CN1357027A - Flameproof extrudates and flameproof moulded bodies produced by means of pressing methods - Google Patents
Flameproof extrudates and flameproof moulded bodies produced by means of pressing methods Download PDFInfo
- Publication number
- CN1357027A CN1357027A CN99814549A CN99814549A CN1357027A CN 1357027 A CN1357027 A CN 1357027A CN 99814549 A CN99814549 A CN 99814549A CN 99814549 A CN99814549 A CN 99814549A CN 1357027 A CN1357027 A CN 1357027A
- Authority
- CN
- China
- Prior art keywords
- weight part
- extrudate
- thermoplastic composition
- weight
- compression moulding
- 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.)
- Pending
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- 238000003825 pressing Methods 0.000 title description 2
- -1 pentabrombenzyl Chemical group 0.000 claims abstract description 39
- 229920001283 Polyalkylene terephthalate Polymers 0.000 claims abstract description 21
- 239000000203 mixture Substances 0.000 claims description 33
- 239000004417 polycarbonate Substances 0.000 claims description 29
- 229920000515 polycarbonate Polymers 0.000 claims description 29
- 229920001169 thermoplastic Polymers 0.000 claims description 25
- 239000004416 thermosoftening plastic Substances 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 20
- 238000000748 compression moulding Methods 0.000 claims description 14
- 238000000576 coating method Methods 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 10
- 230000000996 additive effect Effects 0.000 claims description 10
- 229920002125 Sokalan® Polymers 0.000 claims description 9
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 229940058905 antimony compound for treatment of leishmaniasis and trypanosomiasis Drugs 0.000 claims description 5
- 150000001463 antimony compounds Chemical class 0.000 claims description 5
- 229920000098 polyolefin Polymers 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000000314 lubricant Substances 0.000 claims description 2
- 239000000049 pigment Substances 0.000 claims description 2
- 239000003381 stabilizer Substances 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 39
- 125000003118 aryl group Chemical group 0.000 description 34
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 27
- 238000000034 method Methods 0.000 description 17
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 16
- 238000002360 preparation method Methods 0.000 description 14
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 12
- 229920001707 polybutylene terephthalate Polymers 0.000 description 12
- 150000001263 acyl chlorides Chemical class 0.000 description 8
- 238000002485 combustion reaction Methods 0.000 description 8
- 239000000206 moulding compound Substances 0.000 description 8
- 239000006085 branching agent Substances 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 229920001400 block copolymer Polymers 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000001294 propane Substances 0.000 description 6
- 239000000523 sample Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical group OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 230000002265 prevention Effects 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 3
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 3
- 229930185605 Bisphenol Natural products 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 125000005843 halogen group Chemical group 0.000 description 3
- 150000002367 halogens Chemical class 0.000 description 3
- 229940051250 hexylene glycol Drugs 0.000 description 3
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229920001634 Copolyester Polymers 0.000 description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- YGYAWVDWMABLBF-UHFFFAOYSA-N Phosgene Chemical compound ClC(Cl)=O YGYAWVDWMABLBF-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- VCCBEIPGXKNHFW-UHFFFAOYSA-N biphenyl-4,4'-diol Chemical group C1=CC(O)=CC=C1C1=CC=C(O)C=C1 VCCBEIPGXKNHFW-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 125000001246 bromo group Chemical group Br* 0.000 description 2
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical group OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 description 2
- 125000005587 carbonate group Chemical group 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical group 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- MIHINWMALJZIBX-UHFFFAOYSA-N cyclohexa-2,4-dien-1-ol Chemical compound OC1CC=CC=C1 MIHINWMALJZIBX-UHFFFAOYSA-N 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000004079 fireproofing Methods 0.000 description 2
- 150000005826 halohydrocarbons Chemical class 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 125000004464 hydroxyphenyl group Chemical group 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 125000005386 organosiloxy group Chemical group 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 230000001915 proofreading effect Effects 0.000 description 2
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 2
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- YIYBRXKMQFDHSM-UHFFFAOYSA-N 2,2'-Dihydroxybenzophenone Chemical compound OC1=CC=CC=C1C(=O)C1=CC=CC=C1O YIYBRXKMQFDHSM-UHFFFAOYSA-N 0.000 description 1
- XSXWOBXNYNULJG-UHFFFAOYSA-N 2-(2,4,4-trimethylpentan-2-yl)phenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1O XSXWOBXNYNULJG-UHFFFAOYSA-N 0.000 description 1
- VXHYVVAUHMGCEX-UHFFFAOYSA-N 2-(2-hydroxyphenoxy)phenol Chemical compound OC1=CC=CC=C1OC1=CC=CC=C1O VXHYVVAUHMGCEX-UHFFFAOYSA-N 0.000 description 1
- XSVZEASGNTZBRQ-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfinylphenol Chemical compound OC1=CC=CC=C1S(=O)C1=CC=CC=C1O XSVZEASGNTZBRQ-UHFFFAOYSA-N 0.000 description 1
- QUWAJPZDCZDTJS-UHFFFAOYSA-N 2-(2-hydroxyphenyl)sulfonylphenol Chemical compound OC1=CC=CC=C1S(=O)(=O)C1=CC=CC=C1O QUWAJPZDCZDTJS-UHFFFAOYSA-N 0.000 description 1
- KAIRTVANLJFYQS-UHFFFAOYSA-N 2-(3,5-dimethylheptyl)phenol Chemical compound CCC(C)CC(C)CCC1=CC=CC=C1O KAIRTVANLJFYQS-UHFFFAOYSA-N 0.000 description 1
- NFAOATPOYUWEHM-UHFFFAOYSA-N 2-(6-methylheptyl)phenol Chemical compound CC(C)CCCCCC1=CC=CC=C1O NFAOATPOYUWEHM-UHFFFAOYSA-N 0.000 description 1
- KYGLCUAXJICESS-UHFFFAOYSA-N 2-[2,3-di(propan-2-yl)phenyl]phenol Chemical compound CC(C)C1=CC=CC(C=2C(=CC=CC=2)O)=C1C(C)C KYGLCUAXJICESS-UHFFFAOYSA-N 0.000 description 1
- WRLVTKZXVVEUPL-UHFFFAOYSA-N 2-chloro-4-propylphenol Chemical compound CCCC1=CC=C(O)C(Cl)=C1 WRLVTKZXVVEUPL-UHFFFAOYSA-N 0.000 description 1
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 1
- UIFVAJJGMKREPN-UHFFFAOYSA-N 3-(4-propylphenyl)propan-1-ol Chemical compound CCCC1=CC=C(CCCO)C=C1 UIFVAJJGMKREPN-UHFFFAOYSA-N 0.000 description 1
- WNLHHAAYHRAAKQ-UHFFFAOYSA-N 4-(2-methylbutyl)phenol Chemical compound CCC(C)CC1=CC=C(O)C=C1 WNLHHAAYHRAAKQ-UHFFFAOYSA-N 0.000 description 1
