JP5421356B2 - ブタジエン/ビニル芳香族共重合体を臭素化する方法 - Google Patents
ブタジエン/ビニル芳香族共重合体を臭素化する方法 Download PDFInfo
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- JP5421356B2 JP5421356B2 JP2011504092A JP2011504092A JP5421356B2 JP 5421356 B2 JP5421356 B2 JP 5421356B2 JP 2011504092 A JP2011504092 A JP 2011504092A JP 2011504092 A JP2011504092 A JP 2011504092A JP 5421356 B2 JP5421356 B2 JP 5421356B2
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- JP
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- Prior art keywords
- butadiene polymer
- solvent
- brominated
- quaternary ammonium
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 118
- 238000000034 method Methods 0.000 title claims description 72
- 229920002554 vinyl polymer Polymers 0.000 title claims description 16
- 229920001577 copolymer Polymers 0.000 title description 20
- 239000002904 solvent Substances 0.000 claims description 124
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 123
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 claims description 110
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 56
- 239000000243 solution Substances 0.000 claims description 53
- 239000002245 particle Substances 0.000 claims description 37
- 230000008569 process Effects 0.000 claims description 36
- 239000002002 slurry Substances 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 239000008346 aqueous phase Substances 0.000 claims description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 15
- 239000000178 monomer Substances 0.000 claims description 15
- 239000003638 chemical reducing agent Substances 0.000 claims description 14
- 230000000996 additive effect Effects 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- -1 tetrapropylammonium tribromide Chemical compound 0.000 claims description 11
- 229920001400 block copolymer Polymers 0.000 claims description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229920000578 graft copolymer Polymers 0.000 claims description 6
- 229920005604 random copolymer Polymers 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 6
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 claims description 5
- SGXVTRUKGXCZQB-UHFFFAOYSA-N Br[Br-]Br.CC[N+](CC)(CC)CC Chemical compound Br[Br-]Br.CC[N+](CC)(CC)CC SGXVTRUKGXCZQB-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 claims description 4
- JPOXNPPZZKNXOV-UHFFFAOYSA-N bromochloromethane Chemical compound ClCBr JPOXNPPZZKNXOV-UHFFFAOYSA-N 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 claims description 2
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
- NVBCFOQYDFKXJJ-UHFFFAOYSA-N 3-formyl-1h-indole-5-carbonitrile Chemical compound C1=C(C#N)C=C2C(C=O)=CNC2=C1 NVBCFOQYDFKXJJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910014265 BrCl Inorganic materials 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- KTLFENNEPHBKJD-UHFFFAOYSA-K benzyl(trimethyl)azanium;tribromide Chemical compound [Br-].[Br-].[Br-].C[N+](C)(C)CC1=CC=CC=C1.C[N+](C)(C)CC1=CC=CC=C1.C[N+](C)(C)CC1=CC=CC=C1 KTLFENNEPHBKJD-UHFFFAOYSA-K 0.000 claims description 2
- CODNYICXDISAEA-UHFFFAOYSA-N bromine monochloride Chemical compound BrCl CODNYICXDISAEA-UHFFFAOYSA-N 0.000 claims description 2
- FJBFPHVGVWTDIP-UHFFFAOYSA-N dibromomethane Chemical compound BrCBr FJBFPHVGVWTDIP-UHFFFAOYSA-N 0.000 claims description 2
- 229940117389 dichlorobenzene Drugs 0.000 claims description 2
