KR20010006140A - Thermoplastic Molding Materials - Google Patents
Thermoplastic Molding Materials Download PDFInfo
- Publication number
- KR20010006140A KR20010006140A KR1019997009219A KR19997009219A KR20010006140A KR 20010006140 A KR20010006140 A KR 20010006140A KR 1019997009219 A KR1019997009219 A KR 1019997009219A KR 19997009219 A KR19997009219 A KR 19997009219A KR 20010006140 A KR20010006140 A KR 20010006140A
- Authority
- KR
- South Korea
- Prior art keywords
- thermoplastic molding
- weight
- phyllosilicate
- molding composition
- vinylaromatic
- Prior art date
Links
- 238000009757 thermoplastic moulding Methods 0.000 title claims abstract description 10
- 239000012778 molding material Substances 0.000 title abstract 2
- 229910052615 phyllosilicate Inorganic materials 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 20
- 239000011229 interlayer Substances 0.000 claims abstract description 6
- 239000000654 additive Substances 0.000 claims abstract description 5
- 239000006057 Non-nutritive feed additive Substances 0.000 claims abstract description 4
- -1 sepilite Inorganic materials 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 42
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 22
- 239000000178 monomer Substances 0.000 claims description 20
- 239000010410 layer Substances 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 229910052736 halogen Inorganic materials 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 8
- 239000004569 hydrophobicizing agent Substances 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 5
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 5
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 239000012968 metallocene catalyst Substances 0.000 claims description 4
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- KTZVZZJJVJQZHV-UHFFFAOYSA-N 1-chloro-4-ethenylbenzene Chemical compound ClC1=CC=C(C=C)C=C1 KTZVZZJJVJQZHV-UHFFFAOYSA-N 0.000 claims description 2
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 claims description 2
- UVHXEHGUEKARKZ-UHFFFAOYSA-N 1-ethenylanthracene Chemical compound C1=CC=C2C=C3C(C=C)=CC=CC3=CC2=C1 UVHXEHGUEKARKZ-UHFFFAOYSA-N 0.000 claims description 2
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- RJDOZRNNYVAULJ-UHFFFAOYSA-L [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[F-].[F-].[Mg++].[Mg++].[Mg++].[Al+3].[Si+4].[Si+4].[Si+4].[K+] RJDOZRNNYVAULJ-UHFFFAOYSA-L 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000000440 bentonite Substances 0.000 claims description 2
- 229910000278 bentonite Inorganic materials 0.000 claims description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims description 2
- 239000000835 fiber Substances 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910052900 illite Inorganic materials 0.000 claims description 2
- 239000011159 matrix material Substances 0.000 claims description 2
- 239000010445 mica Substances 0.000 claims description 2
- 229910052618 mica group Inorganic materials 0.000 claims description 2
- VGIBGUSAECPPNB-UHFFFAOYSA-L nonaaluminum;magnesium;tripotassium;1,3-dioxido-2,4,5-trioxa-1,3-disilabicyclo[1.1.1]pentane;iron(2+);oxygen(2-);fluoride;hydroxide Chemical compound [OH-].[O-2].[O-2].[O-2].[O-2].[O-2].[F-].[Mg+2].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[Al+3].[K+].[K+].[K+].[Fe+2].O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2.O1[Si]2([O-])O[Si]1([O-])O2 VGIBGUSAECPPNB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000273 nontronite Inorganic materials 0.000 claims description 2
- HDBWAWNLGGMZRQ-UHFFFAOYSA-N p-Vinylbiphenyl Chemical group C1=CC(C=C)=CC=C1C1=CC=CC=C1 HDBWAWNLGGMZRQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052625 palygorskite Inorganic materials 0.000 claims description 2
- 229910000275 saponite Inorganic materials 0.000 claims description 2
- 229910021647 smectite Inorganic materials 0.000 claims description 2
- 239000000454 talc Substances 0.000 claims description 2
- 229910052623 talc Inorganic materials 0.000 claims description 2
- 229920001169 thermoplastic Polymers 0.000 claims description 2
- 239000004416 thermosoftening plastic Substances 0.000 claims description 2
- 229910001588 amesite Inorganic materials 0.000 claims 1
- 229910000514 dolomite Inorganic materials 0.000 claims 1
- 239000010459 dolomite Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 description 29
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 150000003254 radicals Chemical group 0.000 description 14
- 125000004432 carbon atom Chemical group C* 0.000 description 13
- 238000000465 moulding Methods 0.000 description 12
- 239000004793 Polystyrene Substances 0.000 description 10
- 150000001768 cations Chemical class 0.000 description 10
- 229920002223 polystyrene Polymers 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- PBKONEOXTCPAFI-UHFFFAOYSA-N 1,2,4-trichlorobenzene Chemical compound ClC1=CC=C(Cl)C(Cl)=C1 PBKONEOXTCPAFI-UHFFFAOYSA-N 0.000 description 9
- 238000009826 distribution Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920010524 Syndiotactic polystyrene Polymers 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- 150000008040 ionic compounds Chemical class 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 5
- CPOFMOWDMVWCLF-UHFFFAOYSA-N methyl(oxo)alumane Chemical compound C[Al]=O CPOFMOWDMVWCLF-UHFFFAOYSA-N 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 125000000753 cycloalkyl group Chemical group 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 238000005342 ion exchange Methods 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- 239000007848 Bronsted acid Substances 0.000 description 3
- DPSOUODMTOWXTB-UHFFFAOYSA-N CC1=C(C)C(C)([Ti])C(C)=C1C Chemical compound CC1=C(C)C(C)([Ti])C(C)=C1C DPSOUODMTOWXTB-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000002841 Lewis acid Substances 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 125000003545 alkoxy group Chemical group 0.000 description 3
- 125000005234 alkyl aluminium group Chemical group 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 238000003556 assay Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 229910052732 germanium Inorganic materials 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-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
- AQSJGOWTSHOLKH-UHFFFAOYSA-N phosphite(3-) Chemical class [O-]P([O-])[O-] AQSJGOWTSHOLKH-UHFFFAOYSA-N 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010421 standard material Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- PAMIQIKDUOTOBW-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1 PAMIQIKDUOTOBW-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical group [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000005341 cation exchange Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical group [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 125000001188 haloalkyl group Chemical group 0.000 description 2
- 125000003106 haloaryl group Chemical group 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BVWUEIUNONATML-UHFFFAOYSA-N n-benzylethenamine Chemical compound C=CNCC1=CC=CC=C1 BVWUEIUNONATML-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 229910052758 niobium Inorganic materials 0.000 description 2
- 239000010955 niobium Substances 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 150000004760 silicates Chemical class 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 150000003568 thioethers Chemical class 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- LWNGJAHMBMVCJR-UHFFFAOYSA-N (2,3,4,5,6-pentafluorophenoxy)boronic acid Chemical compound OB(O)OC1=C(F)C(F)=C(F)C(F)=C1F LWNGJAHMBMVCJR-UHFFFAOYSA-N 0.000 description 1
- SBKRBXBQFDKYSO-UHFFFAOYSA-N (3-tert-butyl-4-hydroxy-5-methylphenyl) propanoate Chemical compound CCC(=O)OC1=CC(C)=C(O)C(C(C)(C)C)=C1 SBKRBXBQFDKYSO-UHFFFAOYSA-N 0.000 description 1
- MVENWBWESJVKKC-UHFFFAOYSA-N (4-ethenylnaphthalen-1-yl)-trimethylazanium Chemical compound C[N+](C1=CC=C(C2=CC=CC=C12)C=C)(C)C MVENWBWESJVKKC-UHFFFAOYSA-N 0.000 description 1
- GLWROHHPDMJADW-UHFFFAOYSA-N (4-ethenylphenyl)methylphosphane Chemical compound PCC1=CC=C(C=C)C=C1 GLWROHHPDMJADW-UHFFFAOYSA-N 0.000 description 1
- QCEOZLISXJGWSW-UHFFFAOYSA-K 1,2,3,4,5-pentamethylcyclopentane;trichlorotitanium Chemical compound [Cl-].[Cl-].[Cl-].CC1=C(C)C(C)([Ti+3])C(C)=C1C QCEOZLISXJGWSW-UHFFFAOYSA-K 0.000 description 1
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 1
- ULQISTXYYBZJSJ-UHFFFAOYSA-N 12-hydroxyoctadecanoic acid Chemical compound CCCCCCC(O)CCCCCCCCCCC(O)=O ULQISTXYYBZJSJ-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- KIHBGTRZFAVZRV-UHFFFAOYSA-N 2-Hydroxyoctadecanoic acid Natural products CCCCCCCCCCCCCCCCC(O)C(O)=O KIHBGTRZFAVZRV-UHFFFAOYSA-N 0.000 description 1
- LQIIEHBULBHJKX-UHFFFAOYSA-N 2-methylpropylalumane Chemical compound CC(C)C[AlH2] LQIIEHBULBHJKX-UHFFFAOYSA-N 0.000 description 1
- UWRZIZXBOLBCON-UHFFFAOYSA-N 2-phenylethenamine Chemical compound NC=CC1=CC=CC=C1 UWRZIZXBOLBCON-UHFFFAOYSA-N 0.000 description 1
- PRWJPWSKLXYEPD-UHFFFAOYSA-N 4-[4,4-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butan-2-yl]-2-tert-butyl-5-methylphenol Chemical compound C=1C(C(C)(C)C)=C(O)C=C(C)C=1C(C)CC(C=1C(=CC(O)=C(C=1)C(C)(C)C)C)C1=CC(C(C)(C)C)=C(O)C=C1C PRWJPWSKLXYEPD-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KBXCFLXEWFCLED-UHFFFAOYSA-N CC1=C(C(=C(C1(C)[Ti](C)(C)C)C)C)C Chemical compound CC1=C(C(=C(C1(C)[Ti](C)(C)C)C)C)C KBXCFLXEWFCLED-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- GHKOFFNLGXMVNJ-UHFFFAOYSA-N Didodecyl thiobispropanoate Chemical compound CCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCC GHKOFFNLGXMVNJ-UHFFFAOYSA-N 0.000 description 1