- ASURBSPIYIISGI-UHFFFAOYSA-N 4-(3,3,5-trimethylcyclohexyl)phenol Chemical compound C1C(C)(C)CC(C)CC1C1=CC=C(O)C=C1 ASURBSPIYIISGI-UHFFFAOYSA-N 0.000 description 1
- UITKHKNFVCYWNG-UHFFFAOYSA-N 4-(3,4-dicarboxybenzoyl)phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 UITKHKNFVCYWNG-UHFFFAOYSA-N 0.000 description 1
- CUAUDSWILJWDOD-UHFFFAOYSA-N 4-(3,5-dimethylheptyl)phenol Chemical compound CCC(C)CC(C)CCC1=CC=C(O)C=C1 CUAUDSWILJWDOD-UHFFFAOYSA-N 0.000 description 1
- HJSPWKGEPDZNLK-UHFFFAOYSA-N 4-benzylphenol Chemical class C1=CC(O)=CC=C1CC1=CC=CC=C1 HJSPWKGEPDZNLK-UHFFFAOYSA-N 0.000 description 1
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 1
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 description 1
- DRAVTYHHOIJUOB-UHFFFAOYSA-N 4-hept-1-enylphenol Chemical compound CCCCCC=CC1=CC=C(O)C=C1 DRAVTYHHOIJUOB-UHFFFAOYSA-N 0.000 description 1
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- KNDDEFBFJLKPFE-UHFFFAOYSA-N 4-n-Heptylphenol Chemical compound CCCCCCCC1=CC=C(O)C=C1 KNDDEFBFJLKPFE-UHFFFAOYSA-N 0.000 description 1
- YVPZFPKENDZQEJ-UHFFFAOYSA-N 4-propylcyclohexan-1-ol Chemical compound CCCC1CCC(O)CC1 YVPZFPKENDZQEJ-UHFFFAOYSA-N 0.000 description 1
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FDEQQCOTLPPCAO-UHFFFAOYSA-N Cl.OC(O)=O Chemical class Cl.OC(O)=O FDEQQCOTLPPCAO-UHFFFAOYSA-N 0.000 description 1
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical group CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 1
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- AJBXRBRVQMZREG-UHFFFAOYSA-N OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)CCC Chemical compound OC(CC)(C1=CC=CC=C1)O.OC1=CC=C(C=C1)CCC AJBXRBRVQMZREG-UHFFFAOYSA-N 0.000 description 1
- JPYHHZQJCSQRJY-UHFFFAOYSA-N Phloroglucinol Natural products CCC=CCC=CCC=CCC=CCCCCC(=O)C1=C(O)C=C(O)C=C1O JPYHHZQJCSQRJY-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
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- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
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- 125000001118 alkylidene group Chemical group 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
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- 238000000149 argon plasma sintering Methods 0.000 description 1
- 150000004646 arylidenes Chemical class 0.000 description 1
- 125000004104 aryloxy group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
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- 239000004305 biphenyl Substances 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
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- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
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- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
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- 125000004185 ester group Chemical group 0.000 description 1
- FYIBGDKNYYMMAG-UHFFFAOYSA-N ethane-1,2-diol;terephthalic acid Chemical compound OCCO.OC(=O)C1=CC=C(C(O)=O)C=C1 FYIBGDKNYYMMAG-UHFFFAOYSA-N 0.000 description 1
- 230000009970 fire resistant effect Effects 0.000 description 1
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- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
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- OJURWUUOVGOHJZ-UHFFFAOYSA-N methyl 2-[(2-acetyloxyphenyl)methyl-[2-[(2-acetyloxyphenyl)methyl-(2-methoxy-2-oxoethyl)amino]ethyl]amino]acetate Chemical compound C=1C=CC=C(OC(C)=O)C=1CN(CC(=O)OC)CCN(CC(=O)OC)CC1=CC=CC=C1OC(C)=O OJURWUUOVGOHJZ-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
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- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 description 1
- OLAPPGSPBNVTRF-UHFFFAOYSA-N naphthalene-1,4,5,8-tetracarboxylic acid Chemical compound C1=CC(C(O)=O)=C2C(C(=O)O)=CC=C(C(O)=O)C2=C1C(O)=O OLAPPGSPBNVTRF-UHFFFAOYSA-N 0.000 description 1
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical compound C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 229940090668 parachlorophenol Drugs 0.000 description 1
- 229940059574 pentaerithrityl Drugs 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000005003 perfluorobutyl group Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)* 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- QCDYQQDYXPDABM-UHFFFAOYSA-N phloroglucinol Chemical compound OC1=CC(O)=CC(O)=C1 QCDYQQDYXPDABM-UHFFFAOYSA-N 0.000 description 1
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- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 1
- 229960001755 resorcinol Drugs 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000009757 thermoplastic moulding Methods 0.000 description 1
- 229920005992 thermoplastic resin Polymers 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 238000005809 transesterification reaction Methods 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Chemical group 0.000 description 1
- JLYXXMFPNIAWKQ-UHFFFAOYSA-N γ Benzene hexachloride Chemical compound ClC1C(Cl)C(Cl)C(Cl)C(Cl)C1Cl JLYXXMFPNIAWKQ-UHFFFAOYSA-N 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
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
-
- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur, or oxygen atoms in addition to the carboxy oxygen
- C08L33/16—Homopolymers or copolymers of esters containing halogen atoms
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2300/00—Characterised by the use of unspecified polymers
- C08J2300/22—Thermoplastic resins
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- 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
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- Engineering & Computer Science (AREA)
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- Materials Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
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- Organic Insulating Materials (AREA)
Abstract
The invention relates to flameproof extrudates, especially films, sheets and cable sheaths, with a polyalkylene terephthalate and pentabrombenzyl polyacrylate (PBBPA) base. The inventive extrudates have an improved breaking stress and elongation at break, improved electrical properties and an improved surface finish.
Description
The present invention relates to based on polyalkylene terephthalates and polyacrylic acid pentabromobenzyl ester (PBBPA), have the tear strength of improvement and tear fire prevention extrudate, especially film, sheet material and the electric wire coatings of elongation (rupture stress and extension at break), electrical property and surface quality.
For example can know for 80 (1990) the 3rd～4 pages, can make plastics, have fire performance as thermosetting resin, elastomerics, polymeric amide, polycarbonate etc. by using halohydrocarbon from document Kunststoffe (plastics).
