CN1563189A - Flame retardant fiberglass enhanced PCT composite materal in low smoke - Google Patents
Flame retardant fiberglass enhanced PCT composite materal in low smoke Download PDFInfo
- Publication number
- CN1563189A CN1563189A CN 200410017806 CN200410017806A CN1563189A CN 1563189 A CN1563189 A CN 1563189A CN 200410017806 CN200410017806 CN 200410017806 CN 200410017806 A CN200410017806 A CN 200410017806A CN 1563189 A CN1563189 A CN 1563189A
- Authority
- CN
- China
- Prior art keywords
- glass fibre
- pbt
- matrix material
- flame retardant
- smoke
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003063 flame retardant Substances 0.000 title claims description 27
- 239000000779 smoke Substances 0.000 title claims description 20
- 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 description 19
- 239000002131 composite material Substances 0.000 title abstract description 10
- 239000011152 fibreglass Substances 0.000 title 1
- 239000003365 glass fiber Substances 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 3
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 56
- 229920001707 polybutylene terephthalate Polymers 0.000 claims description 52
- 239000011159 matrix material Substances 0.000 claims description 38
- 239000003112 inhibitor Substances 0.000 claims description 31
- 125000001246 bromo group Chemical class Br* 0.000 claims description 27
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 26
- VTYYLEPIZMXCLO-UHFFFAOYSA-L calcium carbonate Substances [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 25
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 19
- 230000003179 granulation Effects 0.000 claims description 18
- 238000005469 granulation Methods 0.000 claims description 18
- -1 octadecyl ester Chemical class 0.000 claims description 15
- 239000002245 particle Substances 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- 230000003647 oxidation Effects 0.000 claims description 12
- 238000007254 oxidation reaction Methods 0.000 claims description 12
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 10
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 7
- 238000000354 decomposition reaction Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 230000003014 reinforcing effect Effects 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- 229920000181 Ethylene propylene rubber Polymers 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- PZRWFKGUFWPFID-UHFFFAOYSA-N 3,9-dioctadecoxy-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5.5]undecane Chemical compound C1OP(OCCCCCCCCCCCCCCCCCC)OCC21COP(OCCCCCCCCCCCCCCCCCC)OC2 PZRWFKGUFWPFID-UHFFFAOYSA-N 0.000 claims description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229920001038 ethylene copolymer Polymers 0.000 claims description 3
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 3
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 3
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005908 glyceryl ester group Chemical group 0.000 claims description 2
- 229920000578 graft copolymer Polymers 0.000 claims description 2
- 125000005395 methacrylic acid group Chemical group 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- GQIUQDDJKHLHTB-UHFFFAOYSA-N trichloro(ethenyl)silane Chemical compound Cl[Si](Cl)(Cl)C=C GQIUQDDJKHLHTB-UHFFFAOYSA-N 0.000 claims description 2
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 239000005050 vinyl trichlorosilane Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 34
- 239000000126 substance Substances 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 abstract 2
- 239000004809 Teflon Substances 0.000 abstract 1
- 229920006362 Teflon® Polymers 0.000 abstract 1
- 235000010290 biphenyl Nutrition 0.000 abstract 1
- 239000004305 biphenyl Substances 0.000 abstract 1
- WUOBERCRSABHOT-UHFFFAOYSA-N diantimony Chemical compound [Sb]#[Sb] WUOBERCRSABHOT-UHFFFAOYSA-N 0.000 abstract 1
- 238000007580 dry-mixing Methods 0.000 abstract 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract 1
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000005453 pelletization Methods 0.000 abstract 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 16
- 239000007822 coupling agent Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 11
- 239000011787 zinc oxide Substances 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- BIKXLKXABVUSMH-UHFFFAOYSA-N trizinc;diborate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]B([O-])[O-].[O-]B([O-])[O-] BIKXLKXABVUSMH-UHFFFAOYSA-N 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 4
- 239000000292 calcium oxide Substances 0.000 description 4
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 235000019504 cigarettes Nutrition 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 2
