KR100295601B1 - Process for selective hydrogenation of conjugated diene polymer - Google Patents
Process for selective hydrogenation of conjugated diene polymer Download PDFInfo
- Publication number
- KR100295601B1 KR100295601B1 KR1019990001292A KR19990001292A KR100295601B1 KR 100295601 B1 KR100295601 B1 KR 100295601B1 KR 1019990001292 A KR1019990001292 A KR 1019990001292A KR 19990001292 A KR19990001292 A KR 19990001292A KR 100295601 B1 KR100295601 B1 KR 100295601B1
- Authority
- KR
- South Korea
- Prior art keywords
- conjugated diene
- hydrogenation
- monocyclopentadienyl
- polymer
- titanium
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 135
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 99
- 150000001993 dienes Chemical class 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 45
- 230000008569 process Effects 0.000 title claims description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 45
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000001257 hydrogen Substances 0.000 claims abstract description 36
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 36
- 239000000178 monomer Substances 0.000 claims abstract description 29
- 229910000103 lithium hydride Inorganic materials 0.000 claims abstract description 19
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 5
- 125000000058 cyclopentadienyl group Chemical group C1(=CC=CC1)* 0.000 claims abstract description 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- 125000004104 aryloxy group Chemical group 0.000 claims abstract description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims abstract description 3
- 125000005843 halogen group Chemical group 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 61
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 41
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 20
- -1 monocyclopentadienyl (2,4-dimethylpyrrolyl) titanium dioxide Chemical compound 0.000 claims description 20
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- SUWITGBNLXLVBO-UHFFFAOYSA-N C1=CC=CC1[Ti]C1=CC=CN1 Chemical compound C1=CC=CC1[Ti]C1=CC=CN1 SUWITGBNLXLVBO-UHFFFAOYSA-N 0.000 claims description 9
- GZUXJHMPEANEGY-UHFFFAOYSA-N bromomethane Chemical compound BrC GZUXJHMPEANEGY-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910052783 alkali metal Inorganic materials 0.000 claims description 6
- 150000001340 alkali metals Chemical class 0.000 claims description 6
- 239000003999 initiator Substances 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- JBETYTFRQUTJEX-UHFFFAOYSA-L CC1=CC([Ti+2]C2C=CC=C2)=C(C)N1.[Cl-].[Cl-] Chemical compound CC1=CC([Ti+2]C2C=CC=C2)=C(C)N1.[Cl-].[Cl-] JBETYTFRQUTJEX-UHFFFAOYSA-L 0.000 claims description 5
- FZKMEFJRXGRWSU-UHFFFAOYSA-L [Cl-].[Cl-].C1(C=CC=C1)[Ti+2]C=1NC=CC=1 Chemical compound [Cl-].[Cl-].C1(C=CC=C1)[Ti+2]C=1NC=CC=1 FZKMEFJRXGRWSU-UHFFFAOYSA-L 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 150000002900 organolithium compounds Chemical class 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- KCXMKQUNVWSEMD-UHFFFAOYSA-N benzyl chloride Chemical compound ClCC1=CC=CC=C1 KCXMKQUNVWSEMD-UHFFFAOYSA-N 0.000 claims description 4
- 229940073608 benzyl chloride Drugs 0.000 claims description 4
- DCFKHNIGBAHNSS-UHFFFAOYSA-N chloro(triethyl)silane Chemical compound CC[Si](Cl)(CC)CC DCFKHNIGBAHNSS-UHFFFAOYSA-N 0.000 claims description 4
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 claims description 4
- 150000002642 lithium compounds Chemical class 0.000 claims description 4
- 229940102396 methyl bromide Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- CSRZQMIRAZTJOY-UHFFFAOYSA-N trimethylsilyl iodide Chemical compound C[Si](C)(C)I CSRZQMIRAZTJOY-UHFFFAOYSA-N 0.000 claims description 4
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 claims description 3
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 2
- VFWCMGCRMGJXDK-UHFFFAOYSA-N 1-chlorobutane Chemical compound CCCCCl VFWCMGCRMGJXDK-UHFFFAOYSA-N 0.000 claims description 2