Has good fire-resistant effect though contain the plastic components of halohydrocarbon as can be seen from above-mentioned reference, but owing to wherein used the Halogen fire-proof additive, so its surface quality is relatively poor, therefore can not produce fireproof membrane or the very thin moulded product of wall thickness from PBT.
That EP-A 344 700 has narrated is single-and polyacrylic acid pentabromobenzyl ester and as the purposes of thermoplastic resin fireproofing agent.But there are not to describe the extrudate with the performance that requires, for example film and sheet material in the document.
The purpose of this invention is to provide based on polyalkylene terephthalates and a kind of commercially available inexpensive thereby be the fire prevention extrudate of economic fireproofing agent, as film, sheet material and electric wire coatings, this extrudate has the tear strength of the electrical property of great surface quality, improvement and improvement and tears elongation (rupture stress and extension at break), and can be from thermoplastic composition with simple method conventional art, for example method productions such as extrusion molding, blowing, pressing mold.
Have now found that, with compression moulding production based on polyalkylene terephthalates and contain the extrudate (film, sheet material and electric wire coatings) of polyacrylic acid pentabromobenzyl ester (PBBPA) and moulded product has excellent surface quality and good flowability, has extraordinary fire performance simultaneously, and high tear strength and tear elongation (rupture stress and extension at break), its electrical property excellence, other performance is also good, and thermoplastic matrix is not damaged yet.Of the present inventionly be that further this thermoplastic composition based on polyalkylene terephthalates and PBBPA can be with good method, for example be processed into extrudate (film, sheet material and electric wire coatings), and be processed into moulded product by compression moulding by methods such as extrusion molding, blowing, loom involve.Extrudate (film, sheet material and electric wire coatings) and the moulded product produced with compression moulding according to the present invention can adopt conventional art, and for example deep-draw is further processed, and print and/or laser beam marking.
The invention provides moulded product and the extrudate produced by compression moulding, especially film, sheet material and electric wire coatings, these products are all based on the thermoplastic composition that contains following component:
A) 55-97.7 weight part, preferred 60-95.5 weight part, the polyalkylene terephthalates of 70-95 weight part especially,
B) 2-30 weight part, preferred 3-25 weight part, the polyacrylic acid pentabromobenzyl ester of 4-20 weight part especially,
C) 0.3-12 weight part, preferred 0.5-10 weight part, especially the antimony compounds of 1-8 weight part and
D) polycarbonate of 0-90 weight part and/or polyestercarbonate,
A wherein)+B)+C)+D) summation is 100, and the polyalkylene terephthalates of maximum 10 weight parts can replace with polyolefine.
Extrudate (film, sheet material and electric wire coatings) and can be with the moulded product of compression moulding production from containing said components A) to D) thermoplastic composition obtain.The characteristics of this thermoplastic composition be have good fire resistance properties, thermoplastic matrix is not damaged, and also has the electrical property of great surface quality and improvement simultaneously, and because its good flowability, thereby is particularly suitable for producing film and sheet material.
The thermoplastic composition that the present invention also relates to contain said components is used to produce fire prevention extrudate (film, sheet material and electric wire coatings) that performances such as extension at break, rupture stress and surface quality make moderate progress and the purposes of the fireproof molded articles produced with compression moulding.
Term " film " is often referred to can rolled-up material, and sheet material is inflexible normally then, therefore can not roll.
Film in the scope of the invention generally has＜1200 μ m, preferred 25-1000 μ m, the especially thickness of 50-850 μ m.
Sheet material in the scope of the invention generally has several centimetres of 1.2mm-, preferred 1.2mm-4cm, the especially thickness of 1.2mm-2.5cm.
Component A
Polyalkylene terephthalates (component A) in the scope of the invention is the reaction product of aromatic dicarboxylic acid or its reactive derivatives (for example dimethyl ester or acid anhydride) and aliphatic series, cyclic aliphatic or araliphatic glycol, and the mixture of these reaction product.
Preferred polyalkylene terephthalates can be passed through currently known methods (Kunststoff-Handbuch (plastics handbook) from terephthalic acid (or its reactive derivatives) and the aliphatic series or the cycloaliphatic diol that contain 2-10 carbon atom, the VIII volume, the 695th page is risen, Karl-Hanser publishing company, Munich, 1973) preparation.
Preferred polyalkylene terephthalates contains and accounts at least 80 moles of % of dicarboxylic acid, the terephthalic acid group of preferred 90 moles of % and account at least 80 moles of % of diol component, the ethylene glycol of preferred 90 moles of % and/or 1,4-butyleneglycol group or itself and 1, the mixture of 4-cyclohexanediol.
Preferred polyalkylene terephthalates is except that containing the terephthalic acid group, also can contain other aromatic dicarboxylic acid group that contains 8-14 carbon atom of 20 moles of % at the most or contain the aliphatic dicarboxylic acid group of 4-12 carbon atom, for example phthalic acid, m-phthalic acid, 2,6-naphthalic acid, 4,4 '-group of diphenyl dicarboxylic acid, succsinic acid, hexanodioic acid, sebacic acid, nonane diacid, hexamethylene ring oxalic acid.
Preferred polyalkylene terephthalates is removed and is contained ethylene glycol and/or 1, outside the 4-butyleneglycol group, also can contain other aliphatic diol that contains 3-12 carbon atom of 20 moles of % at the most or contain the group of the cycloaliphatic diol of 6-21 carbon atom, for example, 1, ammediol, 2-ethyl-1, ammediol, neopentyl glycol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 4-cyclohexanediol, 1, the 4-cyclohexanedimethanol, 3-methyl-2, the 4-pentanediol, 2-methyl-2, the 4-pentanediol, 2,2,4-trimethylammonium-1,3-pentanediol and-1,6,2-ethyl-1, the 3-hexylene glycol, 2,2-diethyl-1, ammediol, 2, the 5-hexylene glycol, 1,4-two (beta-hydroxy oxyethyl group)-benzene, 2,2-two (4-hydroxy-cyclohexyl)-propane, 2,4-dihydroxyl-1,1,3,3-tetramethyl--tetramethylene, 2,2-two (3-beta-hydroxy ethoxyl phenenyl) propane and 2, (DE-OS 2407674 for the group of 2-two (4-hydroxypropyl phenyl)-propane, 2407776,2715932).
Can by add three of relatively small amount-or tetravalent alcohol or three-or the quaternary carboxylic acid make polyalkylene terephthalates branching, described in DE-OS 1900270 and US-A 3692744, the example of preferred branching agent is 1,3,5-benzenetricarboxylic acid, trimellitic acid, trimethylolethane and TriMethylolPropane(TMP) and tetramethylolmethane.
Suggestion is used and is accounted for the acid constituents branching agent of 1 mole of % at the most.
