HU209957B - Process for manufacturing of extrudated foam-bodies - Google Patents
Process for manufacturing of extrudated foam-bodies Download PDFInfo
- Publication number
- HU209957B HU209957B HU901191A HU119190A HU209957B HU 209957 B HU209957 B HU 209957B HU 901191 A HU901191 A HU 901191A HU 119190 A HU119190 A HU 119190A HU 209957 B HU209957 B HU 209957B
- Authority
- HU
- Hungary
- Prior art keywords
- blowing agent
- mixture
- weight
- plastic
- carbon dioxide
- Prior art date
Links
- 238000000034 method Methods 0.000 title claims abstract description 55
- 230000008569 process Effects 0.000 title claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 239000004604 Blowing Agent Substances 0.000 claims abstract description 84
- 239000000203 mixture Substances 0.000 claims abstract description 72
- BHNZEZWIUMJCGF-UHFFFAOYSA-N 1-chloro-1,1-difluoroethane Chemical compound CC(F)(F)Cl BHNZEZWIUMJCGF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 125000003118 aryl group Chemical group 0.000 claims abstract description 12
- LVGUZGTVOIAKKC-UHFFFAOYSA-N 1,1,1,2-tetrafluoroethane Chemical compound FCC(F)(F)F LVGUZGTVOIAKKC-UHFFFAOYSA-N 0.000 claims abstract description 10
- BOUGCJDAQLKBQH-UHFFFAOYSA-N 1-chloro-1,2,2,2-tetrafluoroethane Chemical compound FC(Cl)C(F)(F)F BOUGCJDAQLKBQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 57
- 238000001125 extrusion Methods 0.000 claims description 30
- 239000001569 carbon dioxide Substances 0.000 claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 229920003023 plastic Polymers 0.000 claims description 24
- 239000004033 plastic Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000004793 Polystyrene Substances 0.000 claims description 11
- 229920002223 polystyrene Polymers 0.000 claims description 11
- 239000002667 nucleating agent Substances 0.000 claims description 10
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 9
- 229960003750 ethyl chloride Drugs 0.000 claims description 9
- 239000000454 talc Substances 0.000 claims description 9
- 229910052623 talc Inorganic materials 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 6
- 125000003342 alkenyl group Chemical group 0.000 claims description 5
- 238000005187 foaming Methods 0.000 claims description 5
- 229920001169 thermoplastic Polymers 0.000 claims description 5
- SKDFWEPBABSFMG-UHFFFAOYSA-N 1,2-dichloro-1,1-difluoroethane Chemical compound FC(F)(Cl)CCl SKDFWEPBABSFMG-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 150000001350 alkyl halides Chemical class 0.000 claims description 4
- ATEBGNALLCMSGS-UHFFFAOYSA-N 2-chloro-1,1-difluoroethane Chemical compound FC(F)CCl ATEBGNALLCMSGS-UHFFFAOYSA-N 0.000 claims description 3
- 235000000177 Indigofera tinctoria Nutrition 0.000 claims description 3
- 239000000378 calcium silicate Substances 0.000 claims description 3
- 229910052918 calcium silicate Inorganic materials 0.000 claims description 3
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 claims description 3
- 229940097275 indigo Drugs 0.000 claims description 3
- COHYTHOBJLSHDF-UHFFFAOYSA-N indigo powder Natural products N1C2=CC=CC=C2C(=O)C1=C1C(=O)C2=CC=CC=C2N1 COHYTHOBJLSHDF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012815 thermoplastic material Substances 0.000 claims description 3
- 150000004820 halides Chemical class 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 239000006260 foam Substances 0.000 abstract description 37
- 229920005989 resin Polymers 0.000 abstract description 8
- 239000011347 resin Substances 0.000 abstract description 8
- 238000001816 cooling Methods 0.000 abstract description 3
- 238000007664 blowing Methods 0.000 abstract 1
- 239000012530 fluid Substances 0.000 abstract 1
- 229920005992 thermoplastic resin Polymers 0.000 abstract 1
- 210000004027 cell Anatomy 0.000 description 41
- 229920000642 polymer Polymers 0.000 description 36
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 26
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 description 21
- 235000019404 dichlorodifluoromethane Nutrition 0.000 description 17
- 239000004338 Dichlorodifluoromethane Substances 0.000 description 13
- 229940042935 dichlorodifluoromethane Drugs 0.000 description 13
- VOPWNXZWBYDODV-UHFFFAOYSA-N Chlorodifluoromethane Chemical compound FC(F)Cl VOPWNXZWBYDODV-UHFFFAOYSA-N 0.000 description 12
- 229920006327 polystyrene foam Polymers 0.000 description 12
- 239000000463 material Substances 0.000 description 9
- 239000003063 flame retardant Substances 0.000 description 8
- 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 description 6
- -1 carbon halides Chemical class 0.000 description 6
- 239000000178 monomer Substances 0.000 description 6
- 229940051271 1,1-difluoroethane Drugs 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 229920002959 polymer blend Polymers 0.000 description 5
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 229940050176 methyl chloride Drugs 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- OHMHBGPWCHTMQE-UHFFFAOYSA-N 2,2-dichloro-1,1,1-trifluoroethane Chemical compound FC(F)(F)C(Cl)Cl OHMHBGPWCHTMQE-UHFFFAOYSA-N 0.000 description 2
- OMIHGPLIXGGMJB-UHFFFAOYSA-N 7-oxabicyclo[4.1.0]hepta-1,3,5-triene Chemical class C1=CC=C2OC2=C1 OMIHGPLIXGGMJB-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 210000003850 cellular structure Anatomy 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- AFYPFACVUDMOHA-UHFFFAOYSA-N chlorotrifluoromethane Chemical compound FC(F)(F)Cl AFYPFACVUDMOHA-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000004088 foaming agent Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- CRSOQBOWXPBRES-UHFFFAOYSA-N neopentane Chemical compound CC(C)(C)C CRSOQBOWXPBRES-UHFFFAOYSA-N 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000001424 substituent group Chemical group 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- NPNPZTNLOVBDOC-UHFFFAOYSA-N 1,1-difluoroethane Chemical compound CC(F)F NPNPZTNLOVBDOC-UHFFFAOYSA-N 0.000 description 1
- DDMOUSALMHHKOS-UHFFFAOYSA-N 1,2-dichloro-1,1,2,2-tetrafluoroethane Chemical compound FC(F)(Cl)C(F)(F)Cl DDMOUSALMHHKOS-UHFFFAOYSA-N 0.000 description 1
- YJCVRMIJBXTMNR-UHFFFAOYSA-N 1,3-dichloro-2-ethenylbenzene Chemical compound ClC1=CC=CC(Cl)=C1C=C YJCVRMIJBXTMNR-UHFFFAOYSA-N 0.000 description 1
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- YACLCMMBHTUQON-UHFFFAOYSA-N 1-chloro-1-fluoroethane Chemical compound CC(F)Cl YACLCMMBHTUQON-UHFFFAOYSA-N 0.000 description 1
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 description 1
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 description 1
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- ISRGONDNXBCDBM-UHFFFAOYSA-N 2-chlorostyrene Chemical compound ClC1=CC=CC=C1C=C ISRGONDNXBCDBM-UHFFFAOYSA-N 0.000 description 1
- AYKYXWQEBUNJCN-UHFFFAOYSA-N 3-methylfuran-2,5-dione Chemical compound CC1=CC(=O)OC1=O AYKYXWQEBUNJCN-UHFFFAOYSA-N 0.000 description 1
- OFNISBHGPNMTMS-UHFFFAOYSA-N 3-methylideneoxolane-2,5-dione Chemical compound C=C1CC(=O)OC1=O OFNISBHGPNMTMS-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- XWCDCDSDNJVCLO-UHFFFAOYSA-N Chlorofluoromethane Chemical compound FCCl XWCDCDSDNJVCLO-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001328 Polyvinylidene chloride Polymers 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000008901 benefit Effects 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
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 229960004424 carbon dioxide Drugs 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 230000001413 cellular effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 125000004773 chlorofluoromethyl group Chemical group [H]C(F)(Cl)* 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 235000019864 coconut oil Nutrition 0.000 description 1
- 239000003240 coconut oil Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 125000004772 dichloromethyl group Chemical group [H]C(Cl)(Cl)* 0.000 description 1
- 229940087091 dichlorotetrafluoroethane Drugs 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000004794 expanded polystyrene Substances 0.000 description 1
- 239000003000 extruded plastic Substances 0.000 description 1
- 239000004795 extruded polystyrene foam Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229940057995 liquid paraffin Drugs 0.000 description 1
- 239000007937 lozenge Substances 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pentâ4âenâ2âone Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 239000002984 plastic foam Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000003380 propellant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000003507 refrigerant Substances 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012289 standard assay Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 210000002435 tendon Anatomy 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- CYRMSUTZVYGINF-UHFFFAOYSA-N trichlorofluoromethane Chemical compound FC(Cl)(Cl)Cl CYRMSUTZVYGINF-UHFFFAOYSA-N 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000004078 waterproofing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/001—Combinations of extrusion moulding with other shaping operations
- B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C44/00—Shaping by internal pressure generated in the material, e.g. swelling or foaming ; Producing porous or cellular expanded plastics articles
- B29C44/34—Auxiliary operations
- B29C44/3403—Foaming under special conditions, e.g. in sub-atmospheric pressure, in or on a liquid
- B29C44/3407—Vacuum extrusion using underwater barometric leg
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
- B29C48/07—Flat, e.g. panels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/90—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
- B29C48/919—Thermal treatment of the stream of extruded material, e.g. cooling using a bath, e.g. extruding into an open bath to coagulate or cool the material
-
- 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
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/143—Halogen containing compounds
- C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
- C08L25/02—Homopolymers or copolymers of hydrocarbons
- C08L25/04—Homopolymers or copolymers of styrene
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
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- B29C48/904—Thermal treatment of the stream of extruded material, e.g. cooling with calibration or sizing, i.e. combined with fixing or setting of the final dimensions of the extruded article using dry calibration, i.e. no quenching tank, e.g. with water spray for cooling or lubrication
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/25—Component parts, details or accessories; Auxiliary operations
- B29C48/88—Thermal treatment of the stream of extruded material, e.g. cooling
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- C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
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Description
A leĂrĂĄs terjedelme: 12 oldal (ezen belĂŒl 2 lap ĂĄbra)
HU 209 957 Î sĂ©ge 14,4656,1 kg/m3 (0,9-3,1 lb/ft3) a mƱanyag tömegĂ©re szĂĄmĂtva 3-16 tömegrĂ©sz folyĂ©kony habosĂtĂłszert adagolnak, Ă©s habosĂtĂłszerkĂ©nt az 1-klĂłr-1,1difluor-etĂĄn, 1,1,1,2-tetrafluor-etĂĄn Ă©s 2-klĂłr-1,1,1,2tetrafluor-etĂĄn közĂŒl legalĂĄbb egyet, tovĂĄbbĂĄ adott esetben mĂ©g a mƱanyag tömegĂ©re vonatkoztatva 0,41,5 tömeg% szĂ©ndioxidot, Ă©s/vagy legalĂĄbb egy tovĂĄbbi alkĂĄl-halogenid, diklĂłr-difluor-etĂĄn, Ă©s klĂłrdifluor-etĂĄn közĂŒl vĂĄlasztott habosĂtĂłszert adagolnak, az alkil-halogenid habosĂtĂłszer teljes mennyisĂ©ge a mƱanyag tömegĂ©re szĂĄmĂtva 3-16 tömegrĂ©sz, a habosĂtĂłszerhez adott esetben gĂłckĂ©pzĆ adalĂ©kot is adagolnak, Ă©s az extrudĂĄlĂĄst 6,67-91,42 kPa (2-27 Hg in) nyomĂĄsĂș extrĂșziĂłs tĂ©rben vĂ©gezzĂŒk, Ăgy 14,4â
56,1 kg/m3 (0,9-3,1 lb/ft3) sƱrƱsĂ©gƱ habosĂtott testet (24) kĂ©peznek.
A talĂĄlmĂĄny tĂĄrgya olyan eljĂĄrĂĄs, mellyel darabos vagy tĂĄbla alakĂș, 14,4-56,1 kg/m3 (0,9-3,5 lb/ft3) sƱrƱsĂ©ggel jellemezhetĆ' extrudĂĄlt, habosĂtott termĂ©kek ĂĄllĂthatĂłk elĆ. A talĂĄlmĂĄny elsĆdlegesen azokkal a hĆre lĂĄgyulĂł extrudĂĄlt habokkal foglalkozik, melyeknek a habosĂtĂĄsa vĂĄkuumban törtĂ©nt.