- 239000000347 magnesium hydroxide Substances 0.000 description 2
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 2
- 239000011236 particulate material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- QSRJVOOOWGXUDY-UHFFFAOYSA-N 2-[2-[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoyloxy]ethoxy]ethoxy]ethyl 3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C)=CC(CCC(=O)OCCOCCOCCOC(=O)CCC=2C=C(C(O)=C(C)C=2)C(C)(C)C)=C1 QSRJVOOOWGXUDY-UHFFFAOYSA-N 0.000 description 1
- WSQZNZLOZXSBHA-UHFFFAOYSA-N 3,8-dioxabicyclo[8.2.2]tetradeca-1(12),10,13-triene-2,9-dione Chemical compound O=C1OCCCCOC(=O)C2=CC=C1C=C2 WSQZNZLOZXSBHA-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 description 1
- 229920003314 Elvaloy® Polymers 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 239000004110 Zinc silicate Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- VCNTUJWBXWAWEJ-UHFFFAOYSA-J aluminum;sodium;dicarbonate Chemical compound [Na+].[Al+3].[O-]C([O-])=O.[O-]C([O-])=O VCNTUJWBXWAWEJ-UHFFFAOYSA-J 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BIEHXHIWQHAVFZ-UHFFFAOYSA-M bromoantimony Chemical compound [Sb]Br BIEHXHIWQHAVFZ-UHFFFAOYSA-M 0.000 description 1
- STZJANGYOWJEPH-UHFFFAOYSA-N carbonic acid;molybdenum Chemical compound [Mo].OC(O)=O STZJANGYOWJEPH-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001647 dawsonite Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229960001708 magnesium carbonate Drugs 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 1
- 235000019352 zinc silicate Nutrition 0.000 description 1
- CHJMFFKHPHCQIJ-UHFFFAOYSA-L zinc;octanoate Chemical compound [Zn+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O CHJMFFKHPHCQIJ-UHFFFAOYSA-L 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Compositions Of Macromolecular Compounds (AREA)
Abstract
A glass fibre reinforced PBT composite is prepared from PBT decabromo-ether biphenyl, diantimony trioxide, teflon, nanozine dioxide, nanocalcium carbonate, flexibilizing compatibilizer, antioxygen and glass fibre. Its preparing process includes using PBT as base body, adding abovesaid chemicals and agents on the base body dry-mixing them, melting and extruding mixed material with glass fibre and then pelletizing.
Description
Technical field
A kind of low-smoke and flame retardant type of the present invention glass fiber reinforced polyester butylene terephthalate (calling PBT in the following text) matrix material relates to a kind of polymer composite and preparation method thereof, more specifically relates to a kind of flame retardant type glass fibre that contains smog inhibitor and strengthens the PBT matrix material.
Background technology
Glass fibre strengthens the PBT material and not only has excellent physical and mechanical properties, as physical strength height, resistance to fatigue and dimensional stability are good, creep is little, ageing-resistant performance is excellent, and its electric property is also very excellent, as its volume specific resistance and dielectric strength height, arc resistance can be good, under moist hot environment electric performance stablity, so be the ideal material of making electronics, electric parts.And general electronics, electric parts all have fire-retardant requirement in various degree.Therefore, the fire-retardant problem that the glass fibre that uses in electronics, electric field strengthens the PBT material is a major issue.Usually the flame-retardant system that is used as glass fibre enhancing PBT material at present still is the bromo-antimony combined system of bromide and stibnide.Though the flame retardant effect of this system is remarkable, it realizes that the fire-retardant mechanism of action is to realize by the free radical that destroys in the gas phase, can improve the amount of being fuming again usually, so this has suppressed the oxidizing reaction in the combustion processes just again, has promoted the formation of cigarette ash.In fire, a large amount of smog that these discharge, not only same entail dangers to field staff's life, and the environment around being harmful to.
For this reason, people have done much quite intensive research to the amount of being fuming that how to suppress fire retardant material.These research work major portions concentrate on oxide compound, metal-salt or the metal hydroxides that uses some metals.
Myszak is in U.S. Patent No. 5,409, and when finding that solid particulate size when bromide that uses and stibnide synergistic fire retardant is less than 500 nanometers in 980, prepared fire retardant material is good flame retardation effect not only, and the living cigarette amount of material when burning is also little.