Only particularly preferably be from terephthalic acid and reactive derivatives (for example its dialkyl) thereof and be selected from ethylene glycol, 1,4-butyleneglycol and 1, the polyalkylene terephthalates of the glycol of 4-cyclohexanediol or its mixture (poly terephthalic acid ethylene glycol and butanediol ester) preparation, and the mixture of this class polyalkylene terephthalates.
Preferred polyalkylene terephthalates also is that especially preferred copolyester is poly terephthalic acid (ethylene glycol/1, a 4-butyleneglycol) ester from least 2 kinds of above-mentioned acid constituentss and/or from the copolyester of at least 2 kinds of above-mentioned alkoxide components preparations.
The limiting viscosity that is preferably used as the polyalkylene terephthalates of component A is generally about 0.4-1.5dl/g, and preferred 0.5-1.3dl/g all measures in phenol/orthodichlorobenzene (1: 1 weight part) mixed solvent of 25 ℃ in all cases.
B component
Polyacrylic acid pentabromobenzyl ester is normally known, and is described in, for example among the EP-A 344700.This product is commercially available (Dead Sea bromine group company, Beer Sheva, Israel).
PBBPA also can carry out in-situ preparing (EP-A 344700) by the pentabromobenzyl mono acrylic ester is joined in the thermoplastic composition.
Component C
Preferred antimony compounds is ANTIMONY TRIOXIDE SB 203 99.8 PCT and/or antimony pentaoxide, and these are compound known normally.
Component D
The preferable amount of polycarbonate accounts for the 0-75 weight part of moulding compound total amount.
The particularly preferred add-on of polycarbonate is the 20-70 weight part of moulding compound total amount.
Aromatic polycarbonate and/or the aromatic polyestercarbonates according to the component D that are suitable for according to the present invention are known in the document, maybe can be by known method preparation in the document (for the preparation of aromatic polycarbonate, can consult, Schnell for example, " chemistry of polycarbonate and physics ", Interscience publishing company, 1964 and DE-AS 1495625, DE-OS 2232877, DE-OS 2703376, DE-OS 2714544, DE-OS 3000610, DE-OS3832396; For the preparation of aromatic polyestercarbonates, can consult, for example DE-OS3077934).
The preparation of aromatic polycarbonate, for example carry out as follows: make dihydric phenols compound and carbonyl halide, preferred phosgene, and/or with aromatic dicarboxylic acid and two carboxylic acid halides, two carboxylic acid halides of preferred benzene dicarboxylic acid react according to interfacial, randomly use chain terminator, for example monohydric phenol, and randomly use and contain three-functionality-degree or the more branching agent of polyfunctionality, for example trihydric phenol or tetrahydric phenol.
The dihydric phenol that is used to prepare aromatic polycarbonate and/or aromatic polyestercarbonates is the dihydric phenol of formula (I) preferably:
Wherein
A
1Represent singly-bound, C
1-C
5Alkylidene group, C
2-C
5Inclined to one side alkylidene group, C
5-C
6Inclined to one side cycloalkylidene ,-O-,-SO-,-CO-,-S-,-SO
2-, C
6-C
12Arylidene, this arylidene can randomly contain heteroatomic aromatic ring with other and condense, or the group shown in the following formula (II):
Or the group shown in the following formula (III):
B is C independently of one another
1-C
8Alkyl, preferred C
1-C
4Alkyl, methyl especially, halogen, preferred chlorine and/or bromine, C
6-C
10Aryl, preferred phenyl, C
7-C
12Aralkyl, phenyl-C
1-C
4Alkyl, preferred benzyl,
X is 0,1 or 2 independently of one another,
P is 1 or 0, and
R
6And R
7Can individually select each Z, and be hydrogen or C independently of one another
1-C
6Alkyl, preferred hydrogen, methyl and/or ethyl,
Z represents carbon, and
M represents the integer of 4-7, and preferred 4 or 5,
Its condition is at least one Z atom,
R
6And R
7Be alkyl simultaneously.
Preferred dihydric phenol be quinhydrones, resorcin(ol), 4,4 '-dihydroxybiphenyl, two (hydroxyphenyl)-C
1-C
5Paraffinic hydrocarbons, two (hydroxyphenyl)-C
5-C
6Naphthenic hydrocarbon, two (hydroxyphenyl) ether, two (hydroxyphenyl) sulfoxide, two (hydroxyphenyl) ketone, two (hydroxyphenyl) sulfone and α, α-two (hydroxyphenyl)-di-isopropyl-benzene, and their bromination and/or chlorating derivatives on nuclear.
The example of preferred dihydric phenol is 4,4 '-xenol, dihydroxyphenyl propane, 2,4-two (4-hydroxy phenyl)-2-methylbutane, 1,1-two (4-hydroxy phenyl)-hexanaphthene, 1,1-two (4-hydroxy phenyl)-3,3,5-trimethyl-cyclohexane, 4,4 '-dihydroxybiphenyl thioether, 4,4 '-dihydroxybiphenyl base sulfone and they two-and tetrabormated or chlorinated derivatives, for example 2,2-two (3-chloro-4-hydroxy phenyl)-propane, 2,2-two (3,5-two chloro-4-hydroxy phenyls)-propane or 2,2-two (3,5-two bromo-4-hydroxy phenyls)-propane.
Particularly preferably be 2,2-two (4-hydroxy phenyl)-propane (dihydroxyphenyl propane).
Dihydric phenol can use separately or use with the form of mixtures of any hope.
Dihydric phenol is known in the document, perhaps can make by the currently known methods in the document.
The chain terminator that is applicable to the preparation thermoplastic aromatic polycarbonate is, for example phenol, para-chlorophenol, p-tert-butylphenol or 2,4, the 6-tribromophenol, and long chain alkylphenol, as according to DE-OS 2842005 4-(1, the 3-tetramethyl butyl) phenol, or total carbon atom number is an alkylphenol or the dialkyl phenol of 8-20 in the alkyl substituent, as 3, the 5-DI-tert-butylphenol compounds, to isooctyl phenol, to tert-octyl phenol, to dodecyl phenol and 2-(3,5-dimethyl heptyl)-phenol and 4-(3,5-dimethyl heptyl)-phenol.Total mole number in dihydric phenol used in a certain particular case is a benchmark, the general 0.5 mole of %～10 mole % of the consumption of chain terminator.
Thermoplastic aromatic polycarbonate's the molecular-weight average (M that records with ultracentrifuge method or light scattering method for example
w) be 10,000-200,000, be preferably 20,000-80,000.
The thermoplastic aromatic polycarbonate can carry out branching with currently known methods, preferably is the three-functionality-degree of the 0.05-2.0 mole % of used dihydric phenol total amount or the compound of polyfunctionality more by adding its amount, and the compound that for example contains 3 or more a plurality of phenolic group carries out branching.