Az extrudĂĄlt mƱanyaghabok igen elĆnyösen alkalmazhatĂłk szĂĄmos terĂŒleten pl. hĆszigetelĂ©s, csomagolĂĄs, dekorĂĄciĂł, stb. A polisztirolhabok egyik kĂŒlönösen fontos felhasznĂĄlĂĄsi terĂŒlete a hĆszigetelĂ©s biztosĂtĂĄsa. Az ilyen tĂpusĂș felhasznĂĄlĂĄsnĂĄl lĂ©nyeges, hogy a mƱanyag hĆszigetelĆ kĂ©pessĂ©ge a lehetĆ leghosszabb ideig megĆrzĆdjön, s hogy a hab szerkezeti stabilitĂĄsa kielĂ©gĂtĆ legyen. A talĂĄlmĂĄny a polimer habok közĂŒl az Ășn. extrudĂĄlt habokkal foglalkozik. Az extrudĂĄlt habok ĂĄltalĂĄban uniform sejtszerkezetƱek, s mint ilyen kĂŒlönösen elĆnyösen hasznĂĄlhatĂłk fel a hĆszigetelĂ©sben.
A polimer haboknak egy mĂĄsik fontos jellemzĆje a sƱrƱsĂ©g, mely ĂĄltalĂĄban 16-80 kg/m3 (1-5 lb/ft3) Ă©rtĂ©khatĂĄrok közĂ© esik. A 32 kg/m3 (1 lb/ft3) sƱrƱsĂ©g polisztirolhabok esetĂ©ben ĂĄltalĂĄnosnak tekinthetĆ, s ilyen kĂ©szĂtmĂ©nyek a kereskedelmi forgalombĂłl beszerezhetĆk. A sƱrƱsĂ©g Ă©s a sejtszerkezet mĂ©retviszonyainak összefĂŒggĂ©se kĂŒlönösen hĆszigetelĂ©sre törtĂ©nĆ felhasznĂĄlĂĄsra szĂĄnt mƱanyaghabok esetĂ©n fontos tĂ©nyezĆ. ĂltalĂĄnossĂĄgban elmondhatĂł, hogy a kĂvĂĄnt sejtszerkezet, azaz kis cellamĂ©ret fenntartĂĄsa mellett a kis (32 kg/m3 alatti) sƱrƱsĂ©gƱ habok elĆĂĄllĂtĂĄsa nem könnyƱ feladat. A sƱrƱsĂ©g csökkenĂ©se ĂĄltalĂĄban a cellamĂ©ret relatĂv növekedĂ©sĂ©vel jĂĄr egyĂŒtt, s azok a kĂsĂ©rletek melyek a kis sƱrƱsĂ©gƱ, s egyben viszonylag kis cellamĂ©retƱ habosĂtott mƱanyagot a habosĂtĂłszer mennyisĂ©gĂ©nek Ă©s az extrudĂĄtum hĆmĂ©rsĂ©kletĂ©nek szabĂĄlyozĂĄsĂĄval kĂvĂĄntĂĄk elĂ©rni, nem jĂĄrtak teljes sikerrel. A cellamĂ©ret csökkentĂ©sĂ©vel a termĂ©k sƱrƱsĂ©ge ĂĄltalĂĄban a magasabb Ă©rtĂ©kek irĂĄnyĂĄba tolĂłdik el.
HosszĂș idĆn keresztĂŒl a polisztirolhabok extrudĂĄlĂĄsĂĄnĂĄl kĂŒlönbözĆ szĂ©nhalogenideket hasznĂĄltak habosĂtĂłszerkĂ©nt, pl. metilĂ©n-klorid, etil-klorid; e habosĂtĂłszereket hasznĂĄlhatjĂĄk egyedĂŒl vagy (ĂĄltalĂĄban CFCnek nevezett) fluorkarbonokkal egyĂŒtt, ilyen pl. a diklĂłr-difluor-metĂĄn. Azokban az eljĂĄrĂĄsokban, melyekben habosĂtĂłszerkĂ©nt metil-kloridot, etil-kloridot hasznĂĄlnak fel, egyedĂŒl vagy mĂĄs habosĂtĂłszerekkel kombinĂĄlva, szĂŒksĂ©g van az extrudĂĄlt anyag bizonyos Ă©rĂ©sĂ©re, egy olyan idĆszakra, melyben a metil- vagy etilklorid elhagyja a cellĂĄt, s a levegĆ a megfelelĆ diffĂșzĂłs folyamatok rĂ©vĂ©n a cella falĂĄn ĂĄt bejuthat abba.
A 4 393 016 sz. USA-beli szabadalmi leĂrĂĄs polisztirolhabok elĆĂĄllĂtĂĄsĂĄt Ărja le etil-klorid, metil-klorid Ă©s diklĂłr-difluor-metĂĄn habosĂtĂłszer keverĂ©k felhasznĂĄlĂĄsĂĄval. A 4 451 417 sz. USA-beli szabadalmi leĂrĂĄs etilklorid Ă©s diklĂłr-difluor-metĂĄn keverĂ©k felhasznĂĄlĂĄsĂĄrĂłl szĂĄmol be.
Napjainkban a kormĂĄnyok Ă©s a környezetvĂ©dĆk jelentĆs erĆfeszĂtĂ©seket követelnek az aeroszolok hajtĂłgĂĄzaikĂ©nt, hƱtĆközegkĂ©nt, habosĂtĂłszerkĂ©nt valamint az elektronikĂĄban Ă©s ƱrhajĂłzĂĄsban egyarĂĄnt felhasznĂĄlt fluorkarbonok (CFC-k) mennyisĂ©gĂ©nek csökkentĂ©sĂ©re, esetleg felhasznĂĄlĂĄsuk teljes beszĂŒntetĂ©sĂ©re. A fentiekben felsorolt cĂ©lokra hasznĂĄlhatĂł fluorkarbonok közĂ© tartozik pl. a CFC-11, mely klĂłr-trifluor-metĂĄn; a CFC-12, mely diklĂłr-difluor-metĂĄn; a CFC-13, 1,2,2triflour-l,l,2-triklĂłr-etĂĄn. Az elmĂșlt Ă©vekben erĆfeszĂtĂ©sek törtĂ©ntek arra vonatkozĂłan, hogy a CFC vegyĂŒleteket szĂ©nhidrogĂ©nekkel, mint butĂĄn vagy inĂ©rt gĂĄzokkal, mint pl. szĂ©n-dioxid helyettesĂtsĂ©k. Ilyen szĂ©n-dioxid Ă©s egy alkĂĄnt tartalmazĂł habosĂtĂłszer keverĂ©k felhasznĂĄlĂĄsĂĄrĂłl szĂĄmolnak be a 4 344 710 Ă©s 4 424 287 sz. USA-beli szabadalmi leĂrĂĄsokban. A CFC-k rĂ©szleges vagy teljes helyettesĂtĂ©sĂ©re egy mĂĄsik javaslat, a hidrogĂ©nt nem tartalmazĂł CFC-k helyettesĂtĂ©se legalĂĄbb egy hidrogĂ©natomot tartalmazĂł fluorszĂ©nhidrogĂ©nekkel. Ezeket az anyagokat ĂĄltalĂĄban lĂĄgy CFC-kĂ©nt, HCFC-kĂ©nt vagy HFC-kĂ©nt szerepeltetik az irodalomban.
A HCFC-k (lĂĄgy CFC, HFC) kĂŒlönleges elĆnye, hogy az Ăłzon rĂ©teget lĂ©nyegesen kevĂ©sbĂ© kĂĄrosĂtjĂĄk, mint a CFC vegyĂŒletek. Az ĂłzonkĂĄrosĂtĂł potenciĂĄl egy relatĂv mĂ©rĆszĂĄm arra vonatkozĂłan, hogy az anyag milyen mĂ©rtĂ©kben kĂĄrosĂtja a sztratoszfĂ©ra Ăłzon rĂ©tegĂ©t. Az alĂĄbbi HCFC vegyĂŒletekrĆl, mint a klĂłr-difluor-metĂĄn (HCFC-22), az l,l-diklĂłr-2,2,2-trifluor-etĂĄn (HCFC-123), az l-klĂłr-l,l-difluor-etĂĄn (HCFC142b), 1,1,1,2-tetrafluor-etĂĄn (MCFC-134a) bebizonyosodott, hogy a CFC vegyĂŒletekhez kĂ©pest kevĂ©sbĂ© kĂĄrosĂtjĂĄk az ĂłzonrĂ©teget, s a CFC vegyĂŒletek helyettesĂtĂ©sĂ©re alkalmasak. Az 1 537 421 sz. angol szabadalmi leĂrĂĄs polisztirol habtestek elĆĂĄllĂtĂĄsĂĄt Ărja le legalĂĄbb egy (A) ĂĄltalĂĄnos kĂ©pletƱ vegyĂŒletet: Râ-CF2-R2 ahol
HU 209 957 Î
R1 jelentése metil-, etil-, klór-metil-, fluor-metil-, klórfluor-metil-, difluor-metil- vagy trifluor-metil-csoport;
R2 jelentĂ©se pedig hidrogĂ©n-, klĂłr- vagy fluoratom vagy trifluor-, illetve metilcsoport; a szubsztituensek jelentĂ©se azzal a megkötĂ©ssel Ă©rtelmezhetĆ, hogy a vegyĂŒlet nem tartalmazhat 3 szĂ©natomnĂĄl többet, s amennyiben csak 2 fluoratomot tartalmaz, a szĂ©natomok szĂĄma kötelezĆen hĂĄrom tartalmazĂł habosĂtĂłszer keverĂ©kkel. Az itt felsorolt habosĂtĂłszerekkel elĆĂĄllĂtott habosĂtott testek sejtszerkezetĂ©ben a cellĂĄk azonosak, s a cellamĂ©ret 0,1-1,2 mm közötti. A habosĂtott testek sƱrƱsĂ©ge 16,02-80,1 kg/m3 (1-5 lb/ft3) közötti.
A talĂĄlmĂĄny egy megvalĂłsĂtĂĄsĂĄnĂĄl a fenti habosĂtĂłszerek közĂŒl egyet vagy többet egy Ășn. mĂĄsodik habosĂtĂłszerrel kombinĂĄlva hasznĂĄlnak fel, ez utĂłbbinak a polimeren valĂł diffĂșziĂłsebessĂ©ge nitrogĂ©nra vonatkoztatva 0,017-nĂ©l nagyobb. Az ilyen âmĂĄsodik habosĂtĂłszerreâ pĂ©lda a metil-klorid, etil-klorid, klĂłr-difluormetĂĄn, fluor-klĂłr-metĂĄn, 1,1-difluor-etĂĄn.
Az 1 562 026 sz. angol szabadalmi leĂrĂĄsban polisztirolhabok elĆĂĄllĂtĂĄsĂĄrĂłl szĂĄmolnak be, az eljĂĄrĂĄs sorĂĄn az 1 537 421 sz. szabadalmi leĂrĂĄsban megadott habosĂtĂłszereket hasznĂĄljĂĄk fel azzal az eltĂ©rĂ©ssel, hogy itt R1 diklĂłr-metil-csoportot jelent.
A 4 636 537 sz. USA-beli szabadalmi leĂrĂĄsban szereplĆ eljĂĄrĂĄsban szĂ©n-dioxid, etil-klorid Ă©s diklĂłrdifluor-metĂĄn (Fâ12) vagy 1-klĂłr-1,1-difluor-etĂĄn (F142b) vagy ezek keverĂ©ke alkotja a habosĂtĂłszer keverĂ©ket. Az elsĆdleges cellamĂ©ret csökkentĂ©sĂ©re gĂłckĂ©pzĆszer is adagolhatĂł a habosĂthatĂł keverĂ©khez. GĂłckĂ©pzĆkĂ©nt hasznĂĄlhatĂł pl. talkum, kalcium-szilikĂĄt, indigĂł stb.
A 3 960 792 sz. USA-beli szabadalmi leĂrĂĄs zĂĄrt cellĂĄs habszerkezetƱ polisztirolhabok elĆĂĄllĂtĂĄsĂĄra szolgĂĄlĂł habosĂtĂłanyag keverĂ©krĆl szĂĄmol be. Az alkalmazott habosĂtĂłanyag keverĂ©k a levegĆhöz viszonyĂtva 0,75-6-szoros diffĂșziĂł sebessĂ©ggel halad a sztirol polimeren ĂĄt. A szabadalmi leĂrĂĄsban ilyen tulajdonsĂĄgĂș keverĂ©kkĂ©nt a metil-klorid Ă©s diklĂłr-difluor-metĂĄn; metil-klorid, neopentĂĄn Ă©s diklĂłr-difluor-metĂĄn; metil-klorid, dikĂłr-difluor-metĂĄn Ă©s diklĂłr-tetrafluoretĂĄn elegyeit soroljĂĄk fel. A felhasznĂĄlt habosĂtĂłszer keverĂ©k csakis olyan lehet, melyben a sztirol polimer nem oldĂłdik.