Batdorf is in U.S. Patent No. 4,965, and the mixture of mineral compound that has adopted the mineral compound of a kind of mineral compound of zinc, the mineral compound of magnesium (not comprising magnesium oxide), molybdenum and copper in 309 is as the method for smog inhibitor.
King is in U.S. Patent No. 3,900, and 441 smog inhibitors that propose are compounds of a kind of zinc, as zinc oxide with a kind of molybdic compound, as the mixture of Sodium orthomolybdate.
Schwarcz etc. are in U.S. Patent No. 3,945, and the smog inhibitor that uses in 974 is a kind of material that can form zinc oxide in combustion processes.
Kay is in U.S. Patent No. 3,957, and the smog inhibitor that proposes in 723 is the mixture between hydrated alumina and the zinc oxide.
Dickens is in U.S. Patent No. 3,965, and the smog inhibitor that proposes in 068 is the mixture between the compound of a kind of compound of nickel and zinc.
Elcik is in U.S. Patent No. 3,983, adopted the mixture of a kind of magnesium hydroxide, zinc borate and antimonous oxide as smog inhibitor in 290.
Kay is in U.S. Patent No. 3,985, and the smog inhibitor that uses in 706 is the mixture of hydrated alumina and zinc borate.
White etc. are in U.S. Patent No. 3,996, and the smog inhibitor that uses in 142 is the mixture of magnesium oxide and a kind of zinc salt.
Kroenke is in U.S. Patent No. 4,055, and the smog inhibitor that uses in 537 is wherein a kind of mixture in trimeric cyanamide molybdate and carbonic acid molybdenum, zinc oxide, zinc borate, the zinc silicate.Barr is in U.S. Patent No. 4,079, and the smog inhibitor that uses in 033 is Ferrox or zinc oxalate or zinc octoate or their mixture.
Deets is in U.S. Patent No. 4,080, smog inhibitor dawsonite, magnesium, carbonate, Ferrox, zinc borate, zinc acetate or the zinc oxide and the magnesian mixture that use in 404.Lawson is in U.S. Patent No. 4,096, and the smog inhibitor that uses in 116 is aluminium hydroxide and the carboxylate salt of cobalt, zinc, iron or magnesium or a kind of mixture in the dicarboxylate at least.
Nichols is in U.S. Patent No. 4,097, and the smog inhibitor that uses in 432 is a kind of special organic compound and the oxyhydroxide of ferric iron or divalent zinc or the mixture of salt.
Elcik is in U.S. Patent No. 4,129, and the smog inhibitor that uses in 535 is the mixture of a kind of magnesium hydroxide, zinc borate and antimonous oxide.
Joyce II etc. are in U.S. Patent No. 4,260, and employed smog inhibitor is the reaction product of compound and some metal-salt, metal oxide, ammonia salt or the silicon salt of one or more phosphorus in 542.
Davis etc. are in U.S. Patent No. 4,272, and the smog inhibitor that uses in 427 is the mixture of magnesiumcarbonate and zinc carbonate.
Huang etc. are in U.S. Patent No. 4,360, and the smog inhibitor that uses in 624 is zinc oxide, magnesium oxide and or calcium oxide and or the mixture of stibnide.
Jacobs is in U.S. Patent No. 4,464, and the smog inhibitor that uses in 502 is zinc oxide and magnesian mixture.
Gupta is in U.S. Patent No. 4,593, and the smog inhibitor that uses in 060 contains tin oxalate or caoxalate or zinc oxide, magnesium oxide, titanium oxide.
These materials in the above-mentioned patent all have certain smoke suppressing effect to fire retardant material, but all there is a general problem, be that these additive dosages that suppress smog are all bigger than normal, general ratio shared in whole fire retardant material is about 7 ~ 10%, therefore influenced the impact property of other performances, particularly material of material widely.
For this reason, be necessary to search out a kind of smoke suppression more efficiently system, with when reaching inhibition smog, guarantee other performances of material, particularly impact property is not affected substantially.
Summary of the invention
The purpose of this invention is to provide that a kind of preparation technology is simple, cost is low, every physical and mechanical properties, particularly impact property, excellent low-smoke and flame retardant glass fibre strengthens the preparation method of PBT matrix material.