Homo-polycarbonate and Copolycarbonate all are suitable for.For preparation according to the present invention as for the Copolycarbonate of component A, also can use 1-25 weight %, the polydiorganosiloxane that contains bis (hydroxy-aromatic) oxygen cardinal extremity base of preferred 2.5～25 weight % (total amount in used dihydric phenol is a benchmark).This compounds is known method preparation in known (seeing also for example United States Patent (USP) 3 419 634) or the available document.The preparation that contains the Copolycarbonate of polydiorganosiloxane is described in, for example among the DE-OS 3 334 782.
Preferred polycarbonate, except the homo-polycarbonate of dihydroxyphenyl propane, also have dihydroxyphenyl propane with account for the dihydric phenol total mole number at the most 15 moles of % remove as preferably or especially preferred and those dihydric phenols that mention, especially 2, the Copolycarbonate of the dihydric phenol beyond 2-two (3,5-two bromo-4-hydroxy phenyls)-propane.
Be used to prepare aromatic polyestercarbonates aromatic dicarboxylic acid two carboxylic acid halides preferably m-phthalic acid, terephthalic acid, biphenyl ether 4,4 '-dicarboxylic acid and 2, the diacid chloride of 6-naphthalene dicarboxylic acids.
Particularly preferably be 1: 20-20: the mixture of 1 the m-phthalic acid and the diacid chloride of terephthalic acid.
In the preparation polyestercarbonate, the carboxylic acid halides of carbonic acid, preferred phosgene are also simultaneously as two functional acid derivatives.
As the chain terminator used of preparation aromatic polyestercarbonates, except already mentioned monohydric phenol, also the row of consideration be their chlorine carbonates and aromatic monocarboxylate's acyl chlorides, they can be randomly by C
1-C
22Alkyl or replaced, and aliphatic C by halogen
2-C
22The acyl chlorides of monocarboxylic acid.
In all cases, the consumption of chain terminator is 0.1-10 mole %, under the situation of phenols chain terminator, based on the mole number of dihydric phenol, and under the situation of monocarboxylic acid acyl chlorides chain terminator, then based on the mole number of dicarboxylic acid diacid chloride.
Aromatic polyestercarbonates also can contain the aromatic hydroxycarboxylic acids that joins wherein.
Aromatic polyestercarbonates can be a line style, also can be by currently known methods branching (can consult DE-OS 2 940 024 and DE-OS 3 007 934 in this respect equally).
As branching agent, can use the carboxylic acid chloride that for example has 3 or more a plurality of functionality, for example 1,3,5-benzenetricarboxylic acid three acyl chlorides, cyanogen urea acid three acyl chlorides, 3,3 ', 4,4 '-benzophenone tetracarboxylic acid four acyl chlorides, 1,4,5,8-naphthalene tetracarboxylic acid four acyl chlorides or 1,2,4,5-pyromellitic acid four acyl chlorides, its consumption are 0.01～1.0 mole of % (is benchmark in used dicarboxylic acid diacid chloride), or have the phenolic compound of 3 or more a plurality of functionality, Phloroglucinol for example, 4,6-dimethyl-2,4,6-three (4-hydroxy phenyl)-heptene, 2,4,4-dimethyl-2,4,6-three (4-hydroxy phenyl)-heptane, 1,3,5-three (4-hydroxy phenyl)-benzene, 1,1,1-three (4-hydroxy phenyl)-ethane, three (4-hydroxy phenyl)-phenylmethanes, 2,2-two (4,4-two (4-hydroxy phenyl)-cyclohexyl)-propane, 2,4-two (4-hydroxy phenyl-sec.-propyl)-phenol, four (4-hydroxy phenyl) methane, 2,6-two (2-hydroxy-5-methyl base-benzyl)-4-methyl-phenol, 2-(4-hydroxy phenyl)-2-(2, the 4-dihydroxy phenyl)-propane, four (4-(4-hydroxy phenyl-sec.-propyl)-phenoxy group)-methane, 1,4-two (4,4 '-two (hydroxyl triphenyl)-methyl)-benzene, its consumption are that benchmark is counted 0.01～1.0 mole of % with used dihydric phenol.The phenols branching agent can use with dihydric phenol when beginning, and the acyl chlorides branching agent can add together with diacid chloride.
The content of carbonate structural unit can change on demand in the Celanex carbonic ether.
In ester group and carbonate group summation is benchmark, and the content of carbonate group preferably is up to 100 moles of %, more preferably is up to 80 moles of %, especially preferably is up to 50 moles of %.
Ester that is comprised in the aromatic polyestercarbonates and carbonic ether can block form or the random distribution mode be present in the polycondensation product.
Relative nature viscosity (the η of aromatic polyestercarbonates
Phase) be 1.18-1.4, preferred 1.22-1.3 (measured at 25 ℃) to the solution of 0.5g polyestercarbonate in the 100ml methylene dichloride.
Thermoplastic aromatic polycarbonate and polyestercarbonate can use separately or use with each other any desired mixture.
Aromatic polycarbonate can prepare by currently known methods, for example carries out melt transesterification by corresponding bis-phenol and diphenyl carbonate, and prepares from the bis-phenol photoreactive gas in solution.Solution can be homogeneous phase (pyridine method) or heterogeneous (two-phase interface method) (see also H.Schnell, " chemistry of polycarbonate and physics ", Polymer Reviews, IX volume, the 33rd page and below, Interscience publishing company, 1964).
The molecular-weight average M of aromatic polycarbonate
wBe generally about 10,000-200,000, preferred 20,000-80,000 (calculating with gel chromatography proofreading and correct the back in advance).
Copolycarbonate in the scope of the invention is polydiorganosiloxane-polycarbonate block copolymer especially, its molecular-weight average M
wBe about 10,000-200,000, preferred 20,000-80,000 (after proofreading and correct in advance, calculating) with gel chromatography, aromatic carbonate structural unit content is about 75-97.5 weight %, preferred 85-97 weight %, polydiorganosiloxane structural unit content is about 25-2.5 weight %, preferred 15-3 weight %, this segmented copolymer is from containing α, ω-two-hydroxyl aryloxy end group and polymerization degree P
nBe 5-100, the polydiorganosiloxane feedstock production of preferred 20-80.
Polydiorganosiloxane-polycarbonate block copolymer also can be a kind of mixture of polydiorganosiloxane-polycarbonate block copolymer and the traditional thermoplastic poly carbonic ether that does not contain polysiloxane, and the total content of polydiorganosiloxane structural unit is about 2.5-25 weight % in this mixture.