A 3 770 668 sz. USA-beli szabadalmi leĂrĂĄs olyan zĂĄrt cellĂĄs habszerkezetƱ polisztirol habtestekrĆl szĂĄmol be, ahol a hab meghatĂĄrozott mennyisĂ©gƱ diklĂłrdifluor-metĂĄnt, triklĂłr-fluor-metĂĄnt vagy 1,2-diklĂłr-tetrafluor-etĂĄnt tartalmaz, s az ĂĄtlagos cellamĂ©ret 0,ÎÎ,45 mm közötti, a habosĂtott testek sƱrƱsĂ©ge pedig a 22,43-28,84 kg/m3 (1,4-1,8 lb/ft3) tartomĂĄnyba esik. A polisztirolhabok habosĂtĂłanyagai az elĆbb felsoroltakon kĂvĂŒl tartalmazhatnak mĂ©g szĂ©nhalogenideket pl. metil-klorid, etil-klorid, vinil-klorid Ă©s ezek keverĂ©kei.
Az extrudĂĄlt szintetikus habosĂtott testek elĆĂĄllĂtĂĄsĂĄra szolgĂĄlĂł ĂĄltalĂĄnos eljĂĄrĂĄs az alĂĄbbi lĂ©pĂ©seket tartalmazza.
Egy alkenil-csoporttal szubsztituĂĄlt aromĂĄs plimert, pl. polisztirolt melegĂtve plasztifikĂĄlunk, majd egy vagy több folyĂ©kony habosĂtĂłszert adunk hozzĂĄ, a polimerrel alaposan elkeverjĂŒk olyan körĂŒlmĂ©nyek között, melyek lehetĆvĂ© teszik az illĂ©kony habosĂtĂłszernek az alapos elkeverĂ©sĂ©t, s megakadĂĄlyozzĂĄk a keverĂ©k habzĂĄsĂĄt. A polimer Ă©s a habosĂtĂłszerek alapos, mĂ©lyrehatĂł keverĂ©s utĂĄn keletkezĆ elegyĂ©t, mely adott esetben tovĂĄbbi adalĂ©kanyagokat is tartalmazhat, pl. gĂłckĂ©pzĆket, Ă©gĂ©sgĂĄtlĂłkat stb. lehƱtjĂŒk, majd a nyomĂĄs csökkentĂ©sĂ©vel Ă©rhetjĂŒk el a keverĂ©k habzĂĄsĂĄt, a kĂvĂĄnt habosĂtott testek keletkezĂ©sĂ©t. A kĂvĂĄnt tulajdonsĂĄgĂș habosĂtott testek a lehƱtött plasztifikĂĄlt polimer-habosĂtĂłszer keverĂ©k alacsonyabb nyomĂĄson valĂł extrĂșziĂłjĂĄval ĂĄllĂthatĂłk elĆ. Bizonyos extrĂșziĂłs eljĂĄrĂĄsokban a habosĂthatĂł elegyet egy vĂĄkuum kamrĂĄba extrudĂĄljuk, s ott a hab expanziĂłja atmoszferikusnĂĄl kisebb nyomĂĄson következik be. VĂĄkuum habextrĂșziĂłs berendezĂ©sre Ă©s eljĂĄrĂĄsokra talĂĄlhatunk pĂ©ldĂĄkat a 3 584 108; a
169 272 Ă©s a 3 822 331 sz. USA-beli szabadalmi leĂrĂĄsokban. A vĂĄkuum extrĂșziĂłs technika felhasznĂĄlĂĄsĂĄnak egyik problĂ©mĂĄja az anyagnak a vĂĄkuum kamrĂĄbĂłl valĂł eltĂĄvolĂtĂĄsĂĄval kapcsolatos, kĂŒlönösen, ha az anyag kĂ©nyes termĂ©szetƱ vagy törĂ©keny, mint pl. a polisztirolhab nagy tĂĄblĂĄk vagy darabos testek formĂĄjĂĄban. Ennek a problĂ©mĂĄnak a megoldĂĄsĂĄra nyĂșjt megoldĂĄst a 3 704 083 Ă©s a 4 044 084 sz. USA-beli szabadalmi leĂrĂĄs egy hidrosztatikus elvƱ elvĂ©teli rendszer felhasznĂĄlĂĄsĂĄval. Az extrĂșziĂłs berendezĂ©s tovĂĄbbi mĂłdosĂtĂĄsĂĄt Ă©s javĂtĂĄsĂĄt jelenti az a kĂ©szĂŒlĂ©k, melyrĆl a
199 310 sz. szabadalmi leĂrĂĄs szĂĄmol be, s mely egy nagy hidrosztatikus elvƱ elvĂ©teli rendszert tartalmaz, amely evakuĂĄlt ĂĄllapotban gyakorlatilag vĂzzel van feltöltve, felsĆ rĂ©szĂ©ben azonban vĂĄkuum kamra talĂĄlhatĂł, ahol az extrudĂĄlĂł szerszĂĄmbĂłl kiömlĆ anyag kellĆkĂ©ppen kiterjedhet.
TalĂĄlmĂĄnyunk 14,4-56,1 kg/m3 tĂ©rfogati tömeggel jellemezhetĆ habosĂtott testek elĆĂĄllĂtĂĄsĂĄra szolgĂĄlĂł eljĂĄrĂĄs. A talĂĄlmĂĄny tehĂĄt eljĂĄrĂĄs hosszirĂĄnyban kiterjedĆ, extrudĂĄlt, hĆre lĂĄgyulĂł alkenil-helyettesĂtett aromĂĄs mƱanyag alapanyagĂș, habosĂtott testek elĆĂĄllĂtĂĄsĂĄra, melynek sorĂĄn a hĆre lĂĄgyulĂł mƱanyagot hĆvel plasztifikĂĄljuk; egy vagy több folyĂ©kony habosĂtĂłszert adunk hozzĂĄ; a habosĂtĂłszert egyenletesen belekeverjĂŒk a mƱanyagba, olyan nyomĂĄson, amely elegendĆ ahhoz, hogy megelĆzze a mƱanyag habosodĂĄsĂĄt, Ăgy habosĂthatĂł mƱanyagkeverĂ©ket kĂ©pezĂŒnk; a habosĂthatĂł mƱanyagkeverĂ©ket extrudĂĄljuk, Ăgy habosĂtott testeket hozunk lĂ©tre; a habosĂtott testeket szobahĆmĂ©rsĂ©kletre lehƱtjĂŒk, Ă©s a habosĂthatĂł mƱanyag elegyhez adott esetben gĂłckĂ©pzĆszert Ă©s adott esetben szĂ©n-dioxidot adagolunk. Az eljĂĄrĂĄst az jellemzi, hogy olyan habosĂtott testeket ĂĄllĂtunk elĆ, melyek sƱrƱsĂ©ge 14,4â
56,1 kg/m3 (0,9-3,1 lb/ft3), a mƱanyag tömegĂ©re szĂĄmĂtva 3-16 tömegrĂ©sz folyĂ©kony habosĂtĂłszert adagolunk a mƱanyagkompozĂciĂłhoz, Ă©s habosĂtĂłszerkĂ©nt az l-klĂłr-l,l-difluor-etĂĄn, 1,1,1,2-tetrafluor-etĂĄn Ă©s 2klĂłr-l,l,l,2-tetrafluor-etĂĄn közĂŒl legalĂĄbb egyet, tovĂĄbbĂĄ adott esetben mĂ©g a mƱanyag tömegĂ©re vonatkoztatva 0,4-1,5 tömeg% szĂ©ndioxidot, Ă©s/vagy legalĂĄbb egy tovĂĄbbi alkil-halogenid, diklĂłr-difluor-etĂĄn,
HU 209 957 Î Ă©s klĂłr-difluor-etĂĄn közĂŒl vĂĄlasztott habosĂtĂłszert adagolunk, az alkil-halogenid habosĂtĂłszer teljes mennyisĂ©ge a mƱanyag tömegĂ©re szĂĄmĂtva 3-16 tömegrĂ©sz, a habosĂtĂłszer adott esetben gĂłckĂ©pzĆ adalĂ©kot is adagolunk, Ă©s az extrudĂĄlĂĄst 6,67-91,42 kPa (2-27 Hg in) nyomĂĄsĂș extrĂșziĂłs tĂ©rben vĂ©gezzĂŒk, Ăgy 14,456,1 kg/m3 (0,9-3,1 lb/ft3) sƱrƱsĂ©gƱ habosĂtott testet kĂ©pezĂŒnk.
A talĂĄlmĂĄny egyik lehetsĂ©ges megvalĂłsĂtĂĄsi mĂłdjĂĄnĂĄl a keverĂ©ket csökkentett nyomĂĄson extrudĂĄljuk. A lĂ©gkörinĂ©l kisebb nyomĂĄsĂș teret egy elnyĂșjtott kamrĂĄban ĂĄllĂtjuk elĆ, a kamra egyik vĂ©gĂ©n a habosĂthatĂł mƱanyag keverĂ©k hatol be egy extrĂșziĂłs szerszĂĄmon Ă©s a mĂĄsik vĂ©gĂ©n a habosĂtott test egy vĂzfĂŒrdĆn keresztĂŒl tĂĄvozik.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄssal elĆĂĄllĂtott habosĂtott testekre jellemzĆ, hogy tĂ©rfogati tömegĂŒk megfelel a kĂvĂĄnalmaknak, sejtszerkezetĂŒk ĂĄtlagos cellamĂ©rete viszonylag kicsi, kb. 0,5 mm vagy ennĂ©l kisebb, nyomĂłszilĂĄrdsĂĄguk Ă©s tĂ©rfogategysĂ©gre esĆ cellaszĂĄmuk nagy.
A talĂĄlmĂĄny jobb megĂ©rtĂ©se kedvéért a következĆkben a megoldĂĄst ĂĄbrĂĄk kapcsĂĄn szemlĂ©ltetjĂŒk. Az
1. ĂĄbra a talĂĄlmĂĄny szerinti eljĂĄrĂĄs kivitelezĂ©sĂ©hez elĆnyösen felhasznĂĄlhatĂł berendezĂ©s sematikus oldalnĂ©zeti metszeti kĂ©pe. A
2. ĂĄbra a kamra bemenĆ oldalĂĄn talĂĄlhatĂł, legyezĆ alakĂș ĂuvĂłka rendszer Ă©s alakĂtĂł mechanizmus nagyĂtott felĂŒlnĂ©zeti rĂ©szletrajza. A
3. ĂĄbra az egyik dugattyĂș-henger egyĂŒttes sematikus ĂĄbrĂĄzolĂĄsa, amely az alakĂtĂł hengerek vagy egyĂ©b felsĆ szĂĄllĂtĂł berendezĂ©sek lebegtetĂ©sĂ©re szolgĂĄl.
A szabadalmi leĂrĂĄsban Ă©s az igĂ©nypontokban szereplĆ rĂ©sz, illetve szĂĄzalĂ©k Ă©rtĂ©kek tömegviszonyokat reprezentĂĄlnak.
J A talĂĄlmĂĄny szerinti eljĂĄrĂĄssal habosĂthatĂłk, s extrudĂĄlhatĂłk az alĂĄbbi hĆre lĂĄgyulĂł mƱanyagok: pl. szubsztituĂĄlt aromĂĄs vinilpolimerek (homo- vagy kopolimerek), poli(fenilĂ©n-Ă©ter)-ek, poli(vinil-klorid), vinilidĂ©n-klorid (80 rĂ©sz) Ă©s akrilnitril (20 rĂ©sz) kopolimerizĂĄciĂłjĂĄnĂĄl keletkezĆ poli(vinilidĂ©n-klorid)-ok, poliolefinek pl. polietilĂ©n Ă©s etilĂ©n valamint vinil-acetĂĄt vagy etil-akrilĂĄt kopolimerjei, stb. Az ilyen tĂpusĂș gyantĂĄk keverĂ©kei a talĂĄlmĂĄny szerinti eljĂĄrĂĄssal habosĂthatĂłk. PĂ©ldĂĄul polisztirol Ă©s poli(fenilĂ©n-Ă©ter) keverĂ©kĂ©bĆl a talĂĄlmĂĄny szerinti eljĂĄrĂĄssal habosĂtott testek alakĂthatĂłk ki. A talĂĄlmĂĄny szerinti eljĂĄrĂĄsban a hĆre lĂĄgyulĂł mƱanyagok közĂŒl elĆnyösen dolgozhatĂłk fel a szubsztituĂĄlt aromĂĄs vinil polimerek.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄssal extrudĂĄlt Ă©s habosĂtott szubsztituĂĄlt aromĂĄs poliolefmek legalĂĄbb 50 t% (I) ĂĄltalĂĄnos kĂ©plet szerint aromĂĄs alkenil vegyĂŒletet tartalmaznak: ahol
Ar aromĂĄs szĂ©nhidrogĂ©ncsoportot vagy benzol homolĂłgok közĂ© tartozĂł halogĂ©ntartalmĂș aromĂĄs szĂ©nhidrogĂ©ncsoportot jelent.