For realizing above purpose, technical scheme of the present invention provides a kind of low-smoke and flame retardant glass fibre and strengthens the PBT matrix material, its characteristics are, add a kind of specific surface area big, by the mixed type nano level smog inhibitor that nano zine oxide and nano-calcium carbonate are formed, each component is mixed with by following weight percent: (%)
PBT?????????????????????????????????????45-75
Ten bromines connect phenylate 8-15
Antimonous oxide 3-5
Tetrafluoroethylene 0.2-1
Nano zine oxide 1-5
Nano-calcium carbonate 1-5
Toughness reinforcing, compatilizer 1.5-20
Oxidation inhibitor 0.2-1
Glass fibre 10-37 wherein, described toughness reinforcing, compatilizer is a kind of ethylene copolymer that contains epoxy-functional, comprises the graft copolymer of the glyceryl ester of ethylene-propylene rubber(EPR) and methacrylic; Described oxidation inhibitor be triglycol two-thermal oxidation stabilizer of a kind of or its combination in 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide, distearyl pentaerythritol diphosphite, thio-2 acid octadecyl ester.The present invention adopts mixture that a kind of nano zine oxide of high-specific surface area and nano-calcium carbonate form to strengthen the smog inhibitor of PBT matrix material as combustion-proof glass fiber, makes that by this properties-correcting agent the be fuming problem of material when the burning solved well.In addition, because this smog inhibitor has the characteristic of high-specific surface area, so its addition can reduce greatly, thereby when guaranteeing to reduce the material amount of being fuming, its influence to material other every physical and mechanical propertiess, particularly impact property significantly reduces.
Among the present invention, PBT is a relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.6～0.9.
In the above-mentioned composite-material formula, it is melt temperature 290-310 ℃ that described ten bromines connect phenylate, heat decomposition temperature＞310 ℃, bromine content＞82%, the white powder of particle diameter 5-10 micron
In the above-mentioned composite-material formula, described antimonous oxide is melt temperature 650-660 ℃, decomposition temperature 1450-1460 ℃, and particle diameter 1500 purpose white powders;
In the above-mentioned composite-material formula, described tetrafluoroethylene is a particle diameter 5-10 micron, apparent density 250-300g/l, fusing point 320-330 ℃.
In the above-mentioned composite-material formula, described nano zine oxide is relative density 0.3-0.5g/ml, particle diameter 10-100 nanometer, specific surface area 120-200m
2/ g.
In the above-mentioned composite-material formula, described nano-calcium carbonate is relative density 2.60-2.75g/cm
3, particle diameter 25-40 nanometer, specific surface area 25-35m
2/ g.
In the above-mentioned composite-material formula, described glass fiber diameter is the 6-17 micron.
The preparation method that a kind of low-smoke and flame retardant glass fibre of the present invention strengthens the PBT matrix material is as follows:
(1) each component by weight percentage composition weigh raw material;
(2) glass fibre is handled through silane coupling agent;
(3) PBT, ten bromines being connected phenylate, antimonous oxide, tetrafluoroethylene, nano zine oxide, nano-calcium carbonate, compatilizer, thermal oxidation stabilizer did in super mixer mixed 3-5 minute;
(4) raw materials mixed is placed dual-screw-stem machine mixed with glass fibre, through melt extrude, granulation, its technology is: in each heating region of screw rod, 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
In order to improve the consistency of glass fibre and PBT, described silane coupling agent is at least vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, a kind of in compound of this group of γ-methyl coloured glaze base propyl trimethoxy silicane and γ-r-chloropropyl trimethoxyl silane.Be preferably γ-An Bingjisanyiyangjiguiwan.
Advantage of the present invention is:
1, the present invention has used smog inhibitor efficiently, and the amount of being fuming of obtained matrix material is little.
2, the prepared low-smoke and flame retardant glass fibre enhancing of the present invention PBT matrix material has the characteristics of high impact strength simultaneously.