- PRXNKYBFWAWBNZ-UHFFFAOYSA-N trimethylphenylammonium tribromide Chemical group Br[Br-]Br.C[N+](C)(C)C1=CC=CC=C1 PRXNKYBFWAWBNZ-UHFFFAOYSA-N 0.000 claims description 2
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims 5
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 claims 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 claims 1
- 238000000605 extraction Methods 0.000 description 75
- 229920000642 polymer Polymers 0.000 description 49
- 239000012071 phase Substances 0.000 description 27
- 238000011084 recovery Methods 0.000 description 26
- 238000005893 bromination reaction Methods 0.000 description 20
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 15
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical group [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 14
- 229910052794 bromium Inorganic materials 0.000 description 14
- 230000031709 bromination Effects 0.000 description 13
- 239000000203 mixture Substances 0.000 description 13
- 229910052783 alkali metal Inorganic materials 0.000 description 10
- 239000005062 Polybutadiene Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920002857 polybutadiene Polymers 0.000 description 9
- 239000011541 reaction mixture Substances 0.000 description 9
- 238000007792 addition Methods 0.000 description 8
- 239000002585 base Substances 0.000 description 8
- 238000004090 dissolution Methods 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 238000000926 separation method Methods 0.000 description 8
- 238000007906 compression Methods 0.000 description 7
- 230000006835 compression Effects 0.000 description 7
- 239000012530 fluid Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 229920000620 organic polymer Polymers 0.000 description 7
- 239000004793 Polystyrene Substances 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- QNRMTGGDHLBXQZ-UHFFFAOYSA-N buta-1,2-diene Chemical group CC=C=C QNRMTGGDHLBXQZ-UHFFFAOYSA-N 0.000 description 6
- 229920002223 polystyrene Polymers 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- GPWHDDKQSYOYBF-UHFFFAOYSA-N ac1l2u0q Chemical compound Br[Br-]Br GPWHDDKQSYOYBF-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 238000013459 approach Methods 0.000 description 5
- 238000005192 partition Methods 0.000 description 5
- 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 4
- 125000003118 aryl group Chemical group 0.000 description 4
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000013557 residual solvent Substances 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 125000001246 bromo group Chemical group Br* 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005227 gel permeation chromatography Methods 0.000 description 3
- 229910052736 halogen Inorganic materials 0.000 description 3
- 150000002367 halogens Chemical group 0.000 description 3
- 229920001519 homopolymer Polymers 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000004014 plasticizer Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000002516 radical scavenger Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- HWCKGOZZJDHMNC-UHFFFAOYSA-M tetraethylammonium bromide Chemical compound [Br-].CC[N+](CC)(CC)CC HWCKGOZZJDHMNC-UHFFFAOYSA-M 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012552 review Methods 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- SSZOCHFYWWVSAI-UHFFFAOYSA-N 1-bromo-2-ethenylbenzene Chemical compound BrC1=CC=CC=C1C=C SSZOCHFYWWVSAI-UHFFFAOYSA-N 0.000 description 1