- 239000003508 Dilauryl thiodipropionate Substances 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910052774 Proactinium Inorganic materials 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 239000004113 Sepiolite Substances 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910004283 SiO 4 Inorganic materials 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- HPTYUNKZVDYXLP-UHFFFAOYSA-N aluminum;trihydroxy(trihydroxysilyloxy)silane;hydrate Chemical compound O.[Al].[Al].O[Si](O)(O)O[Si](O)(O)O HPTYUNKZVDYXLP-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 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
- MNNBVYZDUOXAKT-UHFFFAOYSA-N benzyl(ethenyl)phosphane Chemical compound C=CPCC1=CC=CC=C1 MNNBVYZDUOXAKT-UHFFFAOYSA-N 0.000 description 1
- YVEJDOBFMBXLPV-UHFFFAOYSA-N benzyl-dimethyl-prop-2-enylazanium Chemical compound C=CC[N+](C)(C)CC1=CC=CC=C1 YVEJDOBFMBXLPV-UHFFFAOYSA-N 0.000 description 1
- XFOZBWSTIQRFQW-UHFFFAOYSA-M benzyl-dimethyl-prop-2-enylazanium;chloride Chemical compound [Cl-].C=CC[N+](C)(C)CC1=CC=CC=C1 XFOZBWSTIQRFQW-UHFFFAOYSA-M 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- GRYNBAVIBVAOTH-UHFFFAOYSA-N but-1-enyl benzenesulfonate Chemical compound C(C)C=COS(=O)(=O)C1=CC=CC=C1 GRYNBAVIBVAOTH-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- OATRZMUGANSNMU-UHFFFAOYSA-N diethyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](CC)(CC)C1=CC=CC=C1 OATRZMUGANSNMU-UHFFFAOYSA-N 0.000 description 1
- 235000019304 dilauryl thiodipropionate Nutrition 0.000 description 1
- MXTMXRYBYWOAGX-UHFFFAOYSA-N dimethyl(diphenyl)azanium Chemical compound C=1C=CC=CC=1[N+](C)(C)C1=CC=CC=C1 MXTMXRYBYWOAGX-UHFFFAOYSA-N 0.000 description 1
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- YGANSGVIUGARFR-UHFFFAOYSA-N dipotassium dioxosilane oxo(oxoalumanyloxy)alumane oxygen(2-) Chemical compound [O--].[K+].[K+].O=[Si]=O.O=[Al]O[Al]=O YGANSGVIUGARFR-UHFFFAOYSA-N 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 150000004659 dithiocarbamates Chemical class 0.000 description 1
- NHOGGUYTANYCGQ-UHFFFAOYSA-N ethenoxybenzene Chemical compound C=COC1=CC=CC=C1 NHOGGUYTANYCGQ-UHFFFAOYSA-N 0.000 description 1
- AZDCYKCDXXPQIK-UHFFFAOYSA-N ethenoxymethylbenzene Chemical compound C=COCC1=CC=CC=C1 AZDCYKCDXXPQIK-UHFFFAOYSA-N 0.000 description 1
- JJKOGDFBIDMPLF-UHFFFAOYSA-N ethenyl(phenyl)phosphane Chemical compound C=CPC1=CC=CC=C1 JJKOGDFBIDMPLF-UHFFFAOYSA-N 0.000 description 1
- RYZCGQUXJPHSSF-UHFFFAOYSA-N ethenylsulfanylmethylbenzene Chemical compound C=CSCC1=CC=CC=C1 RYZCGQUXJPHSSF-UHFFFAOYSA-N 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229910052621 halloysite Inorganic materials 0.000 description 1
- 150000002366 halogen compounds Chemical class 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000006289 hydroxybenzyl group Chemical group 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002609 medium Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- ZQKXQUJXLSSJCH-UHFFFAOYSA-N melamine cyanurate Chemical compound NC1=NC(N)=NC(N)=N1.O=C1NC(=O)NC(=O)N1 ZQKXQUJXLSSJCH-UHFFFAOYSA-N 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- 229910052627 muscovite Inorganic materials 0.000 description 1
- YALAVAYMNJCEBU-UHFFFAOYSA-N n-(2-chloro-3-formylpyridin-4-yl)-2,2-dimethylpropanamide Chemical compound CC(C)(C)C(=O)NC1=CC=NC(Cl)=C1C=O YALAVAYMNJCEBU-UHFFFAOYSA-N 0.000 description 1
- 150000002790 naphthalenes Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002832 nitroso derivatives Chemical class 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 150000004010 onium ions Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-O oxonium Chemical compound [OH3+] XLYOFNOQVPJJNP-UHFFFAOYSA-O 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 1
- 125000002097 pentamethylcyclopentadienyl group Chemical group 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- XRBCRPZXSCBRTK-UHFFFAOYSA-N phosphonous acid Chemical class OPO XRBCRPZXSCBRTK-UHFFFAOYSA-N 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 229910052624 sepiolite Inorganic materials 0.000 description 1
- 235000019355 sepiolite Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229910052717 sulfur Chemical group 0.000 description 1
- 239000011593 sulfur Chemical group 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- GBXQPDCOMJJCMJ-UHFFFAOYSA-M trimethyl-[6-(trimethylazaniumyl)hexyl]azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCCCC[N+](C)(C)C GBXQPDCOMJJCMJ-UHFFFAOYSA-M 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 description 1
- WGKLOLBTFWFKOD-UHFFFAOYSA-N tris(2-nonylphenyl) phosphite Chemical compound CCCCCCCCCC1=CC=CC=C1OP(OC=1C(=CC=CC=1)CCCCCCCCC)OC1=CC=CC=C1CCCCCCCCC WGKLOLBTFWFKOD-UHFFFAOYSA-N 0.000 description 1
- OBAJXDYVZBHCGT-UHFFFAOYSA-N tris(pentafluorophenyl)borane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1B(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F OBAJXDYVZBHCGT-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- BOXSVZNGTQTENJ-UHFFFAOYSA-L zinc dibutyldithiocarbamate Chemical compound [Zn+2].CCCCN(C([S-])=S)CCCC.CCCCN(C([S-])=S)CCCC BOXSVZNGTQTENJ-UHFFFAOYSA-L 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F12/00—Homopolymers and 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
- C08F12/02—Monomers containing only one unsaturated aliphatic radical
- C08F12/04—Monomers containing only one unsaturated aliphatic radical containing one ring
-
- 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
- C08K3/34—Silicon-containing compounds
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
- H05K1/0366—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement reinforced, e.g. by fibres, fabrics
Abstract
본 발명은The present invention
(A) 신디오탁틱 펜타드의 함량이 30 몰% 이상인 비닐방향족 중합체 10 내지 99 중량%,(A) 10 to 99% by weight of the vinylaromatic polymer having a content of syndiotactic pentad of 30 mol% or more,
(B) 층간 박리된 필로규산염 0.1 내지 20 중량%,(B) 0.1 to 20% by weight of interlayer exfoliated phyllosilicate,
(C) 다른 첨가제 및 가공 조제 0 내지 50 중량%(여기서, 성분 (A) 내지 (C)의 전체 중량%는 100%임)를 포함하는 열가소성 성형 재료에 관한 것이다.(C) a thermoplastic molding material comprising 0 to 50% by weight of other additives and processing aids, wherein the total weight percentage of components (A) to (C) is 100%.
Description
본 발명은The present invention
(A) 신디오탁틱 펜타드의 함량이 30 몰% 이상인 비닐방향족 중합체 10 내지 99 중량%,(A) 10 to 99% by weight of the vinylaromatic polymer having a content of syndiotactic pentad of 30 mol% or more,
(B) 층간 박리된 필로규산염(delaminated phyllosilicate) 0.1 내지 20 중량%,(B) 0.1 to 20% by weight of delaminated phyllosilicate,
(C) 다른 첨가제 및 가공 조제 0 내지 50 중량%(여기서, 성분 (A) 내지 (C)의 전체 중량%는 100%임)를 포함하는 열가소성 성형 조성물에 관한 것이다.(C) a thermoplastic molding composition comprising 0 to 50% by weight of other additives and processing aids, wherein the total weight percentage of components (A) to (C) is 100%.
본 발명은 또한 그들 성형 조성물의 제조 방법에 관한 것이며, 섬유, 필름 및 임의의 유형의 성형품을 제조하기 위한 그의 용도 및 이런 식으로 수득될 수 있는 성형품에 관한 것이다.The invention also relates to a process for the production of their molding compositions, to their use for the production of fibers, films and shaped articles of any type and to shaped articles obtainable in this way.
그의 성질 프로필에 의하여, 비닐방향족 화합물의 중합체, 특히 폴리스티렌은 예를 들어 팩키징 재료로서 또는 특히 전기 분야 적용에서 금속 또는 플라스틱용 절연 커버로서, 많은 분야에서 사용된다.By their property profile, polymers of vinylaromatic compounds, in particular polystyrene, are used in many fields, for example as packaging materials or as insulation covers for metals or plastics, especially in electrical applications.
영국 특허 제826 021호에서는 이소탁틱 폴리스티렌의 제조 방법에 대해 기술하고 있다. 그러나, 이소탁틱 폴리스티렌은 서서히 결정화되어 사출 성형을 할 수 없다.British Patent 826 021 describes a process for the preparation of isotactic polystyrene. However, isotactic polystyrene is slowly crystallized and cannot be injection molded.
유럽 특허 제535 582호 및 동 제584 646호에서는 메탈로센 착물 및 공촉매 존재하에서 스티렌을 반응시킴으로써 신디오탁틱 폴리스티렌을 제조하는 방법에 대해 기술하고 있다. 신디오탁틱 폴리스티렌은 높은 내약품성, 높은 강성, 양호한 형태 안정성 및 양호한 유전성이 있다.EP 535 582 and 584 646 describe a process for producing syndiotactic polystyrene by reacting styrene in the presence of metallocene complexes and cocatalysts. Syndiotactic polystyrene has high chemical resistance, high rigidity, good form stability and good dielectricity.
특수한 적용에서, 신디오탁틱 폴리스티렌의 강성도 종종 불충분하여, 따라서 일반적으로 유리 섬유와 혼합함으로써 강성을 증가시킨다. 이때 사출 성형물의 표면 성질 및 중합체 용융물의 유동성이 악화된다는 단점이 있다. 동시에 재료의 밀도가 증가한다.In special applications, the stiffness of syndiotactic polystyrene is also often insufficient, thus increasing the stiffness generally by mixing with glass fibers. At this time, there is a disadvantage that the surface properties of the injection molding and the fluidity of the polymer melt deteriorate. At the same time the density of the material increases.
층간 박리된 필로규산염을 포함하는 어탁틱 폴리스티렌은 문헌[A. Akelah, A. Moet, J. Mat. Sci. 1996, 31, 3589-3596]에 공지되어 있다. 이러한 성형 조성물 및(또는) 성형품의 내열성 및 유동성은 많은 적용에서 불충분하다.Atactic polystyrenes comprising interlaminar peeled phyllosilicates are described in A. Akelah, A. Moet, J. Mat. Sci. 1996, 31, 3589-3596. The heat resistance and flowability of such molding compositions and / or molded articles are insufficient in many applications.
본 발명의 목적은 균형된 성질 프로필이 있고 충전제가 존재하는 비닐방향족 중합체를 제공하는 것이다. 특히, 저밀도 및 양호한 표면 성질과 함께, 고내열성 및 양호한 유동성이 배합되어 있어야 한다.It is an object of the present invention to provide vinylaromatic polymers having a balanced property profile and in which fillers are present. In particular, high heat resistance and good fluidity must be combined with low density and good surface properties.
본 발명자들은 이 목적이 처음에 정의한 성형 조성물에 의해 달성된다는 것을 발견하였다. 바람직한 실시양태를 종속항에서 나타낸다.We have found that this object is achieved by the molding composition defined at the outset. Preferred embodiments are shown in the dependent claims.
놀랍게도, 층간 박리된 필로규산염과 신디오탁틱 비닐방향족 중합체를 배합하면 가공하기 쉽고 매우 양호한 내열성, 양호한 표면 성질 및 저밀도를 가진 성형 조성물이 수득된다.Surprisingly, blending the interlaminar peeled phyllosilicate with the syndiotactic vinylaromatic polymer yields a molding composition that is easy to process and has very good heat resistance, good surface properties and low density.