3, the preparation technology of the glass fibre enhancing PBT matrix material of the present invention's proposition is simple, cost is low.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
In the embodiment composite-material formula, it is melt temperature 290-310 ℃ that ten bromines connect phenylate, heat decomposition temperature＞310 ℃, bromine content＞82%, the white powder of particle diameter 5-10 micron; Antimonous oxide is melt temperature 650-660 ℃, decomposition temperature 1450-1460 ℃, and particle diameter 1500 purpose white powders; Tetrafluoroethylene is a particle diameter 5-10 micron, apparent density 250-300g/l, fusing point 320-330 ℃; Nano zine oxide is relative density 0.3-0.5g/ml, particle diameter 10-100 nanometer, specific surface area 120-200m
2/ g; Nano-calcium carbonate is relative density 2.60-2.75g/cm
3, particle diameter 25-40 nanometer, specific surface area 25-35m
2/ g; Toughness reinforcing, compatilizer produces for Dupont company, and trade names are the ethylene copolymer that contains epoxy-functional of Elvaloy PTW; Glass fibre is handled through silane coupling agent KH55, and diameter is the 6-17 micron, and wherein silane coupling agent KH550 is that Yaohua Glass-making Plant, Shanghai produces, and chemical name is a γ-An Bingjisanyiyangjiguiwan; Thermal oxidation stabilizer 245 is that Ciba company produces, and trade names are Irganox 245, chemical name be triglycol two-3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide; Thermal oxidation stabilizer 618 produces for GE company, and trade names are Weston 618, and chemical name is a distearyl pentaerythritol diphosphite; Thermal oxidation stabilizer DSTP is that Britain ICE company produces, and trade names are Negonox DSTP, and chemical name is the thio-2 acid octadecyl ester; PBT is a relative density 1.31 ~ 1.35,220 ~ 230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.6 ~ 0.9.
Embodiment 1
With the PBT weight ratio is that 51.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 1%, nano-calcium carbonate 1%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through 230～255 ℃ melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 2
With the PBT weight ratio is that 49.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 2%, nano-calcium carbonate 2%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 3
With the PBT weight ratio is that 47.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 3%, nano-calcium carbonate 3%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 mouthfuls in two districts, 235～255 mouthfuls in three districts, 240～250 mouthfuls in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 4
With the PBT weight ratio is that 45.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 4%, nano-calcium carbonate 4%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 5
With the PBT weight ratio is that 49.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 1%, nano-calcium carbonate 3%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 6
With the PBT weight ratio is that 48.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 1%, nano-calcium carbonate 4%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 7
With the PBT weight ratio is that 50.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 2%, nano-calcium carbonate 1%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 8
With the PBT weight ratio is that 48.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 2%, nano-calcium carbonate 3%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 9
With the PBT weight ratio is that 47.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 2%, nano-calcium carbonate 4%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 10
With the PBT weight ratio is that 49.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 3%, nano-calcium carbonate 1%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Embodiment 11
With the PBT weight ratio is that 48.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 3%, nano-calcium carbonate 2%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Comparative Examples 1
With the PBT weight ratio is that 53.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Comparative Examples 2
With the PBT weight ratio is that 48.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano zine oxide 5%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Comparative Examples 3
With the PBT weight ratio is that 48.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, nano-calcium carbonate 5%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Comparative Examples 4
With the PBT weight ratio is that 48.3%, ten bromines connect phenylate 10%, antimonous oxide 3.5%, tetrafluoroethylene 0.5%, regular grade zinc oxide 3%, regular grade lime carbonate 2%, PTW2.5% and 1010,0.2% is dried mixed under room temperature state in super mixer, afterwards, glass fibre 30% blending of handling through coupling agent KH550 with the surface at twin screw extruder again, through melt extrude, granulation makes matrix material.Wherein, each heating region temperature setting of screw rod is respectively: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; Staying the time is 1-2 minute, and pressure is 12-18Mpa.
Performance evaluation mode and implementation standard:
With the particulate material of finishing granulation as stated above in 120～140 ℃ convection oven dry 4～8 hours in advance, and then the particulate material that drying is good carried out the injection molding sample preparation on injection moulding machine.The injection mold temperature control is about 100 ℃.
