate and its derivatives (PPFBS), and 2,4, 5-trichlorobenzene sodium sulfonate and its derivatives (STB).
The organic silicon flame retardant is one or more of a polyborosilazane and derivative flame retardant, a cross-linked Polydimethylsiloxane (PDMS) and derivative flame retardant, a methylphenylsiloxane and derivative flame retardant, a polyorganosilsesquioxane, a cage-type silsesquioxane and derivative flame retardant and octaphenylcyclotetrasiloxane. The molecular weight of the methyl phenyl silane flame retardant is 2000-5000, and the melting temperature is 35-95 ℃.
The reinforcing filler is one or more of round alkali-free glass fiber, flat alkali-free glass fiber, wollastonite, calcium carbonate, calcium sulfate whisker, mica powder, talcum powder and hydrotalcite. Particularly, the length-diameter ratio of the glass fiber is 1.5-100, and the flat glass fiber filler with larger length-diameter ratio can enable the material to be 50kW/m2The deformation is delayed under the heat flow test condition, and the increase of smoke density is slowed down. The diameter of the glass fiber is between 10 and 40 mu m, the smaller the diameter is, the material is 50kW/m2The smaller the deformation under the heat flow test conditions, the slower the smoke density rise during the test.
The nano material is one or more of nano silicon dioxide, carbon nano tube and nano montmorillonite. Wherein the nano-silica is silica particles produced by a vapor phase method, the diameter is 500 nm-4000 nm, and the specific surface area is (800-1200) m2(BET method), N2 adsorption capacity of 1.4-5.0 ml/g. The carbon nano tube is a single-wall or multi-wall carbon nano tube, the diameter is between 1nm and 7nm, the length-diameter ratio L/D is between 10 and 1000, the oil absorption value is more than 300ml/100g, and the nitrogen adsorption BET specific surface area is 400m2More than g. The nano montmorillonite is prepared by chemical intercalation method, the interlayer spacing is more than 5nm, the diameter-thickness ratio is more than 200, and the specific surface area is 500m2More than g.
The production method of the low-smoke density flame-retardant PC composition comprises the following steps: after the raw material particles and the powder are uniformly stirred, the mixture is processed by a method that the length-diameter ratio is 40: 1, injection molding 75mm by 75mm 2mm plates, testing ISO5660 smoke density under 50kW/m2A flameless mode. Temperature of the twin-screw extruder: 150 ℃ in the first section, 255 ℃ in the second section and a third section255 ℃ in the fourth section, 255 ℃ in the fifth section, 250 ℃ in the sixth section, 260 ℃ in the seventh section, 250 ℃ in the eighth section, 250 ℃ in the ninth section and 250 ℃ in the tenth section. The rotation speed of a main screw of the double-screw extruder is 400 +/-50 rpm, the rotation speed of a side feeder is 40 +/-10 Hz, and the vacuum pressure is>0.07MPa。
The invention has the beneficial effects that: due to the addition of the compound flame retardant system and the nano system, the low smoke density can be achieved on the premise of reducing the addition of the flame retardant, so that the flame retardant can be applied to the field of rail transit and the field of buildings. In the PC flame retardant material with low smoke density, the flame retardant material is 250 kW/m in ISO 5659-2The flame retardant itself is decomposed by the heat flux radiation of (1), and although the increase in smoke density can be reduced, VOF4, Dm are difficult to be made lower, such as VOF (4)<Dm is less than 600 within 300 and 10min, and the flame retardant can be prepared by adding inorganic nanoparticles with less influence on physical properties, and under the premise of reducing the addition amount of the flame retardant, ISO 5659-250 kW/m2VOF (4) under heat flux radiation<Dm is less than 600 within 300 and 10 min.
According to the common technical scheme in the prior art, the mechanical property is reduced due to excessive addition of the flame retardant. According to the invention, by compounding a flame retardant system and adding an inorganic nano material, the flame retardant efficiency can be improved by a larger nano specific surface, and the release of combustible gas during material degradation is slowed down and reduced, so that the smoke generation and combustion of the material are slowed down, the low smoke density flame retardant effect is achieved while the addition amount of the flame retardant is reduced, and the flame retardant system can be applied to the fields of rail transit, aerospace, buildings and the like with strict requirements on the smoke density of material combustion.
The low-smoke density flame-retardant PC composition also has the following advantages: firstly, PC is degraded under a heat radiation source to generate combustible gas, the nano material has high surface energy and high specific surface area, after the PC is carbonized by the flame retardant, the PC can be adsorbed by the nano material and becomes a carbon layer with higher strength, the carbonized PC plays a heat insulation role in a matrix, the heat transfer and mass transfer of the material under the degradation and irradiation of the material are delayed, and the efficiency of the flame retardant is improved; secondly, the nano material can adsorb the flame retardant, delay the degradation of the flame retardant at high temperature and improve the carbon forming efficiency of the flame retardant to PC; thirdly, the base material and the degraded combustible gas need to overcome the surface of the blocking carbon layer and the nanometer material to reach the surface of the material, and the combustible gas generated at the initial stage of the degradation of the material needs to overcome more interfaces to slow down the escape speed of the gas from the matrix.