신규 성형 조성물은 성분 A)로서 신디오탁틱 펜타드의 함량이 30 몰% 이상, 바람직하게는 50 몰% 이상, 특히 90 몰% 이상인, 비닐방향족 중합체를 10 내지 99 중량%, 바람직하게는 30 내지 99 중량%, 특히 50 내지 98 중량%로 포함한다.The novel molding compositions comprise 10 to 99% by weight, preferably 30 to 30%, of vinylaromatic polymers having a content of syndiotactic pentad of at least 30 mol%, preferably at least 50 mol%, in particular at least 90 mol%, as component A). 99 weight percent, especially 50-98 weight percent.
신디오탁틱 펜타드의 비율은 일반적으로13C-NMR 분광분석법으로 측정한다. 좀더 자세하게는, 문헌[M. Kobayashi, T. Nakaoki, N. Ishihara, Macromolecules 1990, 23, 78; J. D. Savage, Y. K. Wang, H. D. Stidham, M. Corbett, S. L. Hsu, Macromolecules 1992, 25, 3164; A. Grassi, P. Longo, G. Guerra, Makromol. Chem., Rapid Commun. 1989, 10, 687; M. A. Gomez, A. E. Tonelli, Macromolecules 1990, 23, 3385 및 D. Capitani, C. de Rosa, A. Ferrando, A. Grassi, A. L. Segre, Macromolecules 1992, 25, 3874]을 참조할 수 있다.The proportion of syndiotactic pentad is generally determined by 13 C-NMR spectroscopy. In more detail, M. Kobayashi, T. Nakaoki, N. Ishihara, Macromolecules 1990, 23, 78; JD Savage, YK Wang, HD Stidham, M. Corbett, SL Hsu, Macromolecules 1992, 25, 3164; A. Grassi, P. Longo, G. Guerra, Makromol. Chem., Rapid Commun. 1989, 10, 687; MA Gomez, AE Tonelli, Macromolecules 1990, 23, 3385 and D. Capitani, C. de Rosa, A. Ferrando, A. Grassi, AL Segre, Macromolecules 1992, 25, 3874.
성분 A)는 바람직하게는 화학식 I의 비닐방향족 단량체로부터 제조된다.Component A) is preferably prepared from vinylaromatic monomers of formula (I).
여기서, R1은 수소 또는 C1내지 C4알킬이고, R2내지 R6은 서로 독립적으로 수소, C1내지 C12알킬, C6내지 C18아릴 또는 할로겐이거나, 또는 인접한 2개의 라디칼은 함께 탄소 원자수가 4 내지 15인 기이다.Wherein R 1 is hydrogen or C 1 to C 4 alkyl and R 2 to R 6 are independently of each other hydrogen, C 1 to C 12 alkyl, C 6 to C 18 aryl or halogen, or two adjacent radicals together Group having 4 to 15 carbon atoms.
R1이 수소이고, R2내지 R6이 수소, C1내지 C4알킬, 염소, 페닐, 비페닐, 나프탈렌 또는 안트라센이거나 또는 인접한 2개의 라디칼과 함께 예를 들어 화학식 I의 화합물로서 나프탈렌 유도체 또는 안트라센 유도체가 되는, 탄소 원자수가 4 내지 12인 기인 화학식 I의 비닐방향족 단량체를 사용하는 것이 바람직하다.R 1 is hydrogen and R 2 to R 6 are hydrogen, C 1 to C 4 alkyl, chlorine, phenyl, biphenyl, naphthalene or anthracene or together with two adjacent radicals a naphthalene derivative, for example as a compound of formula (I) or Preference is given to using vinylaromatic monomers of the formula (I) which are groups having from 4 to 12 carbon atoms, which are anthracene derivatives.
이러한 바람직한 화합물의 예는 스티렌, p-메틸스티렌, p-클로로스티렌, 2,4-디메틸스티렌, 4-비닐비페닐, 비닐나프탈렌 또는 비닐안트라센이다.Examples of such preferred compounds are styrene, p-methylstyrene, p-chlorostyrene, 2,4-dimethylstyrene, 4-vinylbiphenyl, vinylnaphthalene or vinylanthracene.
상이한 비닐방향족 화합물의 혼합물이 또한 사용될 수 있으나 단지 1종의 비닐방향족 화합물을 사용하는 것이 바람직하다.Mixtures of different vinylaromatic compounds may also be used but it is preferred to use only one vinylaromatic compound.
특히 바람직한 비닐방향족 화합물은 스티렌과 p-메틸스티렌이다.Particularly preferred vinylaromatic compounds are styrene and p-methylstyrene.
화학식 I의 비닐방향족 화합물의 제조는 그 자체로 공지되어 있으며, 예를 들어 문헌[Beilstein 5, 367, 474, 485]에 기술되어 있다.The preparation of vinylaromatic compounds of formula I is known per se and are described, for example, in Beilstein 5, 367, 474, 485.
본 발명의 목적을 위하여, 비닐방향족 중합체 A)는 또한 양이온 형성제의 촉매 및, 필요할 경우, 알루미늄 화합물의 촉매 존재하에서, 2개 이상의 비닐방향족 관능성 라디칼을 포함하는, 블록을 제조하는 분지 형성 단량체와 상기에서 언급한 비닐방향족 단량체를 중합함으로써 수득될 수 있는 스타형 중합체이다.For the purposes of the present invention, vinylaromatic polymer A) also comprises branching monomers for making blocks, comprising at least two vinylaromatic functional radicals, in the presence of a catalyst of a cation former and, if necessary, a catalyst of an aluminum compound. And star polymers which can be obtained by polymerizing the above-mentioned vinylaromatic monomers.
이들은 분자량이 500,000 내지 10,000,000으로 높은 동시에 290℃, 10 kg 적재하에서 용융 점도가 500 ml/10분으로 낮으며, 유사한 분자량의 신디오탁틱 스티렌과 비교하여 상당히 더 높은 말단기 관능가를 가진다. 말단기 관능가는 일반적으로 0.5 몰% 초과, 특히 바람직하게는 0.8 몰%를 초과한다.They have a high molecular weight of 500,000 to 10,000,000 and at the same time have a low melt viscosity of 500 ml / 10 min at a load of 290 ° C., 10 kg, and have significantly higher end group functionality compared to syndiotactic styrene of similar molecular weight. The end group functionality is generally greater than 0.5 mol%, particularly preferably greater than 0.8 mol%.
이들 성질은 블록을 제조하는 분지 형성 단량체에 대한 비닐방향족 단량체의 몰비를 통해 폭넓게 조정될 수 있다.These properties can be broadly adjusted through the molar ratio of vinylaromatic monomer to the branching monomer from which the block is made.
사용되는 분지 형성 단량체는 화학식 II의 화합물일 수 있다.The branching monomer used may be a compound of formula (II).
여기서, Ra는 수소, 할로겐, 또는 탄소 원자수가 20 이하인 불활성 유기 라디칼이고, p가 2 이상일 경우, Ra는 동일하거나 또는 상이할 수 있고 그들에 결합된 금속 원자와 함께 2개의 라디칼 Ra는 3 내지 8원의 고리를 형성할 수 있으며, M이 전이 금속일 경우, Ra는 또한 전형적인 착물 리간드일 수 있고,Wherein R a is hydrogen, halogen, or an inert organic radical having 20 or fewer carbon atoms, and when p is 2 or more, R a may be the same or different and two radicals R a together with metal atoms bonded to them Can form a 3-8 membered ring, and when M is a transition metal, R a can also be a typical complex ligand,
Rb는 수소, C1내지 C4알킬 또는 페닐이고,R b is hydrogen, C 1 to C 4 alkyl or phenyl,
Rc는 수소, C1내지 C4알킬, 페닐, 염소 또는 탄소 원자수가 2 내지 6인 불포화 탄화수소 라디칼이고,R c is hydrogen, C 1 to C 4 alkyl, phenyl, chlorine or an unsaturated hydrocarbon radical having 2 to 6 carbon atoms,
M은 C, Si, Ge, Sn, B, Al, Ga, N, P, Sb, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd이고,M is C, Si, Ge, Sn, B, Al, Ga, N, P, Sb, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Zn, Cd,
n은 2 내지 6이며,n is 2 to 6,
m은 0 내지 20이고,m is 0 to 20,
p는 0 내지 4이되,p is 0 to 4,
단, n+p의 합계는 M의 원자가에 해당한다.However, the sum of n + p corresponds to the valence of M.
이들 단량체는, 예를 들어 적절한 탄소 화합물, 금속 화합물 또는 전이 금속 화합물과 클로로알킬스티렌의 그리냐드 화합물, 예를 들어 할로겐 화합물을 통해 수득될 수 있다. M이 규소, 게르마늄 또는 주석일 경우, 이러한 반응의 예는 문헌[K. Nakanishi, J. Chem. Soc. Perkin Trans I, 1990, p. 3362]에 기술되어 있다.These monomers can be obtained, for example, via suitable carbon compounds, metal compounds or transition metal compounds and Grignard compounds of chloroalkylstyrene, for example halogen compounds. If M is silicon, germanium or tin, examples of such reactions are described in K. Nakanishi, J. Chem. Soc. Perkin Trans I, 1990, p. 3362.
M이 탄소, 규소, 게르마늄, 주석 또는 티타늄인 화학식 I의 블록을 제조하는 분지 형성 단량체는 쉽게 수득되므로 특히 바람직하다. 지수 m은 바람직하게는 0 내지 8이고, 특히 바람직하게는 0 내지 4이다.Branching monomers for preparing blocks of the formula (I) in which M is carbon, silicon, germanium, tin or titanium are particularly preferred because they are readily obtained. The index m is preferably 0 to 8, particularly preferably 0 to 4.
신규 성형 조성물은 성분 B)로서 층간 박리된 필로규산염을 0.1 내지 20 중량%, 바람직하게는 1 내지 10 중량%, 특히 2 내지 9 중량%로 포함한다.The novel molding composition comprises 0.1 to 20% by weight, preferably 1 to 10% by weight, in particular 2 to 9% by weight of interlayer exfoliated phyllosilicate as component B).
필로규산염이라는 용어는 일반적으로 SiO44면체가 2차원 망상 연속 구조물로 연결되어 있는 규산염을 의미한다. (음이온에 대한 실험식은 (Si2O5 2-)n이다). 개개의 층은 그들 사이에 놓인 양이온에 의해 연결되고 천연 필로규산염의 양이온은 주로 Na, K, Mg, Al 및(또는) Ca이다.The term phyllosilicate generally refers to silicates in which SiO 4 tetrahedra are connected in a two-dimensional network continuous structure. ( Equation for anion is (Si 2 O 5 2- ) n ). The individual layers are connected by cations placed between them and the cations of natural phyllosilicates are mainly Na, K, Mg, Al and / or Ca.
층간 박리 전에 이러한 규산염의 층 두께는 일반적으로 5 내지 100 Å, 바람직하게는 5 내지 50 Å, 특히 8 내지 20 Å이다.The layer thickness of such silicates before delamination is generally 5 to 100 kPa, preferably 5 to 50 kPa, in particular 8 to 20 kPa.