- QTWJRLJHJPIABL-UHFFFAOYSA-N 2-methylphenol;3-methylphenol;4-methylphenol Chemical compound CC1=CC=C(O)C=C1.CC1=CC=CC(O)=C1.CC1=CC=CC=C1O QTWJRLJHJPIABL-UHFFFAOYSA-N 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- NLZUEZXRPGMBCV-UHFFFAOYSA-N Butylhydroxytoluene Chemical compound CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 NLZUEZXRPGMBCV-UHFFFAOYSA-N 0.000 claims description 2
- SMYGXGHJCHAKSZ-UHFFFAOYSA-L C1=CC=CC1[Ti+2]C1=CC=CN1.[Br-].[Br-] Chemical compound C1=CC=CC1[Ti+2]C1=CC=CN1.[Br-].[Br-] SMYGXGHJCHAKSZ-UHFFFAOYSA-L 0.000 claims description 2
- IDKBPRCHTFNVQF-UHFFFAOYSA-L C1=CC=CC1[Ti+2]C1=CC=CN1.[F-].[F-] Chemical compound C1=CC=CC1[Ti+2]C1=CC=CN1.[F-].[F-] IDKBPRCHTFNVQF-UHFFFAOYSA-L 0.000 claims description 2
- UNUXPGRWKRSSMH-UHFFFAOYSA-L CC1=CC([Ti+2]C2C=CC=C2)=C(C)N1.[F-].[F-] Chemical compound CC1=CC([Ti+2]C2C=CC=C2)=C(C)N1.[F-].[F-] UNUXPGRWKRSSMH-UHFFFAOYSA-L 0.000 claims description 2
- XTLRNJSIXPACED-UHFFFAOYSA-N CC1=CC([Ti]C2C=CC=C2)=C(C)N1 Chemical compound CC1=CC([Ti]C2C=CC=C2)=C(C)N1 XTLRNJSIXPACED-UHFFFAOYSA-N 0.000 claims description 2
- OHMVJDMFGOIDBF-UHFFFAOYSA-L CC1=CNC(C)=C1[Ti+2]C1C=CC=C1.[Br-].[Br-] Chemical compound CC1=CNC(C)=C1[Ti+2]C1C=CC=C1.[Br-].[Br-] OHMVJDMFGOIDBF-UHFFFAOYSA-L 0.000 claims description 2
- XNXPWVWHCSDLGI-UHFFFAOYSA-L CC1=CNC(C)=C1[Ti+2]C1C=CC=C1.[Cl-].[Cl-] Chemical compound CC1=CNC(C)=C1[Ti+2]C1C=CC=C1.[Cl-].[Cl-] XNXPWVWHCSDLGI-UHFFFAOYSA-L 0.000 claims description 2
- VOVDTSPXQLGLGY-UHFFFAOYSA-L CC1=CNC(C)=C1[Ti+2]C1C=CC=C1.[F-].[F-] Chemical compound CC1=CNC(C)=C1[Ti+2]C1C=CC=C1.[F-].[F-] VOVDTSPXQLGLGY-UHFFFAOYSA-L 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 2
- AGEZXYOZHKGVCM-UHFFFAOYSA-N benzyl bromide Chemical compound BrCC1=CC=CC=C1 AGEZXYOZHKGVCM-UHFFFAOYSA-N 0.000 claims description 2
- NIRUTWLZGUITFB-UHFFFAOYSA-N bromo(tributyl)silane Chemical compound CCCC[Si](Br)(CCCC)CCCC NIRUTWLZGUITFB-UHFFFAOYSA-N 0.000 claims description 2
- IYYIVELXUANFED-UHFFFAOYSA-N bromo(trimethyl)silane Chemical compound C[Si](C)(C)Br IYYIVELXUANFED-UHFFFAOYSA-N 0.000 claims description 2
- VSCMNSZBNLOXNR-UHFFFAOYSA-N bromo(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Br)C1=CC=CC=C1 VSCMNSZBNLOXNR-UHFFFAOYSA-N 0.000 claims description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 claims description 2
- KMGBZBJJOKUPIA-UHFFFAOYSA-N butyl iodide Chemical compound CCCCI KMGBZBJJOKUPIA-UHFFFAOYSA-N 0.000 claims description 2
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 claims description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 claims description 2
- 229930003836 cresol Natural products 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229960003750 ethyl chloride Drugs 0.000 claims description 2
- CTIKAHQFRQTTAY-UHFFFAOYSA-N fluoro(trimethyl)silane Chemical compound C[Si](C)(C)F CTIKAHQFRQTTAY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002366 halogen compounds Chemical class 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 2
- NNRANHIFAQDLRA-UHFFFAOYSA-N iodo(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(I)C1=CC=CC=C1 NNRANHIFAQDLRA-UHFFFAOYSA-N 0.000 claims description 2
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 claims description 2
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 2
- XJTQJERLRPWUGL-UHFFFAOYSA-N iodomethylbenzene Chemical compound ICC1=CC=CC=C1 XJTQJERLRPWUGL-UHFFFAOYSA-N 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N phthalic acid di-n-butyl ester Natural products CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 2
- JSQJUDVTRRCSRU-UHFFFAOYSA-N tributyl(chloro)silane Chemical compound CCCC[Si](Cl)(CCCC)CCCC JSQJUDVTRRCSRU-UHFFFAOYSA-N 0.000 claims description 2
- RYHGFALZTBTGDK-UHFFFAOYSA-N tributyl(iodo)silane Chemical compound CCCC[Si](I)(CCCC)CCCC RYHGFALZTBTGDK-UHFFFAOYSA-N 0.000 claims description 2
- QVMRVWAOMIXFFW-UHFFFAOYSA-N triethyl(fluoro)silane Chemical compound CC[Si](F)(CC)CC QVMRVWAOMIXFFW-UHFFFAOYSA-N 0.000 claims description 2