R jelentĂ©se hidrogĂ©natom vagy metilcsoport. A polimerizĂĄlĂĄs sorĂĄn megmaradĂł monomer legalĂĄbb egy etilĂ©n tĂpusĂș telĂtetlen, az aromĂĄs vegyĂŒlettel kopolimerizĂĄlĂłdni kĂ©pes monomert tartalmaz.
Az (I) ĂĄltalĂĄnos kĂ©pletnek megfelelĆ aromĂĄs alkenil vegyĂŒlet egyes eljĂĄrĂĄsokban lehet a (II) ĂĄltalĂĄnos kĂ©pletƱ vegyĂŒlet, ahol
R1, R3, R4, R5 Ă©s R6 egymĂĄstĂłl fĂŒggetlenĂŒl hidrogĂ©n-, klĂłr- vagy brĂłmatom, vagy 1-4 szĂ©natomos alkilcsoport Ă©s
R2 hidrogĂ©natom vagy metilcsoport, a szubsztituensek jelentĂ©sei azzal a megkötĂ©ssel Ă©rtelmezhetĆk, hogy a monomer összes szĂ©natomszĂĄma nem haladhatja meg a 12-t.
Az alkenil-szubsztituĂĄlt aromĂĄs monomerek közĂ© tartozik a sztirol, α-metil-sztirol, o-metil-sztirol, mmetil-sztirol, p-metil-sztirol, o-klĂłr-sztirol, p-klĂłr-sztirol, 2,6-diklĂłr-sztirol, o-brĂłm-sztirol, stb. Az etilĂ©n tĂpusĂș telĂtetlen monomerre, mely az elĆbb felsorolt sztirol szĂĄrmazĂ©kokkal kopolimerizĂĄlhatĂł, az alĂĄbbi pĂ©ldĂĄk sorolhatĂłk fel: metil-metakrilĂĄt, akrilsav-nitril, alma-savanhidrid, metil-maleinsavanhidrid, metilĂ©n-borostyĂĄnkĆsavanhidirid, stb.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄsban az alkenilcsoporttal szubsztituĂĄlt aromĂĄs polimerek közĂŒl elĆnyösen hasznĂĄlhatĂłk fel a sztirol tĂpusĂș polimerek. A polisztirolok lehetnek sztirol homopolimerek vagy sztirolnak Ă©s egy vagy több kopolimerizĂĄlhatĂł etilĂ©n tĂpusĂș, telĂtetlen monomernek a kopolimerjei. Ilyen sztirolpolimerek Ă©s sztirolkopolimerek a kereskedelemben több forrĂĄsbĂłl a több eltĂ©rĆ molekulatömeggel jellemzett minĆsĂ©gben beszerezhetĆk. A polimerek molekulatömege szĂĄmtalan mĂłdszerrel, a szakemberek szĂĄmĂĄra ismert mĂłdon hatĂĄrozhatĂł meg, ilyen pĂ©ldĂĄul a viszkozitĂĄs meghatĂĄrozĂĄsa, a fĂ©nytörĂ©s Ă©s az ultracentrifugĂĄlis szedimentĂĄciĂł Ă©rtĂ©keinek vizsgĂĄlata. A polimer olvadĂ©k egy adott keresztmetszetƱ nyĂlĂĄson keresztĂŒl törtĂ©nĆ ĂĄramlĂĄsi sebessĂ©ge, melyet olvadĂ©k folyĂĄsi indexnek (MFI) is neveznek, szintĂ©n felvilĂĄgosĂtĂĄst adhat a molekulatömeg viszonyokrĂłl. Az MFI mĂłdszer viszonylag kis költsĂ©g vonzatĂș, egyszerƱen kivitelezhetĆ technika. A mĂłdszer rĂ©szletei szĂĄmos publikĂĄciĂłban megtalĂĄlhatĂłk, pl. P. J. Flory a Principles of Polimer Chemistry cĂmen megjelent (Comell University Press, Ithacs, New York, 1953) könyvĂ©ben. A 100 000-500 000 közötti molekulatömegƱ polimerek az ĂĄltalĂĄban hasznosĂthatĂłk, elĆnyösek a 150 000-450 000 közöttiek, s mĂ©g elĆnyösebbek a 250 000-350 000 közötti molekulatömegƱek. A felhasznĂĄlhatĂł sztirolpolimerek (a tovĂĄbbiakban polisztirolokkĂ©nt hivatkozunk rĂĄjuk) szĂĄmos kereskedelmi forrĂĄsbĂłl beszerezhetĆk, s az Ăgy beszerzett polisztirolok több tulajdonsĂĄgukban kĂŒlönböznek, pl. eltĂ©rĆek az olvadĂ©k folyĂĄsi indexek, polisztirolok beszerezhetĆk pĂ©ldĂĄul az ARCO Chemical Company-tĂłl âDYLENEâ ĂĄltalĂĄnos mĂĄrkajelzĂ©ssel, ilyen pl. a DYLENE D-8, valamint a Polysar Ltd.-tĆl (Sarnia, Ontario).
A talĂĄlmĂĄny szerinti eljĂĄrĂĄssal elĆĂĄllĂtott extrudĂĄlt, habosĂtott termĂ©kek tulajdonsĂĄgai a gyĂĄrtĂĄshoz felhasznĂĄlt polimer molekulatömegĂ©nek megvĂĄltoztatĂĄsĂĄval szabĂĄlyozhatĂłk Ă©s mĂłdosĂthatĂłk. PĂ©ldĂĄul kisebb sƱrƱsĂ©gƱ polisztirolhabok Ă©s mĂłdosĂthatĂłk. PĂ©ldĂĄul kisebb sƱrƱsĂ©gƱ polisztirolhabok elĆĂĄllĂtĂĄsa egyszerƱbbĂ© tehetĆ nagy molekulatömegƱ polimerek felhasznĂĄlĂĄsĂĄ4
HU 209 957 Î val, s nagyobb sƱrƱsĂ©gƱ habosĂtott testek elĆĂĄllĂtĂĄsa egyszerƱsĂthetĆ kisebb molekulatömegƱ vagy nagyobb viszkozitĂĄsĂș polimerek felhasznĂĄlĂĄsĂĄval.
SpeciĂĄlis sztirolkopolimerek ĂĄllĂthatĂłk elĆ pĂ©ldĂĄul az alĂĄbbi keverĂ©kekbĆl: 701% sztirol Ă©s 301% akrilnitril; 80 t% sztirol Ă©s 20 t% vinil-toluol; 75 t% sztirol Ă©s 251% metil-metakrilĂĄt; stb.
Az illĂ©kony Ă©s folyĂ©kony habosĂtĂłszerek, melyeket a talĂĄlmĂĄny szerinti eljĂĄrĂĄs alkalmaz, az alĂĄbb felsorolandĂł vegyĂŒletek közĂŒl legalĂĄbb egyet tartalmaznak: l-klĂłr-l,l-difluor-etĂĄn (HCFC-142b), 1,1,1,2-tetrafluor-etĂĄn (HFC-134a), 2-klĂłr-1,1,1,2-tetrafluor-etĂĄn (HCFC-124). A melegĂtĂ©ssel plasztifikĂĄlt alkenil-csoporttal szubsztituĂĄlt aromĂĄs polimerhez. 100 tömegrĂ©sz polimerre vonatkoztatva 3-16 tömegrĂ©sz vagy mĂ©g ezt is meghaladĂł mennyisĂ©gƱ habosĂtĂłszert adunk. A polimerbe kevert habosĂtĂłszer mennyisĂ©gĂ©nek mĂłdosĂtĂĄsa, a habosĂtĂłszer keverĂ©ket alkotĂł komponensek minĆsĂ©gĂ©tĆl valĂł fĂŒggĂ©sen tĂșl, lehetĆsĂ©get nyĂșjt a kĂvĂĄnt kĂŒlönbözĆ jellemzĆjƱ extrudĂĄlt habtestek elĆĂĄllĂtĂĄsĂĄra.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄsban felhasznĂĄlt habosĂtĂłszer a l-klĂłr-l,l-difluor-etĂĄn (HCFC-142b), 1,1,1,2tetrafluor-etĂĄn (HFC-134a), 2-klĂłr-1,1,1,2-tetrafluoretĂĄn (HCFC-124) mellett egyĂ©b illĂ©kony komponenseket is tartalmazhat, melyek szintĂ©n hatĂ©kony habosĂtĂłszerek. Az adott esetben alkalmazott, kiegĂ©szĂtĆ habosĂtĂłszerekre pĂ©lda a diklĂłr-difluor-metĂĄn (CFC-12) Ă©s a klĂłr-difluor-metĂĄn (HCFC-22), szĂ©n-dioxid Ă©s a fentiek keverĂ©kei. A habosĂtĂłszer keverĂ©kek 25-75 t% 1klĂłr-l,l-difluĂłr-etĂĄnt, 1,1,1,2-tetrafluor-etĂĄnt vagy 2klĂłr-l,l,l,2-tetrafluor-etĂĄnt tartalmaznak, illetve 2575 t%-ban tartalmazzĂĄk CFC-12 Ă©s HCFC-22 közĂŒl legalĂĄbb az egyiket. A kĂŒlönösen elĆnyös habosĂtĂłszer komplexek 30-70 t% 1,1,1,2-tetrafluor-etĂĄnt, 7030 t% 1-klĂłr-l; 1-difluor-etĂĄnt; 50-70 t% 1-klĂłr-1,1difluor-etĂĄnt Ă©s 30-50 t% klĂłr-difluor-metĂĄnt; a 6080 t% 1-klĂłr-l, 1-difluor-etĂĄnt Ă©s 20^10 t% diklĂłr-difluor-metĂĄnt tartalmaznak; elĆnyösek mĂ©g az olyan kombinĂĄciĂłk, melyek szĂ©n-dioxid mellett 60 t% 1klĂłr-1,1-difluor-etĂĄnt Ă©s 40 t% diklĂłr-difluor-metĂĄnt vagy 68 t% 1-klĂłr-l,1-difluor-etĂĄnt Ă©s 32 t% diklĂłrdifluor-metĂĄnt tartalmaznak. A szĂ©n-dioxid Ă©s a CFC tĂpusĂș habosĂtĂłszerek kombinĂĄciĂłja azt eredmĂ©nyezi a habosĂtott testek elĆĂĄllĂtĂĄsa sorĂĄn, hogy a hasonlĂł CFC-vel elĆĂĄllĂtott, hasonlĂł sƱrƱsĂ©gƱ testekkel összevetve, a cellamĂ©ret szĂ©n-dioxid felhasznĂĄlĂĄsa mellett kisebb lesz. TovĂĄbbĂĄ a szĂ©n-dioxidot is tartalmazĂł habosĂtĂłszer keverĂ©kek az extrudĂĄlt, expandĂĄltatott polisztirolhabok nyomĂłszilĂĄrdsĂĄgĂĄt összevethetĆ sƱrƱsĂ©g mellett elĆnyösen megnövelik. Amennyiben szĂ©n-dioxidot is alkalmazunk egy vagy több halokarbonnal kombinĂĄlva, a szĂ©n-dioxidot a gyanta tömegĂ©re vonatkoztatva 0,4-1,5 t%-ban lehet felhasznĂĄlni. A fenti habosĂtĂłszerekkel illetve habosĂtĂłszer keverĂ©kkel megfelelĆ minĆsĂ©gƱ extrudĂĄlt polisztirolhabot lehet elĆĂĄllĂtani, s Ăgy nem szĂŒksĂ©ges nagy illĂ©konysĂĄgĂș s nagy diffĂșziĂłs ĂĄllandĂłjĂș anyagokat, mint pl. metil-klorid vagy etil-klorid, hasznĂĄlni. Alkoholok felhasznĂĄlĂĄsa nem szĂŒksĂ©ges, s ĂĄltalĂĄban nem is szerepelnek a habosĂtĂłszer keverĂ©kekben. A rĂ©gebbi habosĂtĂłszer keverĂ©kekben szereplĆ alkoholokra az alĂĄbbi pĂ©ldĂĄk emlĂthetĆk: metanol, etanol, izopropil-alkohol.