This polydiorganosiloxane-polycarbonate block copolymer is characterised in that in its polymer chain and contains aromatic carbonate structural unit (1) on the one hand, contains the polydiorganosiloxane of aryloxy end group (2) on the other hand:
Wherein:
Ar is the aryl identical or different with bis-phenol,
R and R
1Can be identical or different, represent straight chained alkyl, branched-alkyl, alkenyl, halo straight chained alkyl, halo branched-alkyl, aryl or halogenated aryl, but preferable methyl, and
Two organosiloxy unit n=a+b+c are 5-100, preferred 20-80.
Alkyl in the top formula (2) is, for example C
1-C
20Alkyl, above alkenyl in the formula (2) be C for example
2-C
6Alkenyl; Aryl in the top formula (2) is C
6-C
14Aryl.Halo is meant partially or completely chloro, bromo or fluoro in the top formula.
The example of alkyl, alkenyl, aryl, haloalkyl and halogenated aryl is methyl, ethyl, propyl group, normal-butyl, the tertiary butyl, vinyl, phenyl, naphthyl, chloromethyl, perfluoro butyl, perfluoro capryl and chloro-phenyl-.
This polydiorganosiloxane-polycarbonate block copolymer is known, for example can consult US-PS 3 189 662, US-PS 3 821 325 and US-PS 3 832 419.
Preferred polydiorganosiloxane-polycarbonate block copolymer prepares as follows: make and contain α, polydiorganosiloxane and other dihydric phenol one of ω-two hydroxyl aryloxy end groups react, randomly follow with using the constant branching agent, for example (see also H.Schnell about this respect by the preparation of two-phase interface method, " chemistry of polycarbonate and physics ", PolymerRev. IX rolls up, the 27th page is risen, Interscience publishing company, New York, 1964), in all cases, the ratio of two sense phenols reactants should be selected like this, makes aromatic carbonate structural unit and the unitary content of two organosiloxies regulation according to the invention in the product.
This α that contains, the polydiorganosiloxane of ω-two hydroxyl aryloxy end groups is known, for example can consult US 3 419 634.
Thermoplastic composition can contain 10 weight parts at the most, especially the polyolefine of 1-8 weight part (is benchmark in gross weight 100 weight parts).The polyolefine that is fit to is the polymkeric substance of aliphatic unsaturated hydrocarbon such as ethene, propylene, butylene or iso-butylene.This polymkeric substance is by traditional method, and for example radical polymerization prepares its molecular-weight average M
w(using gel chromatography) is 3,000-3,000,000.High pressure and low pressure polyolefine all can use.Preferably polyethylene and polypropylene.
This moulding compound can contain nucleator, as little talcum.This moulding compound also can contain conventional additive, as lubricant, releasing agent, processing stabilizers and anti-drops (for example tetrafluoroethylene) and tinting material and pigment.
Sheet material with extrusion molding or compression moulding production can be the assembly of electronics department, wishes to have good electrical properties, also wish to have good fire resistance properties and good mobile and high surface quality simultaneously, and thermoplastic matrix is not damaged.
Therefore, the having of use, for example parts of cabinet parts, patch board and lamp socket and automotive field.
Film by this moulding compound production can be used for electronics department equally, and this film wishes to have good fire resistance properties and good electrical properties, and thermoplastic matrix is not damaged.
Electric wire coatings can be used for, for example electronic applications and automobile making, and this coating wishes to have good fire resistance properties, the thermostability of high-caliber electrical property, good chemical resistance energy and height, and thermoplastic matrix can not be damaged.
With regard to producing film, sheet material and electric wire coatings, each component can be mixed, carry out compounding in common mode at about 260 ℃～320 ℃ with a forcing machine then.
Embodiment
The test method of test moulded product is described
Combustion test is carried out according to UL 94 (IEC 707)
Proof bend test is carried out according to ISO 178
Melt volume-flow rate (volumetric flow index) is carried out according to ISO 1133
Table 1
Electrical property is pressed following mensuration:
| Electrical property | Test conditions | Unit | Standard | Test sample |
| Relative permittivity (specific inductivity) | ??100Hz | ??IEC?250 | Garden sheet 80 * 2 | |
| Relative permittivity (specific inductivity) | ??1MHz | ??IEC?250 | Garden sheet 80 * 2 | |
| The dielectric volume specific resistance | Ohm-cm | ??IEC?93 | Garden sheet 80 * 2 | |
| The specific surface resistivity rate | Ohm | ??IEC?93 | Garden sheet 80 * 2 | |
| Dielectric strength | ??kV/mm | ??IEC?243-1 | Garden sheet 118 * 2 | |
| Tracking index | Testing liquid A | Step | ??IEC?112 | Garden sheet 118 * 4 |
With forcing machine under common condition in embodiment indicated component mix, and carry out compounding, in injection moulding machine, under traditional PBT processing conditions (about 260 ℃ of composition temperature), mixing material is processed into sample then.
Test the performance of each sample.
Used polyacrylic acid pentabromobenzyl ester (PBB-PA) is Eurobrom FR 1025, by the Eurobrom B.V company production of Dutch Rijswijk.
According to embodiments of the invention 1
79.0 weight % polybutylene terephthalate (PBT)
(relative nature viscosity 1.707-1.153, T=25 ℃ 0.5
The % ratio of mixture is the molten of the phenol of 1: 1 weight part and orthodichlorobenzene
Measure in the liquid)
15.0 weight % PBB-PA
5.2 weight % ANTIMONY TRIOXIDE SB 203 99.8 PCT
0.8 weight % additive is according to embodiments of the invention 279.0 weight % polybutylene terephthalates (PBT)
(relative nature viscosity 1.834-1.875, T=25 ℃ 0.5
The % ratio of mixture is the molten of the phenol of 1: 1 weight part and orthodichlorobenzene
Measure in the liquid) 15.0 weight % PBB-PA5.2 weight % ANTIMONY TRIOXIDE SB 203 99.8 PCT, 0.8 weight % additive comparative example, 379.2 weight % polybutylene terephthalates (PBT)
(relative nature viscosity 1.707-1.153, T=25 ℃ 0.5
The % ratio of mixture is the molten of the phenol of 1: 1 weight part and orthodichlorobenzene
Measure in the liquid) 15.0 weight % epoxidation tetrabromo-bisphenols, 5.0 weight % ANTIMONY TRIOXIDE SB 203 99.8 PCT, 0.8 weight % additive comparative example, 480.7 weight % polybutylene terephthalates (PBT)
(relative nature viscosity 1.643-1.705, T=25 ℃ 0.5
The % ratio of mixture is the molten of the phenol of 1: 1 weight part and orthodichlorobenzene
Measure in the liquid) 13.5 weight % ethylidene-two-tetrabromo phthalimide 5.0 weight % ANTIMONY TRIOXIDE SB 203 99.8 PCT 0.8 weight % additive is according to embodiments of the invention 591.4 weight % polybutylene terephthalates (PBT)
(relative nature viscosity 1.707-1.153, T=25 ℃ 0.5
The % ratio of mixture is the molten of the phenol of 1: 1 weight part and orthodichlorobenzene
Measure in the liquid) 6.0 weight % PBB-PA1.8 weight % ANTIMONY TRIOXIDE SB 203 99.8 PCT, 0.8 weight % additive
Table 2 (result)
*Comparative example 3 and embodiment 1 and 5 contrasts.