- WGGLDBIZIQMEGH-UHFFFAOYSA-N 1-bromo-4-ethenylbenzene Chemical compound BrC1=CC=C(C=C)C=C1 WGGLDBIZIQMEGH-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
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-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
- VKVLTUQLNXVANB-UHFFFAOYSA-N 1-ethenyl-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1C=C VKVLTUQLNXVANB-UHFFFAOYSA-N 0.000 description 1
- UAJRSHJHFRVGMG-UHFFFAOYSA-N 1-ethenyl-4-methoxybenzene Chemical compound COC1=CC=C(C=C)C=C1 UAJRSHJHFRVGMG-UHFFFAOYSA-N 0.000 description 1
- YFZHODLXYNDBSM-UHFFFAOYSA-N 1-ethenyl-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(C=C)C=C1 YFZHODLXYNDBSM-UHFFFAOYSA-N 0.000 description 1
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-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
- QEJPOEGPNIVDMK-UHFFFAOYSA-N 3-bromo-2,2-bis(bromomethyl)propan-1-ol Chemical compound OCC(CBr)(CBr)CBr QEJPOEGPNIVDMK-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000012963 UV stabilizer Substances 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 238000010539 anionic addition polymerization reaction Methods 0.000 description 1
- 239000012296 anti-solvent Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical group 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- HORIEOQXBKUKGQ-UHFFFAOYSA-N bis(7-methyloctyl) cyclohexane-1,2-dicarboxylate Chemical compound CC(C)CCCCCCOC(=O)C1CCCCC1C(=O)OCCCCCCC(C)C HORIEOQXBKUKGQ-UHFFFAOYSA-N 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229910052792 caesium Inorganic materials 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000005056 compaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 229910052805 deuterium Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000004806 diisononylester Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 150000002118 epoxides Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229940030980 inova Drugs 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000012432 intermediate storage Methods 0.000 description 1
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 description 1
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- SFBTTWXNCQVIEC-UHFFFAOYSA-N o-Vinylanisole Chemical compound COC1=CC=CC=C1C=C SFBTTWXNCQVIEC-UHFFFAOYSA-N 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
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- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
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- 238000010926 purge Methods 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 150000003856 quaternary ammonium compounds Chemical class 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000009490 roller compaction Methods 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
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- 239000011877 solvent mixture Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- XXSLZJZUSYNITM-UHFFFAOYSA-N tetrabutylammonium tribromide Chemical compound Br[Br-]Br.CCCC[N+](CCCC)(CCCC)CCCC XXSLZJZUSYNITM-UHFFFAOYSA-N 0.000 description 1
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- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
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- C—CHEMISTRY; METALLURGY