Az eljĂĄrĂĄs sorĂĄn a habosĂtĂłszert az ismert mĂłdszerek bĂĄrmelyikĂ©vel az alkenilcsoporttal szubsztituĂĄlt aromĂĄs alapanyaghoz adhatjuk. Az egyik kedvezĆ megvalĂłsĂtĂĄsnĂĄl a habosĂtĂłszert vagy habosĂtĂłszer keverĂ©ket közvetlenĂŒl az anyag megömlesztĂ©sĂ©re Ă©s keverĂ©sĂ©re szolgĂĄlĂł berendezĂ©sbe pl. extruderbe injektĂĄljuk. Amennyiben egynĂ©l több habosĂtĂłszert hasznĂĄlunk, lehetĆsĂ©g van arra, hogy ezeket kĂŒlön-kĂŒlön injektĂĄljuk a megömlesztett anyagba. A talĂĄlmĂĄny szerinti eljĂĄrĂĄs egy elĆnyös foganatosĂtĂĄsi mĂłdjĂĄnĂĄl az 1. ĂĄbrĂĄn lĂĄthatĂł 10 tandem extrudereket alkalmazzuk, oly mĂłdon, hogy az elsĆ extruder vĂ©gzi a habosĂtĂłszer bejuttatĂĄsĂĄt Ă©s keverĂ©sĂ©t, mĂg a mĂĄsodik extruder szabĂĄlyozza az anyag keverĂ©sĂ©t Ă©s lehƱtĂ©sĂ©t. A habosĂthatĂł polimerkeverĂ©k s megömlesztett polimeren Ă©s habosĂtĂłszeren (illetve szereken) kĂvĂŒl tartalmazhat, s ĂĄltalĂĄban tartalmaz is egyĂ©b adalĂ©kanyagokat, melyek bizonyos jellemzĆket Ă©s/vagy tulajdonsĂĄgokat mĂłdosĂtanak. GĂłckĂ©pzĆkkel az elsĆdleges cellamĂ©retet csökkenthetjĂŒk. GĂłckĂ©pzĆkĂ©nt felhasznĂĄlhatĂł anyagok a talkum, kalcium-szilikĂĄt, kalcium-karbonĂĄt, indigĂł Ă©s egyebek. A gĂłckĂ©pzĆszert 100 tömegrĂ©sz polimerre vonatkoztatva 0,05-5,0 tömegrĂ©sz arĂĄnyban szokĂĄs a habosĂthatĂł polimerhez adni. A habosĂtandĂł keverĂ©khez szokĂĄs lĂĄgyĂtĂłkat is adni, ilyen pĂ©ldĂĄul a folyĂ©kony paraffin, hidrogĂ©nezett kĂłkuszolaj, stb. EgyĂ©b hasznos adalĂ©kanyagok mĂ©g az Ă©gĂ©sgĂĄtlĂłk Ă©s stabilizĂĄtorok.
Az extruderbĆl a megömlesztett polimer-habosĂtĂłszer keverĂ©k egy olyan zĂłnĂĄba jut, ahol a keverĂ©k expandĂĄl. BĂĄr ez a zĂłna lehet lĂ©gköri nyomĂĄsĂș is, a talĂĄlmĂĄny szerinti eljĂĄrĂĄs egy elĆnyös megvalĂłsĂtĂĄsa sorĂĄn ez a zĂłna csökkentett nyomĂĄsĂș, azaz a nyomĂĄs a lĂ©gkörinĂ©l kisebb. Ez Ășgy valĂłsĂthatĂł meg, hogy az expanziĂłs zĂłna vĂĄkuumkamrĂĄt tartalmaz, amelyben a nyomĂĄs a kĂvĂĄnt szintre szabĂĄlyozhatĂł, s mely ĂĄltal a habosĂthatĂł polimer keverĂ©k a kamrĂĄn belĂŒl habosĂtott testekkĂ© expandĂĄl. A vĂĄkuumkamrĂĄn belĂŒli nyomĂĄs vĂĄltoztathatĂł, ily mĂłdon a kĂvĂĄnt jellemzĆknek megfelelĆ, kĂŒlönbözĆ tulajdonsĂĄgĂș (cellamĂ©ret, cellatĂ©rfogat Ă©s sƱrƱsĂ©g) habosĂtott testeket nyerhetĂŒnk. A vĂĄkuumkamra nyomĂĄsa kevesebb mint 91,4 kPa (27 Hg in), ĂĄltalĂĄban 6,77-91,4 kPa tartomĂĄnyban talĂĄlhatĂł. NĂ©hĂĄny foganatosĂtĂĄsi mĂłdnĂĄl a nyomĂĄst 6,77-67,7 kPa között tartjuk. ĂltalĂĄban a vĂĄkuum növelĂ©sĂ©vel (alacsonyabb nyomĂĄson) a keverĂ©k felhabzĂĄsa növekszik Ă©s Ăgy kisebb sƱrƱsĂ©gƱ habokat nyerĂŒnk.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄst egy elĆnyös megvalĂłsĂtĂĄsĂĄnĂĄl, mely az 1. ĂĄbrĂĄn lĂĄthatĂł, a fent leĂrt mĂĄsodlagos extruder 12 kimenĆ vĂ©gĂ©t Ășgy alakĂtottuk ki, hogy beleilleszkedjĂ©k, s egyben tömĂtse a 14 hajlĂtott alagĂșt (mely a 15 vĂĄkuumkamrĂĄt zĂĄrja magĂĄba), 13 felsĆ vĂ©gĂ©t, az alagĂșt 16 alsĂł vĂ©ge a 17 vĂztartĂĄlyba merĂŒl, amely a vĂĄkuumkamra mĂĄsik vĂ©gĂ©t tömĂti. A vĂzfĂŒrdĆ lehetĆsĂ©get ad arra, hogy a kĂ©sztermĂ©ket a kamrĂĄbĂłl a vĂĄkuum fenntartĂĄsa mellett kivezethessĂŒk. A vĂĄkuumkamrĂĄban keletkezĆ extrudĂĄlt polisztirolhab a kamrĂĄban elĆre halad, majd a vĂzrĂ©tegen keresztĂŒl a vĂĄkuumkamrĂĄbĂłl a vĂzzĂĄr mĂĄsik oldalĂĄn kijut a lĂ©gköri nyo5
HU 209 957 Î mĂĄsra. Azon tĂșlmenĆen, hogy a kamrĂĄban lĂ©vĆ vĂĄkuumot fenntartja, a vĂzfĂŒrdĆ a habosĂtott testeknek a kamrĂĄn belĂŒli lehƱlĂ©sĂ©t is biztosĂtja.
A mƱködtetĂ©s sorĂĄn ĂĄltalĂĄban az extrudĂĄlt hab a 2. ĂĄbrĂĄn rĂ©szletesebben feltĂŒntetett 20 extrĂșziĂłs szerszĂĄmon tĂĄvozik, a keverĂ©k kiterjedĂ©sĂ©t Ă©s a hab alakĂtĂĄsĂĄt a kiömlĆnyĂlĂĄs sĂkja alatt Ă©s felett elhelyezett 22 Ăvelt hengerek szabĂĄlyozzĂĄk. A kiömlĆnyĂlĂĄsbĂłl tĂĄvozĂł 24 habot - az ĂĄbrĂĄn lĂĄthatĂł alsĂł Ă©s felsĆ hengerek, melyek a 25 meghajtott korongsort hajlĂtott tengelyeken tartalmazzĂĄk - a vastagsĂĄg szempontjĂĄbĂłl alakĂtjĂĄk Ă©s vĂ©gleges szĂ©lessĂ©gre nyĂșjtjĂĄk. Amint az ĂĄbrĂĄn feltĂŒntettĂŒk a 20 legyezĆ alakĂș kiömlĆnyĂlĂĄs alatt Ă©s felett egyarĂĄnt 5 ilyen meghajtott korongsort helyeztĂŒnk el. TovĂĄbbi vastagsĂĄg Ă©s egyenletessĂ©g szabĂĄlyozĂĄs valĂłsĂthatĂł meg azĂĄltal, hogy a hab panelt a 27 pĂĄros, alsĂł Ă©s felsĆ szĂĄllĂtĂłszalagok között vezetjĂŒk ĂĄt. A hab sƱrƱsĂ©gĂ©t rĂ©szben a kamrĂĄban uralkodĂł vĂĄkuum hatĂĄrozza meg. MiutĂĄn az extrudĂĄlt hab vastagsĂĄgĂĄt, szĂ©lessĂ©gĂ©t Ă©s simasĂĄgĂĄt kialakĂtottuk, a vĂzfĂŒrdĆn 31 hajtĂłmƱvel ellĂĄtott 30 szĂĄllĂtĂłszalagon juttatjuk ĂĄt, miközben a hab a vĂzrĂ©tegen ĂĄthaladva lehƱl Ă©s szilĂĄrdabbĂĄ vĂĄlik. A habnak a vĂzzĂĄrĂłn valĂł ĂĄtjuttatĂĄsĂĄra bĂĄrmelyik megfelelĆ berendezĂ©s hasznĂĄlhatĂł, mint pl. az ĂĄbrĂĄn feltĂŒntetett szĂĄllĂtĂłszalag. A talĂĄlmĂĄny szerinti eljĂĄrĂĄs egy elĆnyös megvalĂłsĂtĂĄsĂĄnĂĄl a habosĂtott testeket a vĂzen keresztĂŒl egy felsĆ szĂĄllĂtĂłszalag viszi ĂĄt, a hab a szalaghoz a fajsĂșlya rĂ©vĂ©n felĂșszva tapad. Az ĂĄbrĂĄn feltĂŒntetett legcĂ©lszerƱbbnek tartott megvalĂłsĂtĂĄsnĂĄl a 20 extrĂșziĂłs szerszĂĄm legyezĆ alakĂș, s rajta a 32 Ăves kiömlĆnyĂlĂĄs talĂĄlhatĂł, Ă©s az ezen a legyezĆ alakĂș szerszĂĄmon kiömlĆ keverĂ©k a feltĂŒntetett önbeĂĄllĂł alakĂtĂł hengerek ĂĄltal nyer tovĂĄbbi formĂĄzĂĄst.
Amint azt a 2. Ă©s 3. ĂĄbrĂĄn feltĂŒntettĂŒk, annak Ă©rdekĂ©ben, hogy a 22 hengereket Ă©s a 27 szĂĄllĂtĂłszalagot pontosabban tudjuk szabĂĄlyozni, ezeket a 34 dugattyĂșs henger összeĂĄllĂtĂĄsok rĂ©vĂ©n lebegtetni lehet. Az ilyen dugattyĂșs hengerek 36 rudazata a 37 vezetĆ tengelyhez van kötve, amely a megfelelĆ hengert vagy szĂĄllĂtĂłszalagot tartja. Mindegyikhez lehetsĂ©ges egy ilyen dugattyĂșs henger összeĂĄllĂtĂĄs.
A 41 levegĆ forrĂĄsbĂłl a 42 nyomĂĄsszabĂĄlyozĂłn Ă©s 43 ellenĆrzĆ szelepen keresztĂŒl a 40 vezetĂ©ken ĂĄt sƱrĂtett levegĆt juttatunk be a hengerek alsĂł rĂ©szĂ©ben. Ily mĂłdon a hengerbe juttatott levegĆ nyomĂĄsĂĄnak szabĂĄlyozĂĄsĂĄval elĂ©rhetĆ, hogy a 22 Ăvelt hengert a pneumatikus mechanizmus sajĂĄt sĂșlya ellenĂ©ben lebegtesse. Amikor a lebegĂ©s megvalĂłsult, a dugattyĂșs henger egyik oldalĂĄra levegĆt vezetĂŒnk a 46 tĂĄpbĂłl a 45 vezetĂ©ken, a 47 szabĂĄlyozĂłn Ă©s 48 kontroll szelepen ĂĄt, Ăgy a hengerek a habosĂtott testekre gyakorolt hatĂĄsĂĄt pontosan tudjuk szabĂĄlyozni. A 22 Ăvelt hengerek sugarai eltĂ©rĆek, ezĂ©rt tĂĄra sĂșlyaik is kĂŒlönböznek. Mihelyt a henger lebegĆ ĂĄllapotban kerĂŒl, csak egy csekĂ©ly nyomĂĄskĂŒlönbsĂ©get alkalmazunk, Ăgy a henger ĂĄltal kifejtett erĆ kĂmĂ©letes.