The tensile property test is undertaken by ISO 527-2, and specimen size is 150*10*4mm, and draw speed is 50mm/min; The bending property test is undertaken by ISO 178, and specimen size is 80*10*4mm, and rate of bending is 2mm/min, and span is 64mm; Simple beam impact strength is undertaken by ISO 179, and specimen size is 55*6*4mm, and notch depth is 1/3rd of a sample thickness; Heat-drawn wire is undertaken by ISO 75, and specimen size is 127*12.7*3.2mm, and load is 1.82MPa; The test of the material amount of being fuming is tested by the smoke density of 662 pairs of materials of ASTM E, and specimen size is 7.6*7.6*2.5cm.
Comprehensive mechanical performance is passed through the tensile strength of test gained, elongation at break, and the numerical value of modulus in flexure and shock strength is passed judgment on; The amount of being fuming of material measures examination institute value and passes judgment on by being fuming.
The prescription of embodiment 1-11 and Comparative Examples 1-4 and every The performance test results be each table as follows:
Table 1 embodiment 1-4 prescription and material property table
| The matrix material title | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| ??PBT(％) | ????51.3 | ????49.3 | ????47.3 | ????45.3 |
| Ten bromines connect phenylate (%) | ????10 | ????10 | ????10 | ????10 |
| Antimonous oxide (%) | ????3.5 | ????3.5 | ????3.5 | ????3.5 |
| Tetrafluoroethylene (%) | ????0.5 | ????0.5 | ????0.5 | ????0.5 |
| Nano zine oxide (%) | ????1 | ????2 | ????3 | ????4 |
| Nano-calcium carbonate (%) | ????1 | ????2 | ????3 | ????4 |
| ??PTW(％) | ????2.5 | ????2.5 | ????2.5 | ????2.5 |
| ??1010(％) | ????0.2 | ????0.2 | ????0.2 | ????0.2 |
| Glass fibre (%) | ????30 | ????30 | ????30 | ????30 |
| Heat-drawn wire (1.82MPa) () | ????208 | ????209 | ????210 | ????210 |
| Unnotched impact strength (kJ/m 2) | ????43 | ????42 | ????38 | ????32 |
| Tensile strength (MPa) | ????115 | ????113 | ????112 | ????105 |
| Elongation at break (%) | ????2.5 | ????2.5 | ????2.2 | ????2.0 |
| Flexural strength (MPa) | ????180 | ????177 | ????177 | ????168 |
| Modulus in flexure (MPa) | ????9500 | ????11000 | ????12500 | ????13000 |
| Smoke density | ????215 | ????130 | ????125 | ????120 |
From the embodiment of table 1 as can be seen, nano zine oxide and nano calcium oxide are very big to the amount of the being fuming influence of material, and along with the increase of these two kinds of additive dosages in the material, the amount of being fuming of material significantly reduces.But the data from table can see that the impact property of material is subjected to the influence of these two kinds of auxiliary agents also very big simultaneously, and along with the increase of these two kinds of additive dosages in the material, the impact property of material descends also very obviously.So must reduce the usage quantity of these two kinds of auxiliary agents as far as possible.