합성 및 천연 필로규산염의 예는 몬트모릴로나이트(montmorillonite), 스멕타이트(smectite), 일라이트(illite), 세피올라이트(sepiolite), 팔리고르스카이트(palygorskite), 백운모(muscovite), 알레바르다이트(allevardite), 아메사이트(amesite), 헥토라이트(hectorite), 플루오로헥토라이트(fluorohectorite), 사포나이트(saponite), 바이델라이트(beidellite), 활석, 논트로나이트(nontronite), 스테벤사이트(stevensite), 벤토나이트, 운모, 베어미클라이트(vermiculite), 플루오로베어미클라이트(fluorovermiculite), 할로이사이트(halloysite) 및 불소 함유 합성 운모 변종이 있다.Examples of synthetic and natural phyllosilicates are montmorillonite, smectite, illite, sepiolite, palygorskite, muscovite, allerbarite (allevardite), amsite, hectorite, fluorohectorite, saponite, beidelite, talc, nontronite, stebencite stevensite, bentonite, mica, baremiculite, fluorovermiculite, halloysite and fluorine-containing synthetic mica variants.
본 발명의 목적을 위하여, 층간 박리된 필로규산염은 먼저 소수성화제와 반응시키고 이어서 단량체를 첨가함으로써 층 사이의 거리를 증가시킨(예를 들어 스티렌에 의한, 팽창이라 종종 불리움) 필로규산염을 의미한다.For the purposes of the present invention, interlayer exfoliated phyllosilicate means a phyllosilicate which is first reacted with a hydrophobicizing agent and then added monomer to increase the distance between the layers (sometimes called swelling, eg by styrene).
바람직하게는 성형품에서 층 사이를 40 Å 이상, 바람직하게는 50 Å 이상의 거리가 되게 하는 이층은 소수성화되고 팽창된 필로규산염의 존재하에서 비닐방향족 단량체를 후속적으로 중합함으로써 일어난다(문헌[E. P. Giannelis, Adv. Mater. 8, (1996) p. 29-35] 참조).Preferably, the bilayer which makes the distance between the layers in the molded article at least 40 kPa, preferably at least 50 kPa occurs by subsequently polymerizing the vinylaromatic monomer in the presence of hydrophobized and expanded filosilicate (EP Giannelis, Adv. Mater. 8, (1996) p. 29-35).
층 사이의 거리를 증가(소수성화)시키기 위하여, 필로규산염을 (신규 성형 조성물을 제조하기 전에) 소수성화제(종종 오늄 이온 또는 오늄 염이라 또한 불리움)와 반응시킨다.In order to increase (hydrophobize) the distance between the layers, the phyllosilicate is reacted with a hydrophobicizing agent (often also called onium ions or onium salts) prior to preparing the new molding composition.
필로규산염의 양이온은 유기 소수성화제에 의해 대체된다. 즉, 층 사이의 원하는 거리를 유기 라디칼의 유형에 의해 설정할 수 있고 필로규산염이 배합되는 특정 단량체 또는 중합체의 유형에 좌우될 수 있다.The cation of phyllosilicate is replaced by an organic hydrophobization agent. That is, the desired distance between the layers can be set by the type of organic radical and can depend on the type of specific monomer or polymer in which the phyllosilicate is formulated.
금속 이온 일부 또는 전부가 교환될 수 있다. 모든 금속 이온이 교환되는 것이 바람직하다. 교환 가능한 금속 이온의 양(이온 교환 용량이라 불리움)은 일반적으로 필로규산염 100 g 당 밀리당량(meq)으로 나타낸다.Some or all of the metal ions may be exchanged. It is preferred that all metal ions be exchanged. The amount of exchangeable metal ions (called the ion exchange capacity) is generally expressed in milliequivalents (meq) per 100 g of phyllosilicate.
양이온 교환 용량이 50 meq/100 g 이상, 바람직하게는 80 내지 130 meq/100 g인 필로규산염이 바람직하다.Pylosilicates with a cation exchange capacity of at least 50 meq / 100 g, preferably 80 to 130 meq / 100 g, are preferred.
적당한 유기 소수성화제는 1개 이상의 유기 라디칼을 포함할 수 있는, 옥소늄, 암모늄, 포스포늄 및 술포늄 이온으로부터 유도된다.Suitable organic hydrophobizing agents are derived from oxonium, ammonium, phosphonium and sulfonium ions, which may comprise one or more organic radicals.
적당한 소수성화제의 예는 화학식 III 및(또는) IV의 것이다.Examples of suitable hydrophobicizing agents are those of formula III and / or IV.
여기서,here,
R7, R8, R9및 R10은 서로 독립적으로 수소, 탄소 원자수가 1 내지 40, 바람직하게는 1 내지 20이고, 치환되지 않았거나 또는 1개 이상의 관능기를 포함할 수 있는, 직쇄 또는 분지형, 포화 또는 불포화 탄화수소 라디칼이거나, 또는 2개의 라디칼이 서로 연결되어, 특히 탄소 원자수가 5 내지 10인 헤테로고리 라디칼이 되며,R 7 , R 8 , R 9 and R 10 are independently of each other hydrogen, straight or branched, having from 1 to 40 carbon atoms, preferably 1 to 20, unsubstituted or containing one or more functional groups It is a topographic, saturated or unsaturated hydrocarbon radical, or two radicals are linked to one another, in particular a heterocyclic radical having 5 to 10 carbon atoms,
D는 인 또는 질소이고,D is phosphorus or nitrogen,
E는 산소 또는 황이고,E is oxygen or sulfur,
u는 1 내지 5, 바람직하게는 1 내지 3인 정수이고,u is an integer of 1 to 5, preferably 1 to 3,
G는 음이온이다.G is an anion.
적당한 음이온 G는 양성자성 산, 특히 무기산으로부터 유도되며, 염소, 브롬, 불소 및 요오드와 같은 할로겐으로부터 유도된 이온, 및 황산염, 술포네이트, 인산염, 포스포네이트, 아인산염 및 카르복실레이트가 바람직하고, 특히 아세테이트가 바람직하다.Suitable anions G are derived from protic acids, in particular inorganic acids, with ions derived from halogens such as chlorine, bromine, fluorine and iodine, and sulfates, sulfonates, phosphates, phosphonates, phosphites and carboxylates, , In particular acetate.
출발 재료로서 사용되는 필로규산염은 일반적으로 현탁액의 형태로 반응시킨다. 바람직한 현탁 매질은 물이며, 필요할 경우, 알콜, 특히 탄소 원자수가 1 내지 3인 저분자량 알콜과 혼합된 물이다. 소수성화된 필로규산염은 일반적으로 물보다는 탄화수소와 좀더 상용성이 있기 때문에, 예를 들어 헵탄과 같은 탄화수소를 수성 매질과 함께 사용하는 것이 유리할 수 있다.Filosilicates used as starting materials are generally reacted in the form of suspensions. Preferred suspension media is water and, if necessary, water mixed with alcohols, in particular low molecular weight alcohols having 1 to 3 carbon atoms. Since hydrophobized phyllosilicates are generally more compatible with hydrocarbons than water, it may be advantageous to use hydrocarbons such as heptane with an aqueous medium, for example.
다른 적당한 현탁액 매질의 예는 케톤 및 탄화수소이다. 물과 섞일 수 있는 용매가 일반적으로 바람직하다. 소수성화제를 필로규산염에 첨가할 경우, 이온 교환이 발생하여, 그 결과 필로규산염이 일반적으로 좀더 소수성으로 되어 용매로부터 침전된다. 이온 교환의 부생물로서 생성되는 금속염은 바람직하게는 물에 용해되며, 그 결과 소수성화된 필로규산염을 예를 들어 여과법에 의해 결정질 고체로서 단리시킬 수 있다.Examples of other suitable suspension media are ketones and hydrocarbons. Solvents that can be mixed with water are generally preferred. When a hydrophobizing agent is added to the phyllosilicate, ion exchange occurs, with the result that the phyllosilicate generally becomes more hydrophobic and precipitates out of the solvent. The metal salts produced as by-products of ion exchange are preferably dissolved in water, so that the hydrophobized phyllosilicate can be isolated as a crystalline solid, for example by filtration.
이온 교환은 반응 온도에 대부분 무관하다. 온도는 매질의 결정화점보다 높고 비점보다 낮은 것이 바람직하다. 수성계에서, 온도는 0 내지 100℃, 바람직하게는 40 내지 80℃이다.Ion exchange is largely independent of the reaction temperature. The temperature is preferably higher than the crystallization point of the medium and lower than the boiling point. In an aqueous system, the temperature is 0 to 100 ° C, preferably 40 to 80 ° C.
신디오탁틱 비닐방향족 중합체에 대해, R7, R8, R9및, 필요할 경우, R10이 서로 독립적으로 메틸, 에틸, 프로필, 이소프로필, 클로로메틸, 벤질, p-메틸벤질, 또는 특히 매우 바람직하게는 p-비닐벤질인 소수성화제를 사용하는 것이 바람직하다.For syndiotactic vinylaromatic polymers, R 7 , R 8 , R 9 and, if necessary, R 10 are independently of each other methyl, ethyl, propyl, isopropyl, chloromethyl, benzyl, p-methylbenzyl, or especially very Preference is given to using hydrophobicizing agents which are preferably p-vinylbenzyl.
다른 적당한 비닐방향족 라디칼 R7, R8및 R9는 알콕시스티렌, 실릴기를 포함하는 알킬스티렌, 아미노스티렌, 비닐벤질디메톡시포스파이드, 에틸비닐벤젠술포네이트, 아미노 치환 알킬스티렌, 및 에테르기, 카르복실기 또는 카르복실레이트기를 포함하는 알킬스티렌이다.Other suitable vinylaromatic radicals R 7 , R 8 and R 9 are alkoxystyrene, alkylstyrene including silyl groups, aminostyrene, vinylbenzyldimethoxyphosphide, ethylvinylbenzenesulfonate, amino substituted alkylstyrene, and ether groups, carboxyl groups Or alkyl styrene comprising a carboxylate group.
특히 바람직한 소수성화제는 화학식 IIIa 및(또는) IVa의 것이다.Particularly preferred hydrophobicizing agents are those of formula IIIa and / or IVa.
R7, R8및, 적절한 경우, R9, 및 u 및 G는 화학식 III 및 IV의 화합물에 대해 상기에서 정의한 바와 같고,R 7 , R 8 and, where appropriate, R 9 , and u and G are as defined above for the compounds of Formulas III and IV,
e는 0 내지 20의 정수일 수 있고,e can be an integer from 0 to 20,
R11내지 R14는 서로 독립적으로, 수소, C1내지 C20알킬, C6내지 C18아릴 또는 할로겐이거나, 또는 인접한 2개의 라디칼은 함께 탄소 원자수가 4 내지 15인 기이다.R 11 to R 14 are, independently from each other, hydrogen, C 1 to C 20 alkyl, C 6 to C 18 aryl or halogen, or two adjacent radicals together are groups having 4 to 15 carbon atoms.
바람직한 이온의 예는 트리메틸(o-,m-,p-)비닐벤질암모늄, 트리에틸(o-,m-,p-)비닐벤질암모늄, 디페닐디메틸암모늄, 디페닐디에틸암모늄, 트리메틸(4-비닐나프틸)암모늄, 트리메틸(o-,m-,p-)비닐벤질포스포늄, 디(o-,m-,p-)비닐벤질술포늄, 트리페닐(o-,m-,p-)비닐벤질포스포늄, 트리페닐(o-,m-,p-)비닐페닐포스포늄, 트리(o-,m-,p-)비닐벤질옥소늄 및 트리(o-,m-,p-)비닐페닐옥소늄이다.Examples of preferred ions include trimethyl (o-, m-, p-) vinylbenzylammonium, triethyl (o-, m-, p-) vinylbenzylammonium, diphenyldimethylammonium, diphenyldiethylammonium, trimethyl (4 -Vinylnaphthyl) ammonium, trimethyl (o-, m-, p-) vinylbenzylphosphonium, di (o-, m-, p-) vinylbenzylsulfonium, triphenyl (o-, m-, p- Vinylbenzylphosphonium, triphenyl (o-, m-, p-) vinylphenylphosphonium, tri (o-, m-, p-) vinylbenzyloxonium and tri (o-, m-, p-) Vinylphenyloxonium.