A vĂĄkuum kamra, az alakĂtĂł mechanizmus Ă©s a legyezĆ alakĂș extrudĂĄlĂł szerszĂĄm rĂ©szleteit illetĆen a 4 199 310; a 4 234 529; Ă©s 4 364 722 sz. USA-beli szabadalmi leĂrĂĄsokra utalunk.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄssal elĆĂĄllĂtott alkenilcsoporttal szubsztituĂĄlt poliaromĂĄs habosĂtott testek az alĂĄbbi tulajdonsĂĄgokkal jellemezhetĆk:
sƱrƱsĂ©g: kb. 14,4-56,1 kg/m3 (0,9-3,5 lb/ft3), elĆnyösen 14,4-32 kg/m3 (0,9-1 lb/ft3) vagy 14,4-25,2 kg/m3 (0,9-1,6 lb/ft3) közötti Ă©rtĂ©k;
Ătlagos cellamĂ©ret: kevesebb mint 0,5 mm, elĆnyösen kevesebb, mint 0,3 mm;
cella szĂĄm: kis sƱrƱsĂ©g esetĂ©n 6100/cm3, kis sƱrƱsĂ©g esetĂ©n kĂŒlönösen elĆnyösen 9150/cm3, 20,8-25,2 kg/m3 közötti sƱrƱsĂ©g esetĂ©n 12 200/cm3; 32 kg/m3 sƱrƱsĂ©g felett 18 3OO/cm3.
Az alĂĄbbi pĂ©ldĂĄk a talĂĄlmĂĄny szerinti eljĂĄrĂĄst Ă©s a talĂĄlmĂĄny szerinti eljĂĄrĂĄssal elĆĂĄllĂtott habosĂtott testeket szemlĂ©ltetik. Az alĂĄbbi pĂ©ldĂĄkban felhasznĂĄlt ĂĄltalĂĄnos eljĂĄrĂĄs Ă©s berendezĂ©sek, amennyiben az attĂłl valĂł eltĂ©rĂ©st nem jelezzĂŒk, a következĆk: a kiindulĂĄsi polisztirol polimerbĆl, a visszaaprĂtott polisztirol polimerbĆl, talkumbĂłl Ă©s az Ă©gĂ©sgĂĄtlĂłbĂłl plasztifikĂĄlt keverĂ©ket kĂ©szĂtĂŒnk, s ebbe a keverĂ©kbe dolgozzuk be a habosĂtĂłanyagot, melynek rĂ©vĂ©n habosĂthatĂł polimer keverĂ©ket kapunk. A habosĂthatĂł polimer keverĂ©khez gĂłckĂ©pzĆt Ă©s Ă©gĂ©sgĂĄtlĂł anyagot adunk. A habosĂthatĂł keverĂ©ket az extruder kimenĆ nyĂlĂĄsĂĄn ĂĄt a vĂĄkuum alatt tartott hosszĂșkĂĄs kamra egyik vĂ©gĂ©be extrudĂĄljuk, itt a habosĂthatĂł keverĂ©k szabĂĄlyozott körĂŒlmĂ©nyek között expandĂĄl Ă©s 61 cm (24 in) szĂ©les folytonos tĂĄblĂĄt kĂ©pez, a tĂĄbla vastagsĂĄga a kĂvĂĄnalmaknak megfelelĆen vĂĄltoztathatĂł.
Az 1-5. pĂ©ldĂĄkban a legyezĆ alakĂș extrĂșziĂłs szerszĂĄm Ăvhossza 22 cm (8,66 in), sugara 12,7 cm (5 in) Ă©s szöge 120°. A 6-18. pĂ©ldĂĄkban a legyezĆ alakĂș extrĂșziĂłs szerszĂĄm Ăvhossza 20,90 cm (8,23 in), sugara 12,07 cm (4,75 in) Ă©s szöget 120°. MiutĂĄn a habosĂthatĂł keverĂ©ket a vĂĄkuumkamrĂĄban extrudĂĄljuk, a habosodĂł keverĂ©k expanziĂłjĂĄt a kiömlĆ nyĂlĂĄs alatt Ă©s felett elhelyezett Ăvelt hengerek szabĂĄlyozzĂĄk Ă©s ezek a 3,81-5,08 cm-en (1,5-2,0 in) belĂŒl a kĂvĂĄnt vastagsĂĄgĂș 61 cm szĂ©les vĂ©gtelenĂtett tĂĄblĂĄt ĂĄllĂtjĂĄk elĆ. MĂĄs tĂĄbla vastagsĂĄgot Ășgy Ă©rhetĂŒnk el, hogy szabĂĄlyozzuk az extrĂșziĂłs szerszĂĄm nyĂlĂĄsĂĄt Ă©s az Ăvelt hengerek helyzetĂ©t. A vĂ©gtelenĂtett habtĂĄbla a vĂĄkuumkamrĂĄn keresztĂŒl halad, majd vĂzfĂŒrdĆn keresztĂŒl vezetve lehƱl, s törĂ©kenyebbĂ© vĂĄlik. A vĂ©gtelenĂtett habtĂĄblĂĄkat, miutĂĄn a vĂzfĂŒrdĆn keresztĂŒlhaladtak, a kamra ellentĂ©tes oldalĂĄrĂłl ĂĄthĂșzzuk, igĂ©ny szerint igazĂtjuk, vĂĄgjuk.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄsnak megfelelĆen, a vĂĄkuumkamrĂĄbĂłl kikerĂŒlĆ habtĂĄblĂĄkat ismert mĂłdon vizsgĂĄljuk sƱrƱsĂ©g, cellamĂ©ret, cella szĂĄm, nyomĂłszilĂĄrdsĂĄg, Kfaktor Ă©s egyĂ©b vizsgĂĄlati szempontok szerint. Az ĂĄtlagos cellamĂ©ret a cella X, Y Ă©s Z irĂĄnyba meghatĂĄrozott mĂ©reteinek az ĂĄtlaga. Az X irĂĄny az extrĂșziĂłs folyamat irĂĄnya; Y a technolĂłgiai haladĂĄsi irĂĄnyra merĆleges, Z irĂĄny pedig a vastagsĂĄg. A talĂĄlmĂĄny szerinti eljĂĄrĂĄssal elĆĂĄllĂtott habtestek nyomĂłszilĂĄrdsĂĄgĂĄnak meghatĂĄrozĂĄsĂĄt az ASTM Test Cl65-83 sz. âA hĆszigetelĆk nyomĂłszilĂĄrdsĂĄgi tulajdonsĂĄgainak vizsgĂĄlataâ c. standard vizsgĂĄlati mĂłdszerrel vĂ©geztĂŒk.
Az eljĂĄrĂĄs Ă©s az azt megvalĂłsĂtĂł berendezĂ©s tovĂĄbbi rĂ©szleteit a pĂ©ldĂĄk tartalmazzĂĄk.
HU 209 957 Î
7-5. pĂ©ldĂĄk tömegrĂ©sz nyers sztirol polimer (ARCO Dylene D8 - olvadĂ©k folyĂĄsi indexe (MFI) = 5,0/, 20 tömegrĂ©sz visszaaprĂtott polisztirol, 0,15 tömegrĂ©sz talkum Ă©s 0,85 tömegrĂ©sz Ă©gĂ©sgĂĄtlĂł felhasznĂĄlĂĄsĂĄval plasztikus elegyet ĂĄllĂtunk elĆ. A plasztikus elegybe az alĂĄbbiakban pontosan megadott habosĂtĂłszer keverĂ©ket viszĂŒnk be, Ăgy habost thatĂł polimer keverĂ©ket kapunk. Az eljĂĄrĂĄs tovĂĄbbi rĂ©szleteit Ă©s habosĂtott testek nĂ©hĂĄny tulajdonsĂĄgĂĄt az 1. tĂĄblĂĄzatban mutatjuk be.
7. tĂĄblĂĄzat
| Példa | 1 | 2 | 3 | 4 | 5 |
| habosĂtĂłszer (t%) | |||||
| 32% F-12/68% Fâ142(b) | 8,5 | 8,5 | 8,5 | - | - |
| 40% F-22/60% F6142(b) | - | - | - | 7,4 | 7,4 |
| teljesĂtmĂ©ny (kg/Ăłra) | 445,4 | 445,4 | 445,5 | 446,3 | 446,3 |
| teljesĂtmĂ©ny (lb/hr) | 981,0 | 981,0 | 981,0 | 983,0 | 983,0 |
| vĂĄkuum (kPa) | 49,8 | 45,7 | 45,7 | 45,7 | 45,7 |
| vĂĄkuum (Hg in) | 14,7 | 13,5 | 13,5 | 13,5 | 13,5 |
| termék | |||||
| vastagsĂĄga (cm) | 3,581 | 3,912 | 3,835 | 3,835 | 3,835 |
| vastagsĂĄga (in) | 1,410 | 1,540 | 1,510 | 1,510 | 1,530 |
| sƱrƱség (kg/m3) | 25,15 | 21,79 | 21,95 | 21,31 | 21,95 |
| sƱrƱség (lb/ft3) | 1,57 | 1,36 | 1,37 | 1,33 | 1,37 |
| åtlagos cellaméret (mm) | 0,48 | 0,50 | 0,53 | 0,50 | 0,57 |
| cellaszĂĄm/cm3 | 4412 | 3782 | 3210 | 3819 | 2637 |
| cellaszĂĄm/in | 72 318 | 61 987 | 52611 | 62 594 | 43 216 |
| nyomĂłszilĂĄrdsĂĄg (kPa) | - | 82,12 | 82,74 | 81,50 | 83,64 |
| nyomĂłszilĂĄrdsĂĄg (PSI) | - | 11,91 | 12,00 | 11,82 | 12,13 |
| K-faktor (friss) | 0,149 | 0,161 | 0,178 | 0,150 | 0,154 |
6-8. példåk
A fentiekben leĂrt ĂĄltalĂĄnos eljĂĄrĂĄst ismĂ©teljĂŒk meg, az alkalmazott összetĂ©teli elĆiratot, habosĂtĂłszer mennyisĂ©geket, anyagĂĄramokat, nyomĂĄs Ă©s vĂĄkuum Ă©rtĂ©keket a 2. tĂĄblĂĄzatban foglaltuk össze. LĂ©nyeges jellemzĆje az itt megvalĂłsĂtott eljĂĄrĂĄsoknak, hogy a plasztifikĂĄlt polimerbe bedolgozott habosĂtĂłszer mennyisĂ©gĂ©t 11,1 t%-ra növeltĂŒk. Az Ăgy elĆĂĄllĂtott habtĂĄblĂĄk tulajdonsĂĄgait a 2. tĂĄblĂĄzatban tĂŒntetjĂŒk fel.
2. tĂĄblĂĄzat
| Példa | 6 | 7 | 8 |
| összetĂ©teli elĆirat (t%) | |||
| nyers polimer | ARCO | ARCO | ARCO |
| Példa | 6 | 7 | 8 |
| összetĂ©teli elĆirat (t%) | |||
| visszaĆrölt polimer (%) | 13,80 | 13,80 | 13,80 |
| talkum (%) | 0,24 | 0,37 | 0,37 |
| égésgåtló | 0,90 | 0,92 | 0,92 |
| habosĂtĂłszer (t%) | |||
| 40% F-22/60% F142(b) | 11,1 | 11,1 | 11,1 |
| teljesĂtmĂ©ny (kg/Ăłra) | 348,7 | 352,3 | 360,9 |
| teljesĂtmĂ©ny (lb/hr) | 768 | 776 | 795 |
| extrĂșziĂłs szerszĂĄm nyomĂĄs (kPa) | 3234 | 3238 | 3164 |
| extrĂșziĂłs szerszĂĄm nyomĂĄs (PSIG) | 469 | 471 | 459 |
| vĂĄkuum (kPa) | 51,5 | 71,8 | 71,1 |
| vĂĄkuum (Hg in) | 15,2 | 21,2 | 21,0 |
| a termék | |||
| vastagsĂĄga (cm) | 5,207 | 5,182 | 5,131 |
| vastagsĂĄga (in) | 2,050 | 2,040 | 2,020 |
| sƱrƱség (kg/m3) | 24,19 | 29,96 | 30,92 |
| sƱrƱség (lb/ft3) | 1,51 | 1,87 | 1,93 |
| åtlagos cellaméret (mm) | 0,40 | 0,32 | 0,34 |
| cella szĂĄm/cm3 | 8 068 | 15 232 | 12 954 |
| cella szĂĄm/in3 | 132 216 | 249 623 | 212238 |
| nyomĂłszilĂĄrdsĂĄg (kPa) | 166,1 | 252,8 | 261,5 |
| nyomĂłszilĂĄrdsĂĄg (PSI) | 24,09 | 36,67 | 37,92 |
| K-faktor (friss) | 0,163 | 0,153 | 0,154 |
9-14. példåk
A fentiekben leĂrt ĂĄltalĂĄnos eljĂĄrĂĄst ismĂ©teltĂŒk meg. A pĂ©ldĂĄk egy rĂ©szĂ©nĂ©l az elĆzĆektĆl eltĂ©rĆ nyers sztirol polimert hasznĂĄltunk (Polysar HH-101, olvadĂ©k folyĂĄsi indexe = 2,5) Ă©s a habosĂtĂłszer kombinĂĄciĂł egyik elemekĂ©t szĂ©n-dioxidot hasznĂĄltunk. A tovĂĄbbi vĂĄltoztatĂĄsokat Ă©s a pĂ©ldĂĄk paramĂ©tereit a 3. tĂĄblĂĄzatban foglaltuk össze.