Table 2 embodiment 5-11 prescription and material property table
| The matrix material title | Embodiment 5 | Embodiment 6 | Embodiment 7 | Embodiment 8 | Embodiment 9 | Embodiment 10 | Embodiment 11 |
| ????PBT(％) | ???49.3 | ???48.3 | ???50.3 | ???48.3 | ???47.3 | ???49.3 | ???48.3 |
| Ten bromines connect phenylate (%) | ???10 | ???10 | ???10 | ???10 | ???10 | ???10 | ???10 |
| Antimonous oxide (%) | ???3.5 | ???3.5 | ???3.5 | ???3.5 | ???3.5 | ???3.5 | ???3.5 |
| Tetrafluoroethylene (%) | ???0.5 | ???0.5 | ???0.5 | ???0.5 | ???0.5 | ???0.5 | ???0.5 |
| Nano zine oxide (%) | ???1 | ???1 | ???2 | ???2 | ???2 | ???3 | ???3 |
| Nano-calcium carbonate (%) | ???3 | ???4 | ???1 | ???3 | ???4 | ???1 | ???2 |
| ????PTW(％) | ???2.5 | ???2.5 | ???2.5 | ???2.5 | ???2.5 | ???2.5 | ???2.5 |
| ????1010(％) | ???0.2 | ???0.2 | ???0.2 | ???0.2 | ???0.2 | ???0.2 | ???0.2 |
| Glass fibre (%) | ???30 | ???30 | ???30 | ???30 | ???30 | ???30 | ???30 |
| Heat-drawn wire (1.82MPa) () | ???210 | ???210 | ???210 | ???210 | ???210 | ???210 | ???210 |
| Unnotched impact strength (kJ/m 2) | ???44 | ???38 | ???42 | ???39 | ???35 | ???41 | ???37 |
| Tensile strength (MPa) | ???115 | ???113 | ???112 | ???111 | ???108 | ???110 | ???109 |
| Elongation at break (%) | ???2.5 | ???2.5 | ???2.2 | ???2.2 | ???1.9 | ???2.3 | ???2.2 |
| Flexural strength (MPa) | ???180 | ???177 | ???175 | ???168 | ???162 | ???176 | ???170 |
| Modulus in flexure (MPa) | ???9500 | ???11000 | ???12500 | ???13000 | ???13000 | ???10000 | ???12500 |
| The amount of being fuming (mm) | ???190 | ???170 | ???135 | ???130 | ???128 | ???135 | ???130 |
The embodiment of associative list 1 and table 2 can see, the total addition level of nano zine oxide and nano-calcium carbonate can be controlled at about 3 parts of total mass percentage amounts, and the ratio between nano zine oxide and the nano-calcium carbonate is about 2: 1, the amount of being fuming of material and other physical and mechanical propertiess particularly reach optimal counterbalance effect between the impact property at this moment.
Table 3 Comparative Examples 1-4 prescription and material property table
| The matrix material title | Comparative Examples 1 | Comparative Examples 2 | Comparative Examples 3 | Comparative Examples 4 |
| ????PBT(％) | ????53.3 | ????48.3 | ????48.3 | ???48.3 |
| Ten bromines connect phenylate (%) | ????10 | ????10 | ????10 | ???10 |
| Antimonous oxide (%) | ????3.5 | ????3.5 | ????3.5 | ???3.5 |
| Tetrafluoroethylene (%) | ????0.5 | ????0.5 | ????0.5 | ???0.5 |
| Nano zine oxide (%) | ????- | ????5 | ????- | ???- |
| Nano-calcium carbonate (%) | ????- | ????- | ????5 | ???- |
| Regular grade zinc oxide (%) | ????- | ????- | ????- | ???3 |
| Regular grade lime carbonate (%) | ????- | ????- | ????- | ???2 |
| ????PTW(％) | ????2.5 | ????2.5 | ????2.5 | ???2.5 |
| ????1010(％) | ????0.2 | ????0.2 | ????0.2 | ???0.2 |
| Glass fibre (%) | ????30 | ????30 | ????30 | ???30 |
| Heat-drawn wire (1.82MPa) () | ????211 | ????208 | ????206 | ???210 |
| Unnotched impact strength (kJ/m 2) | ????44 | ????36 | ????38 | ???32 |
| Tensile strength (MPa) | ????115 | ????113 | ????112 | ???105 |
| Elongation at break (%) | ????2.5 | ????2.5 | ????2.2 | ???2.0 |
| Flexural strength (MPa) | ????180 | ????177 | ????175 | ???162 |
| Modulus in flexure (MPa) | ????9500 | ????11000 | ????12500 | ???13000 |
| The amount of being fuming (mm) | ????350 | ????170 | ????190 | ???145 |
Can see that from table 3 Comparative Examples its amount of being fuming of material of not adding any smog inhibitor is very big.And when single interpolation nano zine oxide or nano calcium oxide, they press down cigarette action effect and not obvious to material.In addition, the zinc oxide of regular grade and calcium oxide also exist this problem, and simultaneously, because addition is excessive, the impact property of material also is subjected to very big influence.