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- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/12—Incorporating halogen atoms into the molecule
- C08C19/14—Incorporating halogen atoms into the molecule by reaction with halogens
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- C08F8/00—Chemical modification by after-treatment
- C08F8/18—Introducing halogen atoms or halogen-containing groups
- C08F8/20—Halogenation
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Description
本発明は、スチレンとブタジエンのブロック、ランダムまたはグラフト共重合体のようなブタジエン共重合体を臭素化する方法に関する。
a.原料のブタジエン重合体と三臭化第四級アンモニウムが反応し、臭素化されたブタジエン重合体および一臭化第四級アンモニウム副生成物を生成するような条件下で、原料の脂肪族炭素−炭素二重結合を含むブタジエン重合体を三臭化第四級アンモニウムと接触させる工程(ただし、原料のブタジエン重合体の反応は、反応条件下で原料のブタジエン重合体と三臭化第四級アンモニウムの両方が溶解し、かつ臭素化されたブタジエン重合体が少なくとも部分的に溶解する溶媒の存在下で行われ、そしてその溶媒中の臭素化されたブタジエン重合体の溶液またはスラリーが反応において形成されるように行なわれる。)、
b.還元剤を含む水性の相で臭素化されたブタジエン重合体の溶液またはスラリーを抽出し、一臭化第四級アンモニウム塩水溶液流れおよび臭素化されたブタジエン重合体の洗浄された溶液またはスラリーを形成する工程、
c.工程bにおいて得られた一臭化第四級アンモニウム塩水溶液流れを、元素の臭素および溶媒流れと接触させ、水性のラフィネート流れおよび溶媒中の三臭化第四級アンモニウムの溶液を形成する工程、および
d.工程cで得られた三臭化第四級アンモニウム溶液を工程aへリサイクルする工程。
e.工程bにおいて得られた洗浄された溶液またはスラリーから臭素化されたブタジエン重合体を回収し、固体の臭素化されたブタジエン重合体と溶媒流れを生成する工程、および
f.工程eにおいて得られた溶媒流れの少なくとも一部を工程cへリサイクルする工程。
工程eは、好ましくは、e1)洗浄された溶液またはスラリーを細かい小滴にし、e2)小滴から熱により溶媒を除去して臭素化されたブタジエン重合体の粒子を形成し、そして、熱による溶媒除去工程の前または後に、e3)小滴または粒子を水で洗浄することにより行なわれる。
g.工程e3)の後に、洗浄水から臭素化されたブタジエン重合体の粒子を分離し、洗浄水の少なくとも一部を工程a、工程bまたは工程eの少なくとも1つへリサイクルする工程。
Claims (15)
- a.原料ブタジエン重合体と三臭化第四級アンモニウムが反応して臭素化されたブタジエン重合体および一臭化第四級アンモニウム副生成物を生成する条件下で、原料の脂肪族炭素−炭素二重結合を含むブタジエン重合体を三臭化第四級アンモニウムと接触させる工程(ただし、原料ブタジエン重合体の反応は、原料ブタジエン重合体と三臭化第四級アンモニウムが両方とも反応条件下で可溶でありかつ臭素化されたブタジエン重合体が少なくとも部分的に可溶である溶媒の存在下で行なわれ、そして溶媒中の臭素化されたブタジエン重合体の溶液またはスラリーが、その反応で形成される。)、
b.還元剤を含む水性の相で臭素化されたブタジエン重合体の溶液またはスラリーを抽出し、一臭化第四級アンモニウム塩水溶液流れと臭素化されたブタジエン重合体の洗浄された溶液またはスラリーを生成する工程、
c.工程bで得られた一臭化第四級アンモニウム塩水溶液流れを、元素臭素および溶媒流れと接触させ、水性のラフィネート流れ、および溶媒に三臭化第四級アンモニウムが溶けた溶液を生成する工程、および
d.工程cで得られた三臭化第四級アンモニウム溶液を工程aにリサイクルする工程
を含む方法。 - e.工程bで得られた洗浄された溶液またはスラリーから臭素化されたブタジエン重合体を回収し、固体の臭素化されたブタジエン重合体および溶媒流れを生成する工程、および
f.工程eで得られた溶媒流れの少なくとも一部を工程cにリサイクルする工程
をさらに含む請求項1に記載の方法。 - 工程eが、e1)洗浄された溶液またはスラリーを細かい小滴にする工程、e2)小滴から熱により溶媒を除去し、臭素化されたブタジエン重合体の粒子を形成する工程、および、熱による除去工程の前にまたはその工程の後に、e3)水の中で小滴または粒子を洗浄する工程によって行なわれることを特徴とする請求項2に記載の方法。
- g.工程e3の後に、洗浄水から臭素化されたブタジエン重合体の小滴または粒子を分離し、そして、洗浄水の少なくとも一部を工程a、工程bまたは工程eの少なくとも1つにリサイクルする工程をさらに含む請求項3に記載の方法。
- 工程gは固体の臭素化されたブタジエン重合体を遠心分離機にかけ、そして乾燥することによって行なわれることを特徴とする請求項4に記載の方法。
- 工程eまたは工程gにおいて得られた固体の臭素化されたブタジエン重合体に、少なくとも1種の添加物が添加されることを特徴とする請求項5に記載の方法。
- h.工程gの後に、乾燥した臭素化されたブタジエン重合体を圧縮する工程をさらに含む請求項5または6に記載の方法。
- 工程e2において、小滴が水蒸気ストリッピングされることを特徴とする請求項3〜7のいずれか1項に記載の方法。
- 工程bの後に、臭素化されたブタジエン重合体の小滴または粒子に、少なくとも1種の添加物が添加されることを特徴とする請求項1に記載の方法。
- 工程bにおいて得られた臭素化されたブタジエン重合体の洗浄された溶液またはスラリーに、少なくとも1種の添加物が添加されることを特徴とする請求項4に記載の方法。
- 工程gは臭素化されたブタジエン重合体の粒子を遠心分離機にかけかつ乾燥することによって行なわれ、そして該方法がさらに、h.工程gの後に、乾燥した臭素化されたブタジエン重合体を圧縮する工程を含むことを特徴とする請求項10に記載の方法。
- 溶媒が、四塩化炭素、クロロホルム、ジクロロメタン、ブロモクロロメタン(CH2BrCl)、ジブロモメタン、1,2−ジクロロエタン、シクロヘキサン、トルエン、ブロモベンゼン、クロロベンゼンおよびジクロロベンゼンの1種または2種以上であることを特徴とする請求項1〜11のいずれか1項に記載の方法。
- 三臭化第四級アンモニウムが、三臭化フェニルトリメチルアンモニウム、三臭化ベンジルトリメチルアンモニウム、三臭化テトラメチルアンモニウム、三臭化テトラエチルアンモニウム、三臭化テトラプロピルアンモニウムおよび三臭化テトラ−n−ブチルアンモニウムの少なくとも1種であることを特徴とする請求項1〜12のいずれか1項に記載の方法。
- 原料ブタジエン重合体が、ブタジエン単独重合体、またはブタジエンと少なくとも1種のビニル芳香族単量体のランダム、ブロックまたはグラフト共重合体であることを特徴とする請求項1〜13のいずれか1項に記載の方法。
- 原料ブタジエン重合体がブタジエンとスチレンのブロック共重合体であることを特徴とする請求項1〜4のいずれか1項に記載の方法。
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