| The Flameproof thermoplastic moulding compound | |||||||
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |||
| Performance | Standard | Unit | According to the present invention | According to the present invention | Contrast | Contrast | According to the present invention |
| Relative permittivity 100Hz | IEC?250 | 3.5 | Not test | Not test | 3.4 | Not test | |
| Relative permittivity 1MHz | IEC?250 | 3.5 | Not test | 3.2 | 3.2 | Not test | |
| The dielectric volume specific resistance | IEC?93 | Ohm-centimetre | 4.5E+16 | Not test | ＞10 15 | ＞10 13 | Not test |
| The specific surface resistivity rate | IEC?93 | Ohm | 1.1E+17 | Not test | ＞10 15 | ＞10 13 | Not test |
| Dielectric strength | IEC?243 | kV/mm | 49 | Not test | 28 | 28 | Not test |
| Combustion test | UL?94 | ||||||
| ??3.2mm | Grade | V0 | V0 | V0 | V0 | V0 | |
| ??1.6mm | Grade | V0 | V0 | V0 | V0 | V2 | |
| ??0.8mm | Grade | V0 | V0 | V0 | V0 | Not test | |
| ??0.4mm | Grade | V0 | V0 | Can't make | Can't make | Not test | |
| Proof bend test | ISO?178 | ||||||
| Flexural strength | MPa | 100 | 100 | 95 | 90 | 95 | |
| Flexural elongation | ％ | 5.5 | 5.6 | 5.5 | 5.0 | 7.5 | |
| Modulus in flexure | MPa | 2800 | 2800 | 2700 | 2700 | 2600 | |
| MVR 260 ℃/2.16 kg load | ISO?1133 | cm 3/10 mim | 22 | 17 | 15 * | 20 | 19 |
| Tracking index | IEC?112 | Step | 500 | 500 | 250 | 375 | 600 |
The sample that data declaration is made by moulding compound of the present invention in the table is compared with control sample has obviously the better mechanical property of creep-resistant property, comparable or better flowability (MVR) and higher level.Also can be processed into the thick sample of thin-walled according to composition of the present invention, and in combustion test, reach especially good performance.It is the sample of 0.4mm that comparative example 3 and 4 can't be processed into the thickness of describing according to combustion test.
Film can be mixed and be processed into to listed component also under conventional P BT processing conditions (about 250 ℃ of composition temperature) in the film forcing machine.
The test method of testing film is described
Combustion test is carried out according to UL 94 (IEC 707).
Test according to UL 94V and UL 94 VTM can be used for film.Among the UL 94 the 8.1st and 11.1 joint has pointed out to select the standard of test method.
Tension test is carried out according to ISO 1184.
Having produced thickness is the film of the present invention of 0.1mm～0.8mm, and carries out the combustion test test according to UL 94.
Be processed into the embodiment 1 of film according to the present invention
When thickness is 0.6mm, in test, reach V-0 according to UL 94V.When thickness is 0.1mm, carry out UL 94 VTM test, the result is VTM-0.
According to embodiments of the invention 2
Produced thickness and be 0.125mm-0.75mm according to film of the present invention, and carried out the combustion test test by UL94.
Table 3 combustion test result (embodiment 2)
| Thickness/mm | Test method | |
| UL?94V | ?UL?94?VTM | |
| ??0.125 | Not test (N.T.) | ?VTM-0 |
| ??0.250 | ?V-0 | ?VTM-0 |
| ??0.375 | ?V-0 | ?VTM-0 |
| ??0.750 | ?V-0 | Not test (N.T.) |
The rupture stress of these films, extension at break and Young's modulus are measured in the tension test according to ISO 1884.
Table 4 mechanical properties results (embodiment 2)
| Thickness mm | Rupture stress MPa | Extension at break % | Young's modulus MPa | |||
| Vertically | Laterally | Vertically | Laterally | Vertically | Laterally | |
| ?0.125 | ?37 | ?41 | ?3.4 | ?12.2 | ?2550 | ?2500 |
| ?0.175 | ?46 | ?36 | ?3.4 | ?17.6 | ?2590 | ?2515 |
| ?0.250 | ?44 | ?43 | ?6.4 | ?5.4 | ?2730 | ?2620 |
| ?0.375 | ?43 | ?46 | ?12.3 | ?10.0 | ?2920 | ?2910 |
| ?0.450 | ?45 | ?50 | ?5.2 | ?4.2 | ?3070 | ?2910 |
| ?0.500 | ?50 | ?48 | ?4.5 | ?8.6 | ?3100 | ?3140 |
| ?0.625 | ?52 | ?52 | ?10.0 | ?3.8 | ?3190 | ?3300 |
| ?0.750 | ?52 | ?51 | ?3.9 | ?7.3 | ?3420 | ?3290 |
The comparative example 3
Product can't be processed into film (tear, surface badly damaged).
The comparative example 4
Product can't be processed into film (tear, surface badly damaged).
Compare with simultaneous test, can be processed into especially at the film that has great surface quality aspect luminance brightness and the homogeneity according to moulding compound of the present invention.Simultaneously, reached the good fire resistance energy, and mechanical property levels is also high.
Claims (8)
1. extrudate and the moulded product produced by compression moulding, described product are based on the thermoplastic composition that contains following component:
A) polyalkylene terephthalates of 55-97.7 weight part,
B) the polyacrylic acid pentabromobenzyl ester of 2-30 weight part,
C) antimony compounds of 0.3-12 weight part and
D) polycarbonate of 0-90 weight part and/or polyestercarbonate,
A wherein)+B)+C)+D) summation is 100, and the polyalkylene terephthalates of 10 weight parts can be replaced by polyolefine at the most.
2. according to the extrudate of claim 1 and the moulded product produced by compression moulding, described product is based on the thermoplastic composition that contains following component:
A) polyalkylene terephthalates of 60-95.5 weight part,
B) the polyacrylic acid pentabromobenzyl ester of 3-25 weight part,
C) antimony compounds of 0.5-10 weight part and
D) polycarbonate of 0-75 weight part and/or polyestercarbonate.