트리메틸벤질비닐암모늄 이온이 특히 바람직하다.Trimethylbenzylvinylammonium ions are particularly preferred.
바람직한 술포늄 이온은 (p-,m-,o-)비닐디메틸메틸렌벤질술포늄이다.Preferred sulfonium ions are (p-, m-, o-) vinyldimethylmethylenebenzylsulfonium.
제조는 그 자체로 공지된 방법(예를 들면, 문헌[Stirling, The Chemistry of the Sulfonium Group, Part 1, 1981, p. 267-312 및 p. 313-385, Wiley New York; Deady et al., Austr. J. Chem. 32 (1979), p. 1735; Meerwein et al., Arch. Pharm. 291/63 (1958), p. 541 ff])으로 수행될 수 있다.Preparation is known per se (see, eg, Stirling, The Chemistry of the Sulfonium Group, Part 1, 1981, p. 267-312 and p. 313-385, Wiley New York; Deady et al., Austr. J. Chem. 32 (1979), p. 1735; Meerwein et al., Arch. Pharm. 291/63 (1958), p. 541 ff]).
다른 적당한 소수성화제 및 그의 제조 방법은 특히 국제 특허 출원 공개 제93/4117호, 동 제93/4118호, 유럽 특허 제398 551호 및 독일 특허 제36 32 865호에 기술되어 있다.Other suitable hydrophobicizing agents and methods for their preparation are described in particular in International Patent Application Publication Nos. 93/4117, 93/4118, European Patent 398 551 and German Patent No. 36 32 865.
소수성화 후, 필로규산염은 층 사이의 거리가 10 내지 40 Å, 바람직하게는 13 내지 20 Å이 된다. 층 사이의 거리는 일반적으로 상층의 하부 경계부터 하층의 상부 경계까지의 거리를 의미한다. 라멜라의 길이는 일반적으로 2000 Å 이하, 바람직하게는 1500 Å 이하이다.After hydrophobization, the phyllosilicate has a distance between the layers of 10 to 40 mm 3, preferably of 13 to 20 mm 3. The distance between layers generally means the distance from the lower boundary of the upper layer to the upper boundary of the lower layer. The length of the lamellae is generally 2000 kPa or less, preferably 1500 kPa or less.
상기에서 기술한 방식으로 소수성화된 필로규산염을 이어서 현탁액 또는 고체 형태로 비닐방향족 단량체와 혼합시킬 수 있고, 일반적인 방식으로 중합을 실시한다.The hydrophilized phyllosilicate in the manner described above can then be mixed with the vinylaromatic monomer in suspension or in solid form, and the polymerization is carried out in a general manner.
이때 필로규산염을 비닐방향족 단량체와 0 내지 300℃, 바람직하게는 25 내지 120℃, 특히 40 내지 100℃에서, 5 내지 180분, 바람직하게는 10 내지 120분의 체류 시간 동안 반응(팽창)시킴으로써 층 사이의 거리를 좀더 증가시킬 수 있다. 체류 시간 및 선택된 단량체의 유형에 따라, 층 사이의 거리는 10 내지 150 Å, 바람직하게는 20 내지 50 Å만큼 좀더 증가한다. 이어서 중합은 메탈로센 촉매, 양이온 형성제 및, 필요할 경우, 알루미늄 화합물 존재하에서 일반적인 방식으로 수행된다. 중합은 DIN 11 443에 따라 바람직하게는 10 내지 105Pa, 특히 102내지 104Pa의 전단 응력을 동시에 적용시키면서 수행하는 것이 특히 유리하다.At this time, the phyllosilicate is reacted (expanded) with the vinylaromatic monomer at a temperature of 0 to 300 ° C, preferably 25 to 120 ° C, particularly 40 to 100 ° C, for a residence time of 5 to 180 minutes, preferably 10 to 120 minutes. You can increase the distance between them. Depending on the residence time and the type of monomer selected, the distance between the layers increases further by 10 to 150 mm 3, preferably 20 to 50 mm 3. The polymerization is then carried out in a general manner in the presence of a metallocene catalyst, a cation former and, if necessary, an aluminum compound. The polymerization is particularly advantageously carried out according to DIN 11 443, with simultaneous application of shear stresses, preferably 10 to 10 5 Pa, in particular 10 2 to 10 4 Pa.
소수성화되고, 필요할 경우, 팽창된 필로규산염의 존재하에서 비닐방향족 중합체를 제조하기 위한 적당한 메탈로센 착물은 화학식 V의 것이다.Suitable metallocene complexes for the preparation of vinylaromatic polymers in the presence of hydrophobized and, if necessary, expanded filosilicates are of formula (V).
여기서,here,
R15내지 R19는 수소, C1내지 C10알킬, 그 자체 C1내지 C6알킬 치환체를 포함할 수 있는 고리원이 5 내지 7인 시클로알킬, C6내지 C15아릴 또는 아릴알킬이고, 또한 필요할 경우, 2개의 인접한 라디칼은 함께 탄소 원자수가 4 내지 15인 시클릭기, 또는 Si(R20)3(여기서, R20은 C1내지 C10알킬, C6내지 C15아릴 또는 C3내지 C10시클로알킬임)일 수 있고,R 15 to R 19 are hydrogen, C 1 to C 10 alkyl, cycloalkyl having 5 to 7 ring members which may include C 1 to C 6 alkyl substituents themselves, C 6 to C 15 aryl or arylalkyl, In addition, if necessary, two adjacent radicals together may be a cyclic group having from 4 to 15 carbon atoms, or Si (R 20 ) 3 , wherein R 20 is C 1 to C 10 alkyl, C 6 to C 15 aryl or C 3 To C 10 cycloalkyl),
K는 원소 주기율 표의 3 내지 6아족의 금속 또는 란탄족 계열의 금속이고,K is a metal of the 3-6 subgroup or a lanthanide series metal of the periodic table of elements,
Z1내지 Z5는 수소, 할로겐, C1내지 C10알킬, C6내지 C15아릴, C1내지 C10알콕시 또는 C1내지 C15아릴록시이며,Z 1 to Z 5 are hydrogen, halogen, C 1 to C 10 alkyl, C 6 to C 15 aryl, C 1 to C 10 alkoxy or C 1 to C 15 aryloxy,
Z1내지 Z5는 0, 1, 2, 3, 4 또는 5이고 M의 원자가에 해당하는 Z1+Z2+Z3+Z4+Z5합은 숫자 1보다 적다.Z 1 to Z 5 are 0, 1, 2, 3, 4 or 5 and the sum of Z 1 + Z 2 + Z 3 + Z 4 + Z 5 corresponding to the valence of M is less than the number 1.
화학식 V의 특히 바람직한 메탈로센 착물은Particularly preferred metallocene complexes of formula V are
M이 원소 주기율 표의 4아족의 금속, 특히 티타늄이고,M is a metal of the fourth subgroup of the periodic table of elements, in particular titanium,
Z1내지 Z5가 C1내지 C10알킬, C1내지 C10알콕시 또는 할로겐인 것이다.Z 1 to Z 5 are C 1 to C 10 alkyl, C 1 to C 10 alkoxy or halogen.
이러한 바람직한 메탈로센 착물의 예는 펜타메틸시클로펜타디에닐티타늄 트리클로라이드, 펜타메틸시클로펜타디에닐트리메틸티타늄 및 펜타메틸시클로펜타디에닐티타늄 트리메톡시드이다.Examples of such preferred metallocene complexes are pentamethylcyclopentadienyltitanium trichloride, pentamethylcyclopentadienyltrimethyltitanium and pentamethylcyclopentadienyltitanium trimethoxide.
유럽 특허 제584 646호에 기술되어 있는 것과 같은 메탈로센 착물이 또한 사용될 수 있다.Metallocene complexes such as those described in EP 584 646 may also be used.
2종의 상이한 메탈로센 착물의 혼합물이 특히 적당한 것으로 판명되었으나, 5종 이하의 상이한 메탈로센 착물의 혼합물이 또한 사용가능하다.While mixtures of two different metallocene complexes have been found to be particularly suitable, mixtures of up to five different metallocene complexes may also be used.
펜타메틸시클로펜타디에닐트리메틸과 펜타메틸시클로펜타디에닐 트리메톡시드의 혼합물이 본 발명에서 사용하기에 바람직하다.A mixture of pentamethylcyclopentadienyltrimethyl and pentamethylcyclopentadienyl trimethoxide is preferred for use in the present invention.
이 유형의 착화합물은 그 자체로 공지된 방법으로 합성될 수 있으며, 바람직하게는 티타늄, 지르코늄, 하프늄, 바나듐, 니오븀 또는 탄탈륨의 할로겐화물과 해당하는 치환된 시클릭 탄화수소 음이온을 반응시킴으로써 합성될 수 있다.Complexes of this type can be synthesized by methods known per se, preferably by reacting halides of titanium, zirconium, hafnium, vanadium, niobium or tantalum with the corresponding substituted cyclic hydrocarbon anions. .
특히 문헌[the Journal of Organometallic Chemistry, 369 (1989), 359-370]에서는 해당하는 제조 방법의 예가 있다.In particular, in the Journal of Organometallic Chemistry, 369 (1989), 359-370, there are examples of corresponding preparation methods.
메탈로세늄 이온을 형성하는 적당한 화합물의 예는 화합물 VI 또는 VII의 열린 사슬 또는 시클릭 알루미노옥산 화합물이다.Examples of suitable compounds which form metallocenium ions are the open chain or cyclic aluminoxane compounds of compound VI or VII.
여기서, R21은 C1내지 C4알킬, 바람직하게는 메틸 또는 에틸이고, m은 5 내지 30, 바람직하게는 10 내지 25의 정수이다.Wherein R 21 is C 1 to C 4 alkyl, preferably methyl or ethyl and m is an integer from 5 to 30, preferably from 10 to 25.
이들 올리고머 알루미노옥산 화합물은 특히 유럽 특허 제284 708호 및 미국 특허 제4,794,096호에 기술되어 있듯이, 물과 트리알킬알루미늄 용액을 반응시킴으로써 일반적으로 제조된다.These oligomeric aluminoxane compounds are generally prepared by reacting water with trialkylaluminum solutions, in particular as described in EP 284 708 and US Pat. No. 4,794,096.
생성되는 올리고머 알루미노옥산 화합물은 일반적으로 직쇄 및 고리형 둘 다의 다양한 장쇄 분자들의 혼합물로서 m은 평균값으로 보아야 한다. 알루미노옥산 화합물은 또한 다른 알킬 금속 화합물, 바람직하게는 알킬알루미늄 화합물과 혼합할 수 있다.The resulting oligomeric aluminoxane compound is generally a mixture of various long chain molecules, both straight and cyclic, with m being the average value. The aluminoxane compound may also be mixed with other alkyl metal compounds, preferably alkylaluminum compounds.