Detailed Description
The present invention will be described in detail with reference to specific examples.
Table 1: comparative examples 1 to 5.
Conclusion 1: as can be seen from the table 1, the PPFBS has the functions of catalyzing PC isomerization, reducing potential energy of PC material during decomposition, promoting carbon formation and improving flame retardant efficiency of the phosphorus flame retardant. DMP-HDP has higher decomposition temperature, and is degraded in a PC matrix slowly under the same heat flow, so that the continuous carbon forming effect can be generated. Too much PPFBS addition does not lower the smoke density because the material is dominated by P flame retardant, PC char formation has reached its limit, and too much flame retardant addition does not lower the smoke density.
Table 2: comparative examples 6 to 7.
Conclusion 2: the methyl-phenyl silane can diffuse to the surface of the material under the heat radiation and is crosslinked into a net structure in the PC carbon forming process.
Table 3: examples 1 to 5.
Conclusion 3: the larger the length-diameter ratio of the material is, the structure of the carbon layer is enhanced, so that the gas escape and the heat insulation effect of the material are better.
Table 4: examples 6 to 8.
Conclusion 4: the two-dimensional structure with larger diameter-thickness ratio of the nano montmorillonite and the layered three-dimensional structure have the most excellent performance compared with other nano materials in the aspects of adsorption, heat resistance and heat insulation.
Table 5: comparative example 8 and examples 9-10.
Conclusion 5: it can be seen from table 5 that, after the DMP-HDP is reduced, the more the nano-montmorillonite is added, the more the material releases heat when catalyzing the flame retardant to form carbon and reducing degradation, and further the heating of the radiation source to the inside of the material is slowed down, and lower smoke density is generated.
Table 6: comparative example 9 and examples 11-12.
Conclusion 6: as can be seen from table 6, the smoke density can also be reduced with the addition of more nanomaterial for the sulfonate system alone, but VOF4 and Dm are still high.
Finally, it should be noted that the above-mentioned contents are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, and that the simple modifications or equivalent substitutions of the technical solutions of the present invention by those of ordinary skill in the art can be made without departing from the spirit and scope of the technical solutions of the present invention.
Claims (8)
1. A low smoke density flame retardant PC composition characterized by: the low-smoke density flame-retardant PC composition is prepared from the following raw materials in parts by weight: 10-85 parts of PC resin, 5-50 parts of organosilicon PC, 0.1-2 parts of sulfonate flame retardant, 0-10 parts of phosphorus flame retardant, 0.3-5 parts of organosilicon flame retardant, 2-40 parts of reinforcing filler and 0.5-5 parts of nano material.
2. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the PC resin is bisphenol A polycarbonate, the weight average molecular weight of the PC resin is 25000-50000, and the molecular weight distribution of the PC resin is 1-2.
3. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the organosilicon PC is prepared from dimethylsilane and unsaturated aliphatic monohydric phenol.
4. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the phosphorus flame retardant is one or more of 1,3 phenylene phosphate (2, 6-methylphenyl) tetraester, tetraphenyl bisphenol A diphosphate and derivative flame retardant, tetraphenyl resorcinol diphosphate and derivative flame retardant, triphenyl phosphate flame retardant, resorcinol bis [ di (2, 6-dimethylphenyl) phosphate ], methylphenyl-bis (2, 6-dimethylphenyl) phosphate, di- (2, 6-dimethylphenyl) resorcinol diphosphate, hydroquinone bis (diphenyl phosphate), tetra- (2, 6-dimethylphenyl) hydroquinone diphosphate, p-biphenylene tetraphenyl diphosphate and diphenylene sulfone tetraphenyl diphosphate.
5. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the sulfonate flame retardant is one or more of benzenesulfonyl potassium benzene sulfonate and derivatives thereof, perfluorobutyl potassium sulfonate and derivatives thereof, and 2,4, 5-trichlorobenzene sodium sulfonate and derivatives thereof.
6. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the organic silicon flame retardant is one or more of a polyborosilazane flame retardant and derivatives thereof, a cross-linked polydimethylsiloxane flame retardant and derivatives thereof, a methyl phenyl siloxane and derivatives thereof, a polysilsesquioxane, a cage type silsesquioxane and derivatives thereof and an octaphenyl cyclotetrasiloxane.
7. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the reinforced filling material is one or more of round alkali-free glass fiber, flat alkali-free glass fiber, wollastonite, calcium carbonate, calcium sulfate whisker, mica powder, talcum powder and hydrotalcite.
8. A low smoke density flame retardant PC composition according to claim 1, characterized in that: the nano material is one or more of nano silicon dioxide, carbon nano tube and nano montmorillonite.
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