Claims (9)
1. a low-smoke and flame retardant glass fibre strengthens the PBT matrix material, comprise PBT, glass fibre, it is characterized in that, comprise that also mixed type nanometer smog inhibitor, ten bromines connect phenylate ten bromines and connect phenylate, antimonous oxide, tetrafluoroethylene, nano zine oxide, nano-calcium carbonate, toughness reinforcing and compatilizer and oxidation inhibitor in the glass fibre enhancing PBT matrix material, each component is mixed with (%) by following weight percent:
PBT????????????????????????????45-75
Ten bromines connect phenylate 8-15
Antimonous oxide 3-5
Tetrafluoroethylene 0.2-1
Nano zine oxide 1-5
Nano-calcium carbonate 1-5
Toughness reinforcing, compatilizer 1.5-20
Oxidation inhibitor 0.2-1
Glass fibre 10-37
Wherein, described toughness reinforcing, compatilizer is a kind of ethylene copolymer that contains epoxy-functional, comprises the graft copolymer of the glyceryl ester of ethylene-propylene rubber(EPR) and methacrylic; Described oxidation inhibitor be triglycol two-thermal oxidation stabilizer of a kind of or its combination in 3-(3-tertiary butyl-4-hydroxy-5-aminomethyl phenyl) vinyl cyanide, distearyl pentaerythritol diphosphite, thio-2 acid octadecyl ester.
2. a kind of low-smoke and flame retardant glass fibre according to claim 1 strengthens the PBT matrix material, it is characterized in that described PBT is a relative density 1.31～1.35,220～230 ℃ of fusing points, the polybutylene terephthalate of melt viscosity 0.6～0.9.
3. a kind of low-smoke and flame retardant glass fibre according to claim 1 strengthens the PBT matrix material, it is characterized in that it is melt temperature 290-310 ℃ that described ten bromines connect phenylate, heat decomposition temperature＞310 ℃, bromine content＞82%, the white powder of particle diameter 5-10 micron.
4. a kind of low-smoke and flame retardant glass fibre according to claim 1 strengthens the PBT matrix material, it is characterized in that described antimonous oxide is melt temperature 650-660 ℃, and decomposition temperature 1450-1460 ℃, particle diameter 1500 purpose white powders.
5. a kind of low-smoke and flame retardant glass fibre according to claim 1 strengthens the PBT matrix material, it is characterized in that described tetrafluoroethylene is a particle diameter 5-10 micron, apparent density 250-300g/l, fusing point 320-330 ℃.
6. a kind of low-smoke and flame retardant glass fibre according to claim 1 strengthens the PBT matrix material, it is characterized in that described glass fiber diameter is the 6-17 micron.
7. a kind of low-smoke and flame retardant glass fibre according to claim 1 strengthens the PBT matrix material, it is characterized in that its method is as follows:
(1) each component by weight percentage composition weigh raw material;
(2) glass fibre is handled through silane coupling agent;
(3) PBT, ten bromines being connected phenylate, antimonous oxide, tetrafluoroethylene, nano zine oxide, nano-calcium carbonate, compatilizer, thermal oxidation stabilizer did in super mixer mixed 3-5 minute;
(4) raw materials mixed is placed dual-screw-stem machine mixed with glass fibre, through melt extrude, granulation, its technology is: 230～250 ℃ in a district, 235～255 ℃ in two districts, 235～255 ℃ in three districts, 240～250 ℃ in four districts; The residence time is 1-2 minute, and pressure is 12-18Mpa.
8. a kind of low-smoke and flame retardant glass fibre according to claim 7 strengthens the PBT matrix material, it is characterized in that, described silane coupling agent is at least vinyl trichloro silane, vinyl three (beta-methoxy-oxyethyl group) silane, vinyltriethoxysilane, γ-metacryloxy propyl trimethoxy silicane, β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidoxypropyltrimewasxysilane, N-(beta-aminoethyl)-gamma-amino propyl trimethoxy silicane, γ-An Bingjisanyiyangjiguiwan, N-phenyl-gamma-amino propyl trimethoxy silicane, a kind of in compound of this group of γ-methyl coloured glaze base propyl trimethoxy silicane and γ-r-chloropropyl trimethoxyl silane.
9. a kind of low-smoke and flame retardant glass fibre according to claim 8 strengthens the PBT matrix material, it is characterized in that described silane coupling agent is a γ-An Bingjisanyiyangjiguiwan.
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