- SIAPCJWMELPYOE-UHFFFAOYSA-N lithium hydride Chemical compound [LiH] SIAPCJWMELPYOE-UHFFFAOYSA-N 0.000 claims 4
- 239000003398 denaturant Substances 0.000 claims 2
- PWSZPEBVDGOKQL-UHFFFAOYSA-N F[SiH2]C1=CC=CC=C1 Chemical compound F[SiH2]C1=CC=CC=C1 PWSZPEBVDGOKQL-UHFFFAOYSA-N 0.000 claims 1
- QVMLGSVNQSRJHW-UHFFFAOYSA-N N1C(=CC=C1)[Ti] Chemical compound N1C(=CC=C1)[Ti] QVMLGSVNQSRJHW-UHFFFAOYSA-N 0.000 claims 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 claims 1
- VQPFDLRNOCQMSN-UHFFFAOYSA-N bromosilane Chemical compound Br[SiH3] VQPFDLRNOCQMSN-UHFFFAOYSA-N 0.000 claims 1
- MNKYQPOFRKPUAE-UHFFFAOYSA-N chloro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(Cl)C1=CC=CC=C1 MNKYQPOFRKPUAE-UHFFFAOYSA-N 0.000 claims 1
- IDIOJRGTRFRIJL-UHFFFAOYSA-N iodosilane Chemical compound I[SiH3] IDIOJRGTRFRIJL-UHFFFAOYSA-N 0.000 claims 1
- AUZMWGNTACEWDV-UHFFFAOYSA-L titanium(2+);dibromide Chemical compound Br[Ti]Br AUZMWGNTACEWDV-UHFFFAOYSA-L 0.000 claims 1
- 125000002306 tributylsilyl group Chemical group C(CCC)[Si](CCCC)(CCCC)* 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 abstract description 23
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 17
- 229920002554 vinyl polymer Polymers 0.000 abstract description 17
- 230000000694 effects Effects 0.000 abstract description 12
- 239000010936 titanium Substances 0.000 abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 abstract description 5
- 229920001519 homopolymer Polymers 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052719 titanium Inorganic materials 0.000 abstract description 3
- 238000006467 substitution reaction Methods 0.000 abstract 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 25
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 22
- 239000000243 solution Substances 0.000 description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 15
- 229920000468 styrene butadiene styrene block copolymer Polymers 0.000 description 14
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 13
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 11
- 238000006116 polymerization reaction Methods 0.000 description 9
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 9
- 239000002815 homogeneous catalyst Substances 0.000 description 8
- FACXGONDLDSNOE-UHFFFAOYSA-N buta-1,3-diene;styrene Chemical compound C=CC=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 FACXGONDLDSNOE-UHFFFAOYSA-N 0.000 description 7
- 125000002897 diene group Chemical group 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- 229940038926 butyl chloride Drugs 0.000 description 6
- 239000011261 inert gas Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000004945 aromatic hydrocarbons Chemical group 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 239000002638 heterogeneous catalyst Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- NBRKLOOSMBRFMH-UHFFFAOYSA-N tert-butyl chloride Chemical compound CC(C)(C)Cl NBRKLOOSMBRFMH-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 3
- 150000008046 alkali metal hydrides Chemical class 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 229910052987 metal hydride Inorganic materials 0.000 description 3
- 150000004681 metal hydrides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical group C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 2
- PAPNRQCYSFBWDI-UHFFFAOYSA-N 2,5-Dimethyl-1H-pyrrole Chemical compound CC1=CC=C(C)N1 PAPNRQCYSFBWDI-UHFFFAOYSA-N 0.000 description 2
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 229920001400 block copolymer Polymers 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- AENCLWKVWIIOQH-UHFFFAOYSA-K cyclopentane;trichlorotitanium Chemical compound Cl[Ti](Cl)Cl.[CH]1C=CC=C1 AENCLWKVWIIOQH-UHFFFAOYSA-K 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N endo-cyclopentadiene Natural products C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 239000012442 inert solvent Substances 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 description 2