3. according to the extrudate of claim 1 and the moulded product produced by compression moulding, described product is based on the thermoplastic composition that contains following component:
A) polyalkylene terephthalates of 70-95 weight part,
B) the polyacrylic acid pentabromobenzyl ester of 4-20 weight part,
C) antimony compounds of 1-8 weight part and
D) polycarbonate of 0-75 weight part and/or polyestercarbonate.
According in the aforementioned claim any one based on the extrudate of thermoplastic composition and the moulded product produced by compression moulding, wherein this thermoplastic composition contains conventional additive.
According to claim 5 based on the extrudate of thermoplastic composition and the moulded product produced by compression moulding, wherein this additive is at least a additive that is selected from following a group: nucleator, lubricant, releasing agent, processing stabilizers, tinting material, pigment and anti-drops.
6. according to any one film, sheet material and electric wire coatings in the aforementioned claim.
7. the purposes of the moulded product that is used to produce extrudate that extension at break and rupture stress and surface quality performance make moderate progress according to the thermoplastic composition of any one among the claim 1-5 and produces by compression moulding.
8. according to the purposes of claim 7, be used to produce film, sheet material and electric wire coatings.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19857965.9 | 1998-12-16 | ||
| DE19857965A DE19857965A1 (en) | 1998-12-16 | 1998-12-16 | Flame-retardant extrudates and flame-retardant molded articles produced by pressing processes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1357027A true CN1357027A (en) | 2002-07-03 |
Family
ID=7891238
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99814549A Pending CN1357027A (en) | 1998-12-16 | 1999-12-03 | Flameproof extrudates and flameproof moulded bodies produced by means of pressing methods |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP1144508A3 (en) |
| JP (1) | JP2003500489A (en) |
| KR (1) | KR20010101238A (en) |
| CN (1) | CN1357027A (en) |
| AU (1) | AU3035500A (en) |
| BR (1) | BR9916193A (en) |
| CA (1) | CA2355274A1 (en) |
| DE (1) | DE19857965A1 (en) |
| HK (1) | HK1047758A1 (en) |
| ID (1) | ID28970A (en) |
| IL (1) | IL143222A0 (en) |
| WO (1) | WO2000036013A2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459473A (en) * | 2014-03-10 | 2017-02-22 | 沙特基础工业全球技术有限公司 | Flame retardant polyalkylene terephthalate composition |
| CN108026361A (en) * | 2015-09-11 | 2018-05-11 | 三菱工程塑料株式会社 | Polyester resin composition and its manufacture method |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10254259A1 (en) * | 2002-11-21 | 2004-06-03 | Abb Patent Gmbh | Method for producing a housing for an electrical switching device |
| FR2966464B1 (en) * | 2010-10-26 | 2012-11-02 | Arkema France | HIGH THERMOMECHANICAL, FIRE RETARDANT THERMOPLASTIC COMPOSITIONS, ESPECIALLY FOR ELECTRIC CABLES |
| CN105658716B (en) * | 2013-09-09 | 2018-02-06 | 巴斯夫欧洲公司 | Flame retardant polyester |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4806588A (en) * | 1986-04-15 | 1989-02-21 | Toyo Boseki Kabushiki Kaisha | Polyester resin composition |
| IL86604A (en) * | 1988-06-02 | 1994-01-25 | Bromine Compounds Ltd | Flame-retardant compositions comprising pentabromobenzyl acrylate or their in situ reaction products |
| TW204357B (en) * | 1988-12-29 | 1993-04-21 | Ciba Geigy Ag | |
| JPH06145485A (en) * | 1992-11-10 | 1994-05-24 | Teijin Ltd | Flame-retardant polyester resin composition |
| CA2151585A1 (en) * | 1992-12-14 | 1994-06-23 | Benjamin Weiss | Administration of oligonucleotides antisense to dopamine receptor mrna for diagnosis and treatment of neurological pathologies |
| JP4033520B2 (en) * | 1996-08-12 | 2008-01-16 | ゼネラル・エレクトリック・カンパニイ | Flame retardant polyester composition |
-
1998
- 1998-12-16 DE DE19857965A patent/DE19857965A1/en not_active Ceased
-
1999
- 1999-12-03 BR BR9916193-1A patent/BR9916193A/en not_active IP Right Cessation
- 1999-12-03 AU AU30355/00A patent/AU3035500A/en not_active Abandoned
- 1999-12-03 IL IL14322299A patent/IL143222A0/en unknown
- 1999-12-03 CA CA002355274A patent/CA2355274A1/en not_active Abandoned
- 1999-12-03 ID IDW00200101405A patent/ID28970A/en unknown
- 1999-12-03 WO PCT/EP1999/009494 patent/WO2000036013A2/en not_active Application Discontinuation
- 1999-12-03 CN CN99814549A patent/CN1357027A/en active Pending
- 1999-12-03 EP EP99964521A patent/EP1144508A3/en not_active Withdrawn
- 1999-12-03 JP JP2000588267A patent/JP2003500489A/en active Pending
- 1999-12-03 KR KR1020017007496A patent/KR20010101238A/en not_active Application Discontinuation
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2002
- 2002-12-24 HK HK02109329.1A patent/HK1047758A1/en unknown
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106459473A (en) * | 2014-03-10 | 2017-02-22 | 沙特基础工业全球技术有限公司 | Flame retardant polyalkylene terephthalate composition |
| CN106459473B (en) * | 2014-03-10 | 2021-07-06 | 沙特基础工业全球技术有限公司 | Flame-retardant polyalkylene terephthalate composition |
| CN108026361A (en) * | 2015-09-11 | 2018-05-11 | 三菱工程塑料株式会社 | Polyester resin composition and its manufacture method |
| US10626269B2 (en) | 2015-09-11 | 2020-04-21 | Mitsubishi Engineering-Plastics Corporation | Polyester resin composition and method for producing same |
| CN108026361B (en) * | 2015-09-11 | 2020-05-22 | 三菱工程塑料株式会社 | Polyester resin composition and method for producing same |
Also Published As
| Publication number | Publication date |
|---|---|
| HK1047758A1 (en) | 2003-03-07 |
| IL143222A0 (en) | 2002-04-21 |
| KR20010101238A (en) | 2001-11-14 |
| AU3035500A (en) | 2000-07-03 |
| CA2355274A1 (en) | 2000-06-22 |
| WO2000036013A3 (en) | 2002-05-23 |
| ID28970A (en) | 2001-07-19 |
| WO2000036013A2 (en) | 2000-06-22 |
| JP2003500489A (en) | 2003-01-07 |
| BR9916193A (en) | 2001-09-04 |
| EP1144508A2 (en) | 2001-10-17 |
| DE19857965A1 (en) | 2000-06-21 |
| EP1144508A3 (en) | 2002-09-11 |
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