메탈로세늄 이온을 형성하는 다른 적당한 화합물은 특히 비전하 루이스 강산, 루이스 산 양이온이 있는 이온 화합물 및 양이온으로서 브뢴스테드 산이 있는 이온 화합물이다.Other suitable compounds which form metallocenium ions are in particular uncharged Lewis strong acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acid as cations.
바람직한 비전하 루이스 강산은 화학식 VIII의 화합물이다.Preferred uncharged Lewis strong acids are compounds of formula VIII.
여기서,here,
M1은 주기율 표의 3족의 원소, 특히 B, A1 또는 Ga, 바람직하게는 B이고,M 1 is an element of group 3 of the periodic table, in particular B, A1 or Ga, preferably B,
X1, X2및 X3은 수소이거나, 각 경우에서 알킬 라디칼의 탄소 원자수는 1 내지 10이고 아릴 라디칼의 탄소 원자수는 6 내지 20인, C1내지 C10알킬, C6내지 C15아릴, 알킬아릴, 아릴알킬, 할로알킬 또는 할로아릴이거나, 또는 불소, 염소, 브롬 또는 요오드, 특히 할로아릴, 바람직하게는 펜타플루오로페닐이다.X 1, X 2 and X 3 are hydrogen, the carbon atoms of the alkyl radical in each case is 1 to 10 and the number of carbon atoms of an aryl radical of 6 to 20, C 1 to C 10 alkyl, C 6 to C 15 Aryl, alkylaryl, arylalkyl, haloalkyl or haloaryl, or fluorine, chlorine, bromine or iodine, in particular haloaryl, preferably pentafluorophenyl.
X1, X2및 X3이 동일하고, 바람직하게는 트리스(펜타플루오로페닐)보란인 화학식 VIII의 화합물이 특히 바람직하다. 이들 화합물 및 그의 제조 방법은 그 자체로 공지되어 있고, 예를 들어 국제 특허 출원 공개 제93/3067호에 기술되어 있다.Particular preference is given to compounds of the formula VIII wherein X 1 , X 2 and X 3 are the same and are preferably tris (pentafluorophenyl) borane. These compounds and methods for their preparation are known per se and are described, for example, in International Patent Application Publication No. 93/3067.
루이스 산 양이온이 있는 적당한 이온 화합물은 화학식 IX의 화합물이다.Suitable ionic compounds with Lewis acid cations are compounds of formula (IX).
여기서,here,
A는 주기율 표의 1족 내지 6족 또는 1아족 내지 8아족의 원소이고,A is an element of group 1 to group 6 or group 1 to group 8 of the periodic table,
Q1내지 Qz는 각 경우에서 아릴 라디칼의 탄소 원자수가 6 내지 20이고 알킬 라디칼의 탄소 원자수가 1 내지 28인, C1내지 C28알킬, C6내지 C15아릴, 알킬아릴, 아릴알킬, 할로알킬, 할로아릴이거나, 치환되지 않은 또는 C1내지 C10알킬, 할로겐, C1내지 C28알콕시, C6내지 C15아릴록시, 실릴 또는 메르캅틸로 치환된, C1내지 C10시클로알킬과 같은, 1가 음이온 전하를 띄는 라디칼이고,Q 1 to Q z are C 1 to C 28 alkyl, C 6 to C 15 aryl, alkylaryl, arylalkyl, in each case 6 to 20 carbon atoms in the aryl radical and 1 to 28 carbon atoms in the alkyl radical, haloalkyl, halo, aryl, unsubstituted or C 1 to C 10 alkyl, halogen, C 1 to C 28 alkoxy, C 6 to C 15 aryl, hydroxy, substituted by silyl or Mer kaptil, C 1 to C 10 cycloalkyl, Such as a monovalent anionic charge radical,
a는 1 내지 6의 정수이고,a is an integer from 1 to 6,
z는 0 내지 5의 정수이며,z is an integer from 0 to 5,
d는 a-z의 차이나, d는 1 이상이다.d is the difference of a-z, but d is 1 or more.
카르보늄 양이온, 옥소늄 양이온, 술포늄 양이온 및 양이온 전이 금속 착물이 특히 적당하고, 트리페닐메틸 양이온, 은 양이온 및 1,1'-디메틸페로세닐 양이온이 특별히 적당하다.Carbonium cations, oxonium cations, sulfonium cations and cationic transition metal complexes are particularly suitable, with triphenylmethyl cations, silver cations and 1,1'-dimethylferrocenyl cations being particularly suitable.
그들은 바람직하게는 비배위 반대이온이 있으며, 특히 국제 특허 출원 공개 제91/09882호에 또한 언급되어 있는, 붕소 화합물, 바람직하게는 테트라키스(펜타플루오로페닐)보레이트가 있다.They are preferably uncoordinated counterions, especially boron compounds, preferably tetrakis (pentafluorophenyl) borate, which are also mentioned in International Patent Application Publication No. 91/09882.
양이온으로서 브뢴스테드 산 및 마찬가지로 바람직하게는 비배위 반대이온이 있는 이온 화합물은 국제 특허 출원 공개 제93/3067호에 언급되어 있고, 바람직한 양이온은 N,N-디메틸아닐리늄이다.Bronsted acids as cations and likewise preferably ionic compounds with uncoordinated counterions are mentioned in WO 93/3067, with the preferred cation being N, N-dimethylanilinium.
비닐방향족 화합물은 용액, 벌크, 현탁액 또는 기상으로 중합될 수 있다. 예를 들어, 벤젠, 톨루엔, 에틸벤젠 또는 크실렌과 같은 방향족 탄화수소, 및 디에틸 에테르, 디부틸 에테르, 에틸렌 글리콜 디메틸 에테르 또는 테트라히드로푸란과 같은 에테르, 또는 그밖에 프로판, n-부탄, 이소부탄 또는 펜탄과 같은 지방족 탄화수소, 또는 다양한 용매의 혼합물과 같은 용매을 사용하는 용액 중에서 또는 벌크로 수행하는 것이 바람직하다.Vinylaromatic compounds can be polymerized in solution, in bulk, in suspension or in gas phase. Aromatic hydrocarbons such as, for example, benzene, toluene, ethylbenzene or xylene, and ethers such as diethyl ether, dibutyl ether, ethylene glycol dimethyl ether or tetrahydrofuran, or else propane, n-butane, isobutane or pentane It is preferably carried out in bulk or in solution using a solvent such as an aliphatic hydrocarbon, such as, or a mixture of various solvents.
중합은 매우 다양한 조건, 즉 0 내지 150℃, 바람직하게는 10 내지 100℃ 범위의 적당한 온도, 0.1 내지 100 bar, 바람직하게는 1 내지 5 bar의 적당한 압력, 및 0.1 내지 24시간, 바람직하게는 0.5 내지 6시간의 중합시간에서 수행할 수 있다.The polymerization can be carried out in a wide variety of conditions, that is, a suitable temperature in the range of 0 to 150 ° C., preferably 10 to 100 ° C., a suitable pressure of 0.1 to 100 bar, preferably 1 to 5 bar, and 0.1 to 24 hours, preferably 0.5 It may be carried out at a polymerization time of from 6 hours.
메탈로센 착물은 바람직하게는 지지체 없이 사용될 수 있으나, 그들은 또한 지지체와 함께 사용될 수 있다.Metallocene complexes can preferably be used without a support, but they can also be used with the support.
적당한 지지체의 예는 실리카 겔, 특히 화학식이 SiO2·aAl2O3인 것으로, 여기서, a는 0 내지 2, 바람직하게는 0 내지 0.5 범위의 수로서, 결과적으로 주성분은 알루미노실리케이트 또는 이산화 규소이다. 지지체는 바람직하게는 입자 직경이 1 내지 200 ㎛, 특히 30 내지 80 ㎛이다. 이러한 생성물은 예를 들어 실리카 겔 332(Silica Gel 332, Grace 제품)로서 판매된다.An example of a suitable support is silica gel, in particular in the formula SiO 2 · aAl 2 O 3 , where a is a number in the range 0 to 2, preferably 0 to 0.5, and consequently the main component is aluminosilicate or silicon dioxide. to be. The support preferably has a particle diameter of 1 to 200 μm, in particular 30 to 80 μm. This product is sold, for example, as Silica Gel 332 from Grace.
다른 지지체의 예는 미분된 폴리프로필렌 또는 폴리에틸렌과 같은 미분된 폴리올레핀이며, 또한 폴리에틸렌 글리콜, 폴리부틸렌 테레프탈레이트, 폴리에틸렌 테레프탈레이트, 폴리비닐 알콜, 폴리스티렌, 폴리부타디엔, 폴리카르보네이트 또는 그의 공중합체이다.Examples of other supports are finely divided polyolefins such as finely divided polypropylene or polyethylene, and also polyethylene glycol, polybutylene terephthalate, polyethylene terephthalate, polyvinyl alcohol, polystyrene, polybutadiene, polycarbonate or copolymers thereof. .
중합시, 알킬알루미늄 화합물을 추가로 사용할 수 있으며 트리메틸알루미늄, 트리에틸알루미늄, 트리이소프로필알루미늄, 트리-n-프로필알루미늄, 트리이소부틸알루미늄 및 트리-n-부틸알루미늄이 특히 적당하나, 특히 트리이소부틸알루미늄이 특별히 적당하다.In the polymerization, alkylaluminum compounds may be further used, trimethylaluminum, triethylaluminum, triisopropylaluminum, tri-n-propylaluminum, triisobutylaluminum and tri-n-butylaluminum are particularly suitable, in particular triiso Butyl aluminum is particularly suitable.
이러한 알킬알루미늄 화합물의 첨가는 메탈로세늄 이온을 형성하는 화합물이 비전하 루이스 강산, 루이스 산 양이온이 있는 이온 화합물 및 양이온으로서 브뢴스테드 산이 있는 이온 화합물일 경우 특히 적당하다.The addition of such alkylaluminum compounds is particularly suitable when the compounds forming the metallocenium ions are non-charged Lewis strong acids, ionic compounds with Lewis acid cations and ionic compounds with Bronsted acid as cations.
비닐방향족 화합물 대 메탈로세늄 이온을 형성하는 화합물의 몰비가 102:1 내지 107:1, 바람직하게는 103:1 내지 106:1일 경우 유리한 것으로 판명되었다. 메탈로세늄 이온을 형성하는 화합물 대 메탈로센 착물의 전체 몰양의 몰비는 바람직하게는 10-2:1 내지 107:1, 특히 102:1 내지 105:1 범위이다.It has proved advantageous when the molar ratio of vinylaromatic compound to compound forming metallocene ions is 10 2 : 1 to 10 7 : 1, preferably 10 3 : 1 to 10 6 : 1. The molar ratio of the total molar amount of the compound forming the metallocene ions to the metallocene complex is preferably in the range 10 −2 : 1 to 10 7 : 1, in particular 10 2 : 1 to 10 5 : 1.
2종의 상이한 메탈로센 착물을 바람직하게는 10-3:1 내지 103:1, 특히 10-2:1 내지 102:1 범위의 한 메탈로센 착물 대 다른 메탈로센 착물의 몰비로 또한 사용할 수 있다. 3종 이상의 메탈로센 착물을 사용할 경우, 1종의 메탈로센 착물은 다음으로 높은 농도의 메탈로센 착물과 비교하여 1000배 몰과량으로 존재할 만큼 배합물은 매우 다양할 수 있다. 그러나, 몰과량이 100배 이하일 때 바람직하다.The two different metallocene complexes are preferably in a molar ratio of one metallocene complex to another metallocene complex in the range of 10 −3 : 1 to 10 3 : 1, in particular 10 −2 : 1 to 10 2 : 1 Can also be used. When three or more metallocene complexes are used, the combination can vary widely so that one metallocene complex is present in a 1000-fold molar excess compared to the next highest concentration of metallocene complex. However, it is preferable when the molar excess is 100 times or less.