3. tĂĄblĂĄzat
| Példa | 9 | 10 | 11 | 12 | 13 | 14 |
| összetĂ©teli elĆirat (t%) | ||||||
| nyers polimer | ARCO | ARCO | POLYS AR | POLYS AR | POLYS AR | POLYS AR |
| visszaĆrölt polimer (%) | 18,03 | 18,03 | 18,00 | 18,00 | 18,00 | 18,00 |
| talkum (%) | 0,45 | 0,45 | 0,38 | 0,13 | 0,35 | 0,13 |
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| Példa | 9 | 10 | 11 | 12 | 13 | 14 |
| összetĂ©teli elĆirat (t%) | ||||||
| égésgåtló (%) | 0,99 | 0,99 | 0,90 | 0,93 | 0,93 | 0,93 |
| habosĂtĂłszer (t%) | ||||||
| 32% F12/68% F-142(b) | - | - | - | 10,60 | 10,60 | 10,60 |
| 40% F22/60% F-142(b) | 9,650 | 9,650 | 9,100 | - | - | - |
| CO2 | 0,650 | 0,650 | 0,640 | 0,690 | 0,690 | 0,690 |
| teljesĂt- mĂ©ny (kg/Ăłra) | 364,6 | 366,9 | 367,7 | 360,0 | 357,8 | 357,8 |
| teljesĂt- mĂ©ny (lb/hr) | 803,0 | 808,0 | 810,0 | 793,0 | 788,0 | 788,0 |
| extrĂșziĂłs szerszĂĄm nyomĂĄs (kPa) | 4027 | 3420 | 3834 | 4034 | 4013 | 4013 |
| extrĂșziĂłs szerszĂĄm nyomĂĄs (PSIG) | 584 | 496 | 556 | 585 | 582 | 582 |
| vĂĄkuum (kPa) | 52,5 | 55,5 | 55,5 | 44,0 | 45,0 | 45,4 |
| vĂĄkuum (Hg in) | 15,5 | 16,4 | 16,4 | 13,0 | 13,2 | 13,4 |
| a termék | ||||||
| vastagsĂĄga (cm) | 4,93 | 5,16 | 3,91 | 5,66 | 5,54 | 5,74 |
| vastagĂĄga (in) | 1,94 | 2,03 | 1,54 | 2,23 | 2,18 | 2,26 |
| sƱrƱség (kg/m31 | 24,63 | 24,35 | 24,51 | 20,67 | 20,31 | 20,51 |
| sƱrƱség (lb/ft3) | 1,55 | 1,52 | 1,53 | 1,29 | 1,33 | 1,28 |
| åtlagos cellaméret (mm) | 0,31 | 0,32 | 0,29 | 0,41 | 0,33 | 0,34 |
| cella- szĂĄm/cm3 | 17 236 | 14 802 | 19 290 | 6 842 | 13 618 | 12 290 |
| cellaszĂĄm /in3 | 282444 | 242567 | 316106 | 112124 | 223161 | 201396 |
| nyomĂĄsz szilĂĄrdsĂĄg (kPa) | 196,44 | 187,68 | 152,24 | 95,56 | 88,88 | 98,94 |
| nyomĂĄsz szilĂĄrdsĂĄg (PSI) | 28,49 | 27,16 | 22,08 | 13,86 | 12,89 | 14,35 |
| K-faktor (friss) | 0,164 | 0,165 | 0,154 | 0,175 | 0,170 | 0,174 |
Ahogy ez a 2. Ă©s 3. tĂĄblĂĄzatbĂłl lĂĄthatĂł, bĂĄr az alkalmazott habosĂtĂłszer keverĂ©k mennyisĂ©ge (beleĂ©rtve a szĂ©ndioxidot) a 9-11. pĂ©ldĂĄkban kisebb mint a 6-8. pĂ©ldĂĄkban felhasznĂĄlt 11 t%, az ĂĄtlagos cellamĂ©ret az F-22/F-142b Ă©s szĂ©n-dioxid habosĂtĂłszer kombinĂĄciĂłval elĆĂĄllĂtott haboknĂĄl kb. 25 t%-kal kisebb, mint a 6. pĂ©ldĂĄban elĆĂĄllĂtott hasonlĂł sƱrƱsĂ©gƱ habĂ©. Az 5,08 cm-es (2 in) habtĂĄblĂĄk, melyet az Fâ12/Fâ142(b) keverĂ©kkel Ă©s szĂ©n-dioxiddal ĂĄllĂtunk elĆ, jĂł minĆsĂ©gƱ termĂ©kek, s ĂĄtlagos cellamĂ©retĂŒk mĂ©g 20,5-21,31 kg/m3 (1,28-1,33 lb/ft3) sƱrƱsĂ©g mellett is viszonylag kicsiny (12-14. pĂ©ldĂĄk).
15-18. példåk
Az alkalmazott összetĂ©teli elĆiratot, habosĂtĂłszer mennyisĂ©geket Ă©s egyĂ©b paramĂ©tereket a 4. tĂĄblĂĄzatban foglaltuk össze.
4. tĂĄblĂĄzat
| Példa | 15 | 16 | 17 | 18 |
| összetĂ©teli elĆirat (t%) | ||||
| nyers polimer | ARCO | ARCO | ARCO | POLY- SAR |
| visszaĆrölt polimer (%) | 13,00 | 13,00 | 12,10 | 12,10 |
| talkum (%) | 0,53 | 0,53 | 0,40 | 0,40 |
| égésgåtló (%) | 0,87 | 0,87 | 0,85 | 0,85 |
| habosĂtĂłszer (t%) | ||||
| 32% F-12/68% F142(b) | 10,600 | 10,600 | 10,700 | 9,818 |
| szén-dioxid | - | - | 0,500 | 0,368 |
| teljesĂtmĂ©ny (kg/Ăłra) | 326,9 | 326,9 | 318,7 | 318,7 |
| teljesĂtmĂ©ny (lb/hr) | 720 | 720 | 702 | 702 |
| extrĂșziĂłs szerszĂĄm nyomĂĄs (kPa) | 4564 | 4613 | 5040 | 5033 |
| (PSIG) | 662 | 669 | 731 | 730 |
| vĂĄkuum (kPa) | 45,7 | 44,7 | 37,6 | 37,2 |
| vĂĄkuum (Hg in) | 13,5 | 13,2 | 11,1 | 11,0 |
| termék | ||||
| vastagsĂĄga (cm) | 5,360 | 5,309 | 5,029 | 5,360 |
| vastagsĂĄga (in) | 2,11 | 2,09 | 1,98 | 2,11 |
| sƱrƱsége (kg/m3) | 21,19 | 24,51 | 21,93 | 21,63 |
| sƱrƱsége (lb/ft3) | 1,51 | 1,53 | 1,37 | 1,35 |
| åtlagos cellaméret (mm) | 0,32 | 0,32 | 0,32 | 0,29 |
| cella szĂĄm/cm3 | 14 823 | 14 958 | 15 245 | 20 610 |
| cella szĂĄm/in3 | 243 065 | 245 121 | 249 816 | 337 747 |
| nyomĂłszilĂĄrdsĂĄg (kPa) | 127,14 | 126,39 | 95,01 | 91,01 |
| nyomĂłszilĂĄrdsĂĄg (PSI) | 18,44 | 18,33 | 13,78 | 13,22 |
| K-faktor (friss) | 0,148 | 0,145 | 0,152 | 0,152 |
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Ahogy a 4. tĂĄblĂĄzat eredmĂ©nyeibĆl lĂĄthatĂł, 24,03 kg/m3 (1,5 lb/ft3) sƱrƱsĂ©gƱ polisztirol tĂĄblĂĄk ĂĄllĂthatĂłk elĆ (a 15. Ă©s 16. pĂ©ldĂĄkban ) Acro polimerbĆl, CFC-12-t Ă©s HCFC-142b-t tartalmazĂł habosĂtĂłszer keverĂ©kkel, a hab 0,32 mm-es ĂĄtlagos cellamĂ©rettel jellemezhetĆ. SzĂ©n-dioxid hozzĂĄadĂĄsa (17. pĂ©lda) 21,95 kg/m3 sƱrƱsĂ©gƱ (1,37 lb/ft3) termĂ©ket eredmĂ©nyez az elĆbbivel azonos - 0,32 mm - ĂĄtlagos cellamĂ©ret mellett, annak ellenĂ©re, hogy az alkalmazott gĂłckĂ©pzĆ mennyisĂ©gĂ©t több mint 20%-kal csökkentettĂŒk. A18. pĂ©ldĂĄban, ahol nagyobb molekulatömegƱ Polysar polimert hasznĂĄlunk, az ĂĄtlagos cellamĂ©ret mĂ©g kisebb volt mint az elĆzĆekben, a sƱrƱsĂ©g 21,63 kg/m3-nek (1,35 lb/ft3) adĂłdott.
Amint a fenti leĂrĂĄsbĂłl Ă©s pĂ©ldĂĄkbĂłl lĂĄthatĂł, a talĂĄlmĂĄny szerinti eljĂĄrĂĄssal habtĂĄblĂĄk Ă©s darabos habosĂtott testek ĂĄllĂthatĂłk elĆ l-klĂłr-l,l-difluor-etĂĄn Ă©s (a) esetben diklĂłr-difluor-metĂĄnt, klĂłr-difluĂłr-metĂĄn vagy ezek keverĂ©ke Ă©s vagy (b) esetben szĂ©n-dioxid habosĂtĂłszerkĂ©nt valĂł felhasznĂĄlĂĄsĂĄval; a habtestek megfelelĆ minĆsĂ©gƱek, sĆt bizonyos esetekben jobb minĆsĂ©gƱek, amennyiben a habosĂthatĂł polimer keverĂ©ket atmoszferikusnĂĄl kisebb nyomĂĄsra extrudĂĄljuk. A talĂĄlmĂĄny szerinti eljĂĄrĂĄsban l-klĂłr-l,l-difluor-etĂĄn, diklĂłr-difluormetĂĄn Ă©s/vagy klĂłr-difluor-metĂĄn felhasznĂĄlĂĄsa a tĂĄblĂĄs vagy darabos habosĂtott testek jellemzĆiben javulĂĄst eredmĂ©nyez a habost tĂłszerkĂ©nt csak 1-klĂłr-1,1difluor-etĂĄnt felhasznĂĄlĂł eljĂĄrĂĄsban elĆĂĄllĂtott termĂ©kkel szemben. OptimĂĄlis eredmĂ©nyeket akkor kaptunk, amikor a fent emlĂtett habosĂtĂłszert vagy habosĂtĂłszer keverĂ©ket szĂ©n-dioxiddal kombinĂĄlva hasznĂĄltuk fel. A szĂ©n-dioxidnak a polimer tömegĂ©re vonatkoztatva 0,41,5 t%-os felhasznĂĄlĂĄsa javĂtott minĆsĂ©gƱ habosĂtott testeket eredmĂ©nyez kĂŒlönösen akkor, ha kis sƱrƱsĂ©gƱ (32 kg/m3-nĂ©l kisebb) Ă©s kis ĂĄtlagos cellamĂ©retƱ, 0,20,5 mm tartomĂĄnyba, vagy mĂ©g inkĂĄbb 0,2-0,35 mm tartomĂĄnyba esĆ termĂ©kek elĆĂĄllĂtĂĄsa a cĂ©l.
A talĂĄlmĂĄny szerinti eljĂĄrĂĄst a talĂĄlmĂĄny kedvezĆ megvalĂłsulĂĄsainak ismertetĂ©sĂ©vel bemutatva, a szakemberek szĂĄmĂĄra Ă©rthetĆ, hogy az eljĂĄrĂĄs nagyon sok mĂłdosĂtĂĄssal hajthatĂł vĂ©gre. Ăgy a talĂĄlmĂĄny kiterjed mindazon mĂłdosĂtĂĄsokra, melyek a szabadalmi igĂ©nypontok körĂ©be esnek.