알킬알루미늄 화합물이 사용될 경우, 특히 적당한 것으로 판명된 알킬알루미늄 화합물 대 메탈로센 착물의 전체량의 몰비는 10,000:1 내지 10:1, 바람직하게는 1000:1 내지 100:1이다.When an alkylaluminum compound is used, the molar ratio of the total amount of the alkylaluminum compound to the metallocene complex which is found to be particularly suitable is 10,000: 1 to 10: 1, preferably 1000: 1 to 100: 1.
중합은 바람직하게는 0.5 내지 30 bar, 바람직하게는 1 내지 20 bar 압력하에서 수행된다.The polymerization is preferably carried out under a pressure of 0.5 to 30 bar, preferably 1 to 20 bar.
반응은 일반적으로 -78℃ 내지 150℃, 바람직하게는 0℃ 내지 120℃에서 수행되나, 또한 반응 동안 0℃에서 120℃로 점차 증가시킬 수 있다.The reaction is generally carried out at -78 ° C to 150 ° C, preferably 0 ° C to 120 ° C, but can also be gradually increased from 0 ° C to 120 ° C during the reaction.
중합은 바람직하게는 반응 매질로서 비닐방향족 단량체, 즉 벌크로 수행된다. 알킬알루미노옥산 및 트리알킬알루미늄 화합물을 중합 전에 비닐방향족단량체와 접촉시키고 계량 펌프를 통해 반응기내로 계량 투입할 수 있다. 비닐방향족 단량체의 계량 투입 후, 펌프를 사용하여 메탈로센 촉매를 예를 들어, 시클릭 탄화수소, 또는 이소부탄, n-부탄, tert-부탄, 펜탄, 헥산, 헵탄과 같은 비환식 탄화수소, 또는 벤젠, 톨루엔, 에틸벤젠과 같은 방향족 용매, 또는 테트라히드로푸란과 같은 산소 함유 용매, 디클로로메탄과 같은 할로겐화 용매, N-메틸피페리딘과 같은 질소 함유 용매 등과 같은 일반 유기 용매 중에 용해시키거나, 또는 지지체 촉매일 경우 현탁시켜 계량 투입할 수 있다.The polymerization is preferably carried out in vinylaromatic monomers, ie in bulk, as the reaction medium. The alkylaluminoxane and trialkylaluminum compounds can be contacted with the vinylaromatic monomer prior to polymerization and metered into the reactor via a metering pump. After metering of the vinylaromatic monomer, the metallocene catalyst is used to pump the metallocene catalyst, for example, a cyclic hydrocarbon, or an acyclic hydrocarbon such as isobutane, n-butane, tert-butane, pentane, hexane, heptane, or benzene. Or in an organic solvent such as an aromatic solvent such as toluene, ethylbenzene, or an oxygen-containing solvent such as tetrahydrofuran, a halogenated solvent such as dichloromethane, a nitrogen-containing solvent such as N-methylpiperidine, or a support In the case of a catalyst, it can be suspended and metered in.
적당한 반응기는 교반 반응기, 오토클레이브, 연속 혼련기 및 수직형 반응기(독일 특허 제196 31 365호 참조)이다.Suitable reactors are stirred reactors, autoclaves, continuous kneaders and vertical reactors (see German Patent No. 196 31 365).
제조되는 중합체의 몰 질량은 1000 내지 107g/몰, 바람직하게는 10,000 내지 106g/몰, 특히 50,000 내지 500,000 g/몰 범위이다.The molar mass of the polymers produced is in the range from 1000 to 10 7 g / mol, preferably 10,000 to 10 6 g / mol, in particular 50,000 to 500,000 g / mol.
필로규산염의 존재하에서 상기에서 기술한 바와 같이, 수행되는 적당한 스타형 중합체의 제조는 독일 특허 제196 34 375호에 언급된 방법을 기초로 할 수 있다.As described above in the presence of phyllosilicates, the preparation of suitable star-shaped polymers carried out can be based on the process mentioned in German patent 196 34 375.
신규 성형 조성물은 성분 C)로서 추가 첨가제 및 가공 조제를 50 중량% 이하, 바람직하게는 30 중량% 이하, 특히 8 중량% 이하로 포함할 수 있다.The novel molding compositions may comprise, as component C), further additives and processing aids up to 50% by weight, preferably up to 30% by weight, in particular up to 8% by weight.
15 중량% 이하의 양으로 사용될 수 있는, 적당한 난연제는 적인(red phosphorus) 및 인 함유 화합물, 및 멜라민 및 멜라민 시아누레이트와 같은 질소 함유 화합물이다. 대체로, 임의의 공지된 난연제가 적당한다.Suitable flame retardants, which can be used in amounts up to 15% by weight, are red phosphorus and phosphorus containing compounds, and nitrogen containing compounds such as melamine and melamine cyanurate. In general, any known flame retardant is suitable.
적당한 안정제의 예는 옥타데실-3-(3,5-디-tert-부틸-4-히드록시페닐)프로피오네이트, 트리에틸렌 글리콜 비스-3(3-tert-부틸-4-히드록시-5-메틸페닐)프로피오네이트, 1,1,3-트리스(5-tert-부틸-4-히드록시-2-메틸페닐)부탄, 디라우릴티오디프로피오네이트 및 트리스(노닐페닐)포스파이트 또는 그의 혼합물이다. 안정화를 위해 사용될 수 있는 다른 화합물은 2 중량% 이하 양의 티오비스페놀, 알킬리덴비스페놀, 알킬페놀, 치환 디시클로펜타디엔, 히드록시벤질 화합물, 아실아미노페놀, 폴리히드록시페닐 프로피오네이트, 아민, 티오에테르, 아인산염, 포스포나이트 및 아연 디부틸디티오카바메이트이다.Examples of suitable stabilizers include octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol bis-3 (3-tert-butyl-4-hydroxy-5 -Methylphenyl) propionate, 1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane, dilaurylthiodipropionate and tris (nonylphenyl) phosphite or mixtures thereof to be. Other compounds that may be used for stabilization include thiobisphenols, alkylidenebisphenols, alkylphenols, substituted dicyclopentadienes, hydroxybenzyl compounds, acylaminophenols, polyhydroxyphenyl propionates, amines, in amounts up to 2% by weight. Thioethers, phosphites, phosphonites and zinc dibutyldithiocarbamate.
사용될 수 있는 산화방지제의 예는 단독 또는 혼합물로서 2 중량% 이하 양의 유기 황화물, 아인산염, 퀴논 및 그의 유도체, 방향족 니트로 및 니트로소 화합물, 치환된, 특히 o-이치환, 페놀, 술폰산, 티올 술피네이트, 티오술폭실산, 디티오카바메이트 및 디티오포스포네이트이다.Examples of antioxidants that can be used are organic sulfides, phosphites, quinones and derivatives thereof, aromatic nitro and nitroso compounds, substituted, in particular o-disubstituted, phenol, sulfonic acids, thiol sulfites, alone or in mixtures, in amounts of up to 2% by weight. Acetates, thiosulfoxy acids, dithiocarbamates and dithiophosphonates.
사용되는 윤활제는 저분자량 지방산 에스테르, 지방 알콜, 디카르복실산 에스테르, 칼슘 스테아레이트, 아미드 왁스, 스테아르산 및 히드록시스테아르산, 몬탄 왁스, PE 왁스 및 백유와 같은 파라핀일 수 있다.Lubricants used may be low molecular weight fatty acid esters, fatty alcohols, dicarboxylic acid esters, calcium stearate, amide waxes, stearic acid and hydroxystearic acid, montan wax, PE wax and white oils.
첨가제 C)를 압출기와 같은, 종래 장치를 사용하여 성분 A) 및 B)에 혼합시킬 수 있고, 압출물을 냉각 및 분쇄시킨다.Additive C) can be mixed into components A) and B) using conventional apparatus, such as extruders, and the extrudate is cooled and comminuted.
신규 성형 조성물은 양호한 내열성, 유동성이 있으며 저밀도이다. 이들은 양호한 표면의 성형품으로 어려움없이 변형될 수 있다. 성형품은층 구조(층 A는 열가소성 매트릭스이고 층 B는 층간 박리된 필로규산염임)를 가진다.The novel molding compositions have good heat resistance, flowability and low density. These can be transformed without difficulty into molded articles of good surface. Molded products It has a layer structure (layer A is a thermoplastic matrix and layer B is an interlayer exfoliated filosilicate).
적용의 예는 프린트 회로판, 플러그 커넥터(plug connectors), 칩 케리어(chip carriers) 및 축전기 필름과 같은 전기·전자 성분, 언더후드(under-hood) 코팅물, 표면 코팅물과 같은 자동차 성분, 전자레이지 용기, 및 온수 펌프 및 온수 배관용 외피이다.Examples of applications include electrical and electronic components such as printed circuit boards, plug connectors, chip carriers and capacitor films, automotive components such as under-hood coatings, surface coatings, electronic lazy Containers, and jackets for hot water pumps and hot water piping.
성분 BComponent B
비닐벤질트리메틸암모늄 클로라이드의 제조 및 몬트모릴로나이트와의 반응은 문헌[A. Akelah, A. Moet, J. Mat. Sci. 31, 1996]의 페이지 3590에 있는 2.1 및 2.2의 방법에 기초하여 수행하였다.Preparation of vinylbenzyltrimethylammonium chloride and reaction with montmorillonite are described in A. Akelah, A. Moet, J. Mat. Sci. 31, 1996, based on the methods of 2.1 and 2.2 in page 3590.
몬트모릴로나이트는 양이온 교환 용량이 90 meq/100g이었다. 비닐벤질트리메틸암모늄으로 소수성화된 몬트모릴로나이트는 하기에서 성분 B)로서 언급된다.Montmorillonite had a cation exchange capacity of 90 meq / 100g. Montmorillonite hydrophobized with vinylbenzyltrimethylammonium is referred to below as component B).
＜실시예 1＞<Example 1>
스티렌 104.2 g(1 몰)을 질소의 불활성 분위기인 둥근 바닥 플라스크에서 3.13 g의 성분 B)와 혼합하였다. 혼합물을 1시간 동안 교반시키고 이어서 60℃로 가열하였다. 이 온도에서 15분 동안 좀더 교반하였고 이 혼합물을 위트코(Witco)의 메틸알루미노옥산 (MAO)(톨루엔 중 1.53 M) 8.16 ml 및 알드리치(Aldrich)의 디이소부틸알루미늄 히드라이드 DIBAH(시클로헥산 중 1.0 M) 2.08 ml와 혼합하였다. 이어서 혼합물을 펜타메틸시클로펜타디에닐티타늄 트리메틸 Cp·TiMe39.5 mg(4.16 x 10-5몰)과 혼합하였다. 내용물의 온도를 60℃로 조정하였고 2시간 동안 중합을 진행하였고, 그후 메탄올을 첨가하여 중합을 정지시켰다. 생성된 중합체를 메탄올로 세척하고 50℃, 감압하에서 건조시켰다. 몰 질량 및 그의 분포도를 용매로서 1,2,4-트리클로로벤젠을 사용하는 고온 GPC로 135℃에서 측정하였다. 좁은 분포도를 가진 폴리스티렌 표준 물질을 사용하여 검정하였다. 몰 질량 Mw는 342,900이고, 분포도 폭 D인 Mw/Mn은 2.3이었다.13C NMR로 측정하여 펜타드로 측정하는 신디오탁틱 비율은 98%를 초과하였다. 전환율은 사용된 스티렌 단량체를 기준으로 하여, 78%이었다.104.2 g (1 mol) of styrene were mixed with 3.13 g of component B) in a round bottom flask with an inert atmosphere of nitrogen. The mixture was stirred for 1 hour and then heated to 60 ° C. Stir at this temperature for 15 minutes and mix the mixture with 8.16 ml of Witco's methylaluminoxane (MAO) (1.53 M in toluene) and Diisobutylaluminum hydride DIBAH (Aldrich) in cyclohexane 1.0 M) and 2.08 ml. The mixture was then mixed with 9.5 mg (4.16 x 10 -5 moles) of pentamethylcyclopentadienyltitanium trimethyl CpTiMe 3 . The temperature of the contents was adjusted to 60 ° C. and the polymerization proceeded for 2 hours, after which the polymerization was stopped by adding methanol. The resulting polymer was washed with methanol and dried at 50 ° C. under reduced pressure. The molar mass and its distribution were measured at 135 ° C. by high temperature GPC using 1,2,4-trichlorobenzene as solvent. Assays were made using polystyrene standard materials with narrow distribution. The molar mass M w was 342,900 and M w / M n having a distribution width D was 2.3. The syndiotactic ratio, measured by 13 C NMR, as measured by pentad, exceeded 98%. The conversion was 78% based on the styrene monomer used.
성형 조성물의 배합은 신디오탁틱 폴리스티렌 97 중량%, 성분 B) 3 중량%이었다.The formulation of the molding composition was 97% by weight syndiotactic polystyrene, 3% by weight of component B).
＜실시예 2＞<Example 2>
스티렌 104.2 g(1 몰)을 질소의 불활성 분위기인 둥근 바닥 플라스크에서 5.21 g의 성분 B)와 혼합하였다. 혼합물을 1시간 동안 교반시키고 이어서 60℃로 가열하였다. 이 온도에서 15분 동안 좀더 교반하였고 이 혼합물을 위트코(Witco)의 메틸알루미노옥산 (MAO)(톨루엔 중 1.53 M) 8.16 ml 및 알드리치(Aldrich)의 디이소부틸알루미늄 히드라이드 DIBAH(시클로헥산 중 1.0 M) 2.08 ml와 혼합하였다. 이어서 혼합물을 펜타메틸시클로펜타디에닐티타늄 트리메틸 Cp·TiMe39.5 mg(4.16 x 10-5몰)과 혼합하였다. 내용물의 온도를 60℃로 조정하였고 2시간 동안 중합을 진행하였고, 그후 메탄올을 첨가하여 중합을 정지시켰다. 생성된 중합체를 메탄올로 세척하고 50℃, 감압하에서 건조시켰다. 몰 질량 및 그의 분포도를 용매로서 1,2,4-트리클로로벤젠을 사용하는 고온 GPC로 135℃에서 측정하였다. 좁은 분포도를 가진 폴리스티렌 표준 물질을 사용하여 검정하였다. 몰 질량 Mw는 298,700이고, 분포도 폭 D인 Mw/Mn은 2.4이었다.13C NMR로 측정하여 펜타드로 측정하는 신디오탁틱 비율은 98%를 초과하였다. 전환율은 사용된 스티렌 단량체를 기준으로 하여, 76%이었다.104.2 g (1 mol) of styrene were mixed with 5.21 g of component B) in a round bottom flask with an inert atmosphere of nitrogen. The mixture was stirred for 1 hour and then heated to 60 ° C. Stir at this temperature for 15 minutes and mix the mixture with 8.16 ml of Witco's methylaluminoxane (MAO) (1.53 M in toluene) and Diisobutylaluminum hydride DIBAH (Aldrich) in cyclohexane 1.0 M) and 2.08 ml. The mixture was then mixed with 9.5 mg (4.16 x 10 -5 moles) of pentamethylcyclopentadienyltitanium trimethyl CpTiMe 3 . The temperature of the contents was adjusted to 60 ° C. and the polymerization proceeded for 2 hours, after which the polymerization was stopped by adding methanol. The resulting polymer was washed with methanol and dried at 50 ° C. under reduced pressure. The molar mass and its distribution were measured at 135 ° C. by high temperature GPC using 1,2,4-trichlorobenzene as solvent. Assays were made using polystyrene standard materials with narrow distribution. The molar mass M w was 298,700 and M w / M n having a distribution width D was 2.4. The syndiotactic ratio, measured by 13 C NMR, as measured by pentad, exceeded 98%. The conversion was 76% based on the styrene monomer used.
성형 조성물의 배합은 신디오탁틱 폴리스티렌 95 중량%, 성분 B) 5 중량%이었다.The formulation of the molding composition was 95% by weight of syndiotactic polystyrene and 5% by weight of component B).
＜비교예 1＞<Comparative Example 1>
신디오탁틱 폴리스티렌(Xarec 등록상표 S 100, Idemitsu Petrochemical Corp.(일본 소재) 제품). Mw= 197,000 g/몰, D = 2.0.Syndiotactic polystyrene (from Xarec® S 100, manufactured by Idemitsu Petrochemical Corp., Japan). M w = 197,000 g / mol, D = 2.0.
＜비교예 2＞<Comparative Example 2>
30 중량%의 유리 섬유가 있는 신디오탁틱 폴리스티렌(Xarec 등록상표 S 131, Idemitsu Petrochemical Corp.(일본 소재) 제품). Mw= 201,000 g/몰, D = 2.1.Syndiotactic polystyrene with 30% by weight of glass fibers (Xarec® S 131, manufactured by Idemitsu Petrochemical Corp., Japan). M w = 201,000 g / mol, D = 2.1.
＜비교예 3＞<Comparative Example 3>
문헌[A. Echte, F. Haaf, J. Hambrecht, Angew. Chem. 93 (1981) p. 372]에 기술되어 있는 자유 라디칼 중합에 의해 수득될 수 있는 어탁틱 폴리스티렌. Mw= 158,000 g/몰, D = 3.4.A. Echte, F. Haaf, J. Hambrecht, Angew. Chem. 93 (1981) p. Atactic polystyrene obtainable by free radical polymerization as described in 372. M w = 158,000 g / mol, D = 3.4.
＜비교예 4＞<Comparative Example 4>
문헌[A. Akelah, A. Moet, J. Mat. Sci. 31 (1996), p. 3590]의 방법 2.1 내지 2.3에 의해 수득될 수 있는 5 중량%의 성분 B)가 있는 어탁틱 폴리스티렌. Mw= 158,000 g/몰, D = 3.6.A. Akelah, A. Moet, J. Mat. Sci. 31 (1996), p. 3590] atactic polystyrene with 5% by weight of component B) obtainable by methods 2.1 to 2.3. M w = 158,000 g / mol, D = 3.6.
＜비교예 5＞<Comparative Example 5>
질소의 불활성 분위기인 둥근 바닥 플라스크에 스티렌 1.0 몰(104.2 g)을 60℃로 가열하고 위트코(Witco)의 메틸알루미노옥산 (MAO)(톨루엔 중 1.53 M) 8.16 ml 및 알드리치(Aldrich)의 디이소부틸알루미늄 히드라이드 (DIBAH)(시클로헥산 중 1.0 M) 2.08 ml와 혼합하였다. 이어서 혼합물을 펜타메틸시클로펜타디에닐티타늄 트리메틸 Cp·TiMe39.5 mg(4.16 x 10-5몰)과 혼합하였다. 내용물의 온도를 60℃로 조정하였고 2시간 동안 중합을 진행하였고, 그후 메탄올을 첨가하여 중합을 정지시켰다. 생성된 중합체를 메탄올로 세척하고 50℃, 감압하에서 건조시켰다. 몰 질량 및 그의 분포도를 용매로서 1,2,4-트리클로로벤젠을 사용하는 고온 GPC로 135℃에서 측정하였다. 좁은 분포도를 가진 폴리스티렌 표준 물질을 사용하여 검정하였다. 몰량 Mw은 322,100이고, 분포도 폭 D인 Mw/Mn은 2.1이었다.13C NMR로 측정하여 펜타드로 측정하는 신디오탁틱 비율은 96%를 초과하였다. 전환율은 사용된 스티렌 단량체를 기준으로 하여, 84%이었다.1.0 mole (104.2 g) of styrene was heated to 60 ° C. in a round-bottomed flask with nitrogen inert atmosphere, 8.16 ml of Witco's methylaluminooxane (MAO) (1.53 M in toluene) and Didrich's Didrich Mix with 2.08 ml of isobutylaluminum hydride (DIBAH) (1.0 M in cyclohexane). The mixture was then mixed with 9.5 mg (4.16 x 10 -5 moles) of pentamethylcyclopentadienyltitanium trimethyl CpTiMe 3 . The temperature of the contents was adjusted to 60 ° C. and the polymerization proceeded for 2 hours, after which the polymerization was stopped by adding methanol. The resulting polymer was washed with methanol and dried at 50 ° C. under reduced pressure. The molar mass and its distribution were measured at 135 ° C. by high temperature GPC using 1,2,4-trichlorobenzene as solvent. Assays were made using polystyrene standard materials with narrow distribution. The molar amount M w was 322,100 and M w / M n having a distribution width D was 2.1. The syndiotactic ratio, measured by 13 C NMR, as measured by pentad, exceeded 96%. The conversion was 84% based on the styrene monomer used.
실시예 1, 2 및 비교예 1 내지 5의 성형 조성물을 290 내지 310℃의 용융 온도 및 130 내지 150℃의 주형 표면 온도에서 표준 검사 시편을 사출 성형하였다. 측정 결과 및 검사 방법을 표에 나타낸다.The molding compositions of Examples 1, 2 and Comparative Examples 1-5 were injection molded of standard test specimens at a melt temperature of 290-310 ° C. and a mold surface temperature of 130-150 ° C. A measurement result and an inspection method are shown in a table.
Claims (10)
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| DE19714548A DE19714548A1 (en) | 1997-04-09 | 1997-04-09 | Thermoplastic molding compounds |
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| JP4369134B2 (en) * | 2003-01-31 | 2009-11-18 | 株式会社フジクラ | Substrate and molded product |
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1998
- 1998-03-26 CN CN98802411A patent/CN1246878A/en active Pending
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- 1998-03-26 WO PCT/EP1998/001802 patent/WO1998045362A1/en not_active Application Discontinuation
- 1998-03-26 JP JP54232298A patent/JP2001518954A/en active Pending
- 1998-03-26 CA CA002275197A patent/CA2275197A1/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| CN1246878A (en) | 2000-03-08 |
| EP0973828A1 (en) | 2000-01-26 |
| JP2001518954A (en) | 2001-10-16 |
| CA2275197A1 (en) | 1998-10-15 |
| DE19714548A1 (en) | 1998-10-15 |
| WO1998045362A1 (en) | 1998-10-15 |
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