Claims (10)
- SZABADALMI IGĂNYPONTOK1. EljĂĄrĂĄs hosszirĂĄnyban kiterjedĆ, extrudĂĄlt, alkenilhelyettesĂtett aromĂĄs, hĆre lĂĄgyulĂł mƱanyag alapanyagĂș, habosĂtott testek elĆĂĄllĂtĂĄsĂĄra, melynek sorĂĄn a hĆre lĂĄgyulĂł mƱanyagot hĆvel plasztifikĂĄljuk; egy vagy több folyĂ©kony habosĂtĂłszert adunk hozzĂĄ; a habosĂtĂłszert egyenletesen belekeveijĂŒk a mƱanyagba, olyan nyomĂĄson, amely elegendĆ ahhoz, hogy megelĆzze a mƱanyag habosodĂĄsĂĄt, Ăgy habosĂthatĂł mƱanyag keverĂ©ket kĂ©pezĂŒnk; a habosĂthatĂł mƱanyag keverĂ©ket extrudĂĄljuk, Ăgy habosĂtott testeket hozunk lĂ©tre; a habosĂtott testeket szobahĆmĂ©rsĂ©kletre lehƱtjĂŒk, Ă©s a habosĂthatĂł mƱanyag elegyhez adott esetben gĂłckĂ©pzĆszert Ă©s adott esetben szĂ©n-dioxidot adagolunk, Ă©s Ăgy olyan habosĂtott testeket ĂĄllĂtunk elĆ, melyek sƱrƱsĂ©ge 14,4-56,1 kg/m3 (0,9â3,1 lb/ft3), azzal jellemezve, hogy a mƱanyag tömegĂ©re szĂĄmĂtva 3-16 tömegrĂ©sz folyĂ©kony habosĂtĂłszert adagolunk a mƱanyagkompozĂciĂłhoz, Ă©s habosĂtĂłszerkĂ©nt az 1-klĂłr-1,1-difluĂłr-etĂĄn, 1,1,1,2-tetrafluor-etĂĄn Ă©s 2klĂłr-l,l,l,2-tetrafluor-etĂĄn közĂŒl legalĂĄbb egyet, tovĂĄbbĂĄ adott esetben mĂ©g a mƱanyag tömegĂ©re vonatkoztatva 0,4-1,5 tömeg% szĂ©n-dioxidot, Ă©s/vagy legalĂĄbb egy tovĂĄbbi alkil-halogenid, diklĂłr-difluor-etĂĄn, Ă©s klĂłr-di-fluor-etĂĄn közĂŒl vĂĄlasztott habosĂtĂłszert adagolunk az alkilhalogenid habosĂtĂłszer teljes mennyisĂ©ge a mƱanyag tömegĂ©re szĂĄmĂtva 3-16 tömegrĂ©sz, a habosĂtĂłszerhez adott esetben gĂłckĂ©pzĆ adalĂ©kot is adagolunk, Ă©s az extrudĂĄlĂĄst 6,67-91,42 kPa (2-27 Hg in) nyomĂĄsĂș extrĂșziĂłs tĂ©rben vĂ©gezzĂŒk.
- 2. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, azzal jellemezve, hogy a felhasznĂĄlt habosĂtĂłszer diklĂłr-difluor-etĂĄnt, klĂłr-difluor-etĂĄnt, szĂ©n-dioxidot vagy ezek keverĂ©kĂ©t is tartalmazza.
- 3. Az 1. igénypont szerinti eljårås, azzal jellemezve, hogy a keverék etil-kloridtól, metil-kloridtól, metilalkoholtól, etil- vagy izopropil-alkoholtól mentes.
- 4. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, azzal jellemezve, hogy hĆre lĂĄgyulĂł mƱanyagkĂ©nt alkenil-csoporttal szubsztituĂĄlt aromĂĄs polisztirolt hasznĂĄlunk.
- 5. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, 0,2-0,5 mm közötti ĂĄtlagos cellamĂ©retƱ habosĂtott test elĆĂĄllĂtĂĄsĂĄra azzal jellemezve, hogy a 3-16 t rĂ©sz folyĂ©kony habosĂtĂłszerhez 0,4-1,5 t% szĂ©n-dioxidot is adagolunk a mƱanyag tömegĂ©re vonatkoztatva.
- 6. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, azzal jellemezve, hogy extrĂșziĂłs tĂ©rkĂ©nt egy elnyĂșjtott kamrĂĄt (14) alkalmazunk, melynek egyik vĂ©gĂ©n a keverĂ©ket extrĂșziĂłs szerszĂĄmon keresztĂŒl bejuttatjuk, Ă©s habosĂtott testet (24) az elnyĂșjtott kamra (14) mĂĄsik vĂ©gĂ©nĂ©l lĂ©vĆ vĂztartĂĄlyon (17) keresztĂŒlvezetve a környezeti nyomĂĄsra kijuttatjuk.
- 7. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, azzal jellemezve, hogy a keverĂ©ket Ăves kiömlĆnyĂlĂĄssal (32) rendelkezĆ legyezĆ alakĂș extrĂșziĂłs szerszĂĄmon ĂĄt (20) nyomjuk az extrĂșziĂłs tĂ©rbe, Ăgy folyamatos habosĂtott test (24) felĂŒletet alakĂtunk ki, Ă©s a keverĂ©k extrĂșziĂłjĂĄt Ășgy szabĂĄlyozzuk, hogy az Ăvelt kiömlĆnyĂlĂĄs (32) sĂkja alatt Ă©s felett Ăvelt hengereket (22) helyezĂŒnk el; az Ăvelt hengerek (22) megfelelĆ sebesĂ©ggel forgĂł meghajtott korongsorbĂłl (25) ĂĄllnak, Ă©s a kiömlĆnyĂlĂĄs (32) sĂkja feletti Ăvelt hengerek (22) lebegtetett felfĂŒggesztĂ©sĂ©vel ellenĆrzött lebegĆ nyomĂĄst gyakorolunk az extrĂșziĂłs szerszĂĄmbĂłl (20) kilĂ©pĆ keverĂ©kre.
- 8. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, azzal jellemezve, hogy szĂ©n-dioxidot is tartalmazĂł habosĂtĂłszert alkalmazunk.
- 9. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs azzal jellemezve, hogy a habosĂthatĂł keverĂ©k gĂłckĂ©pzĆszert is - elĆnyösen talkumot, kalcium-szilikĂĄtot, kalcium-kabonĂĄtot vagy indigĂłt tartalmaz.
- 10. Az 1. igĂ©nypont szerinti eljĂĄrĂĄs, azzal jellemezve, hogy habosĂtĂłszerkĂ©nt szĂ©n-dioxidot is tartalmazĂł keverĂ©ket alkalmazunk, gĂłckĂ©pzĆszerkĂ©nt talkumot hasznĂĄlunk.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31664989A | 1989-02-28 | 1989-02-28 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| HU901191D0 HU901191D0 (en) | 1990-05-28 |
| HUT53138A HUT53138A (en) | 1990-09-28 |
| HU209957B true HU209957B (en) | 1994-12-28 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| HU901191A HU209957B (en) | 1989-02-28 | 1990-02-28 | Process for manufacturing of extrudated foam-bodies |
Country Status (16)
| Country | Link |
|---|---|
| EP (1) | EP0385349B1 (hu) |
| JP (1) | JPH02279738A (hu) |
| KR (1) | KR0144147B1 (hu) |
| AT (1) | ATE123506T1 (hu) |
| AU (1) | AU620214B2 (hu) |
| CA (1) | CA2011023C (hu) |
| DE (1) | DE69019842T2 (hu) |
| DK (1) | DK51190A (hu) |
| ES (1) | ES2075077T3 (hu) |
| FI (1) | FI101230B1 (hu) |
| HU (1) | HU209957B (hu) |
| IE (1) | IE67547B1 (hu) |
| IS (1) | IS1551B (hu) |
| MX (1) | MX173966B (hu) |
| NO (1) | NO178770C (hu) |
| NZ (1) | NZ232719A (hu) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0418603A3 (en) * | 1989-08-28 | 1991-07-17 | Daikin Industries, Limited | Blowing compositions |
| US5011866A (en) * | 1989-11-08 | 1991-04-30 | The Dow Chemical Company | Insulating alkenyl aromatic polymer foam |
| GB9001368D0 (en) * | 1990-01-20 | 1990-03-21 | Bp Chem Int Ltd | Blowing agents |
| US5147896A (en) * | 1991-05-20 | 1992-09-15 | E. I. Du Pont De Nemours And Company | Foam blowing agent composition and process for producing foams |
| JP5306572B2 (ja) * | 2005-07-22 | 2013-10-02 | æ ȘćŒäŒç€Ÿă«ăă« | ăčăăŹăłçł»æščèçșæłĄäœăăăłăăźèŁœé æčæł |
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| US3303076A (en) * | 1962-10-25 | 1967-02-07 | Monsanto Co | Method of making laminated polyurethane structures |
| US4044084A (en) * | 1975-08-11 | 1977-08-23 | Phipps Arthur L | Method of removing an article from a chamber having a reduced pressure therein |
| DE2832252A1 (de) * | 1978-07-22 | 1980-01-31 | Hoechst Ag | Impfpistole |
| US4371488A (en) * | 1981-04-02 | 1983-02-01 | U.C. Industries | Method and apparatus for extruding foamed bodies involving the use of adjustable traction shaping rolls |
| JPS62501015A (ja) * | 1985-04-12 | 1987-04-23 | ă¶ăăăŠăă±ăă«ă«ăă«ăłăăâ | ăčăăŹăłéćäœăźçșæłĄäœăźèŁœé æčæłćăłăăă«ăăŁăŠèŁœé ăăçșæłĄäœ |
| AU609736B2 (en) * | 1986-09-19 | 1991-05-09 | Dow Chemical Company, The | Process and apparatus for producing extruded thermoplastic foam bodies |
| CA1309221C (en) * | 1987-04-15 | 1992-10-27 | Kyung W. Suh | Method for the preparation of styrene polymer foam, blowing agents for the preparation of such foam and styrene polymer foams prepared with such blowing agents |
| US4912140A (en) * | 1988-09-21 | 1990-03-27 | The Dow Chemical Company | Expandable and expanded alkenyl aromatic polymer particles |
| JP2922953B2 (ja) * | 1988-10-17 | 1999-07-26 | ă¶ ă㊠ă±ăă«ă« ă«ăłăăăŒ | æç±ăąă«ă±ăă«èłéŠæăăȘăăŒăă©ăŒă |
-
1990
- 1990-02-26 EP EP90103702A patent/EP0385349B1/en not_active Expired - Lifetime
- 1990-02-26 ES ES90103702T patent/ES2075077T3/es not_active Expired - Lifetime
- 1990-02-26 AT AT90103702T patent/ATE123506T1/de not_active IP Right Cessation
- 1990-02-26 IE IE68690A patent/IE67547B1/en not_active IP Right Cessation
- 1990-02-26 DE DE69019842T patent/DE69019842T2/de not_active Expired - Fee Related
- 1990-02-27 IS IS3558A patent/IS1551B/is unknown
- 1990-02-27 FI FI900980A patent/FI101230B1/fi active IP Right Grant
- 1990-02-27 AU AU50189/90A patent/AU620214B2/en not_active Ceased
- 1990-02-27 NO NO900937A patent/NO178770C/no unknown
- 1990-02-27 DK DK051190A patent/DK51190A/da not_active Application Discontinuation
- 1990-02-27 MX MX019683A patent/MX173966B/es unknown
- 1990-02-27 CA CA002011023A patent/CA2011023C/en not_active Expired - Fee Related
- 1990-02-28 HU HU901191A patent/HU209957B/hu unknown
- 1990-02-28 KR KR1019900002595A patent/KR0144147B1/ko not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| DK51190A (da) | 1990-08-29 |
| FI101230B (fi) | 1998-05-15 |
| AU620214B2 (en) | 1992-02-13 |
| EP0385349A3 (en) | 1990-11-07 |
| NZ232719A (en) | 1992-04-28 |
| MX173966B (es) | 1994-04-12 |
| CA2011023A1 (en) | 1990-08-31 |
| AU5018990A (en) | 1990-09-06 |
| NO900937L (no) | 1990-08-29 |
| NO900937D0 (no) | 1990-02-27 |
| KR910015637A (ko) | 1991-09-30 |
| IS3558A7 (is) | 1990-08-29 |
| DE69019842D1 (de) | 1995-07-13 |
| DK51190D0 (da) | 1990-02-27 |
| KR0144147B1 (ko) | 1998-07-15 |
| ES2075077T3 (es) | 1995-10-01 |
| DE69019842T2 (de) | 1995-11-02 |
| NO178770B (no) | 1996-02-19 |
| HU901191D0 (en) | 1990-05-28 |
| FI101230B1 (fi) | 1998-05-15 |
| JPH02279738A (ja) | 1990-11-15 |
| IS1551B (is) | 1994-08-10 |
| NO178770C (no) | 1996-05-29 |
| HUT53138A (en) | 1990-09-28 |
| EP0385349B1 (en) | 1995-06-07 |
| ATE123506T1 (de) | 1995-06-15 |
| IE67547B1 (en) | 1996-04-17 |
| CA2011023C (en) | 2000-01-18 |
| FI900980A0 (fi) | 1990-02-27 |
| EP0385349A2 (en) | 1990-09-05 |
| IE900686L (en) | 1990-08-28 |
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