- 150000003440 styrenes Chemical group 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical group C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 description 1
- SKIIKRJAQOSWFT-UHFFFAOYSA-N 2-[3-[1-(2,2-difluoroethyl)piperidin-4-yl]oxy-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCC(CC1)OC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SKIIKRJAQOSWFT-UHFFFAOYSA-N 0.000 description 1
- SBMYBOVJMOVVQW-UHFFFAOYSA-N 2-[3-[[4-(2,2-difluoroethyl)piperazin-1-yl]methyl]-4-[2-(2,3-dihydro-1H-inden-2-ylamino)pyrimidin-5-yl]pyrazol-1-yl]-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethanone Chemical compound FC(CN1CCN(CC1)CC1=NN(C=C1C=1C=NC(=NC=1)NC1CC2=CC=CC=C2C1)CC(=O)N1CC2=C(CC1)NN=N2)F SBMYBOVJMOVVQW-UHFFFAOYSA-N 0.000 description 1
- VSKJLJHPAFKHBX-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1.C=CC1=CC=CC=C1 VSKJLJHPAFKHBX-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical group C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- QTTAWIGVQMSWMV-UHFFFAOYSA-N 3,4-dimethylhexa-1,3-diene Chemical compound CCC(C)=C(C)C=C QTTAWIGVQMSWMV-UHFFFAOYSA-N 0.000 description 1
- KFDVPJUYSDEJTH-UHFFFAOYSA-N 4-ethenylpyridine Chemical group C=CC1=CC=NC=C1 KFDVPJUYSDEJTH-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004609 Impact Modifier Substances 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000002174 Styrene-butadiene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
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- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- UCKORWKZRPKRQE-UHFFFAOYSA-N bromo(triethyl)silane Chemical compound CC[Si](Br)(CC)CC UCKORWKZRPKRQE-UHFFFAOYSA-N 0.000 description 1
- RTACIUYXLGWTAE-UHFFFAOYSA-N buta-1,3-diene;2-methylbuta-1,3-diene;styrene Chemical compound C=CC=C.CC(=C)C=C.C=CC1=CC=CC=C1 RTACIUYXLGWTAE-UHFFFAOYSA-N 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- PESYEWKSBIWTAK-UHFFFAOYSA-N cyclopenta-1,3-diene;titanium(2+) Chemical class [Ti+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 PESYEWKSBIWTAK-UHFFFAOYSA-N 0.000 description 1
- SRKKQWSERFMTOX-UHFFFAOYSA-N cyclopentane;titanium Chemical compound [Ti].[CH]1C=CC=C1 SRKKQWSERFMTOX-UHFFFAOYSA-N 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- XXLOICMXOBKOLH-UHFFFAOYSA-L diiodotitanium Chemical compound I[Ti]I XXLOICMXOBKOLH-UHFFFAOYSA-L 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- UBGXLEFOIVWVRP-UHFFFAOYSA-N fluoro(triphenyl)silane Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(F)C1=CC=CC=C1 UBGXLEFOIVWVRP-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021482 group 13 metal Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000009905 homogeneous catalytic hydrogenation reaction Methods 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 125000002524 organometallic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 238000012667 polymer degradation Methods 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 229920005990 polystyrene resin Polymers 0.000 description 1
- 229920000346 polystyrene-polyisoprene block-polystyrene Polymers 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011115 styrene butadiene Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229920002725 thermoplastic elastomer Polymers 0.000 description 1
- 150000003609 titanium compounds Chemical class 0.000 description 1
- STAGZMKHHNNCKQ-UHFFFAOYSA-N tributyl(fluoro)silane Chemical compound CCCC[Si](F)(CCCC)CCCC STAGZMKHHNNCKQ-UHFFFAOYSA-N 0.000 description 1
- PPLMQFARLJLZAO-UHFFFAOYSA-N triethyl(iodo)silane Chemical compound CC[Si](I)(CC)CC PPLMQFARLJLZAO-UHFFFAOYSA-N 0.000 description 1
- 239000008096 xylene Substances 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
- C08F8/00—Chemical modification by after-treatment
- C08F8/04—Reduction, e.g. hydrogenation
Abstract
본 발명은 단일중합체 또는 공중합체의 공액디엔 단위의 불포화 이중결합에 선택적으로 수소를 첨가하는 방법에 있어서 촉매로서 다음 화학식 1로 표시되는 고활성을 갖는 새로운 균일 상 유기티타늄 촉매를 사용하는 방법으로, 환원제로서 사용하는 리튬하이드라이드(LiH)를 유기알킬리튬과 수소를 용액 중에서 접촉시켜 만들어 혼합 사용함으로써 매우 높은 수소 첨가율과 수소화 재현성을 나타낼 수 있을 뿐만 아니라 공액디엔계 중합체 및 공액디엔계 모노머와 비닐치환 방향족 모노머와의 공중합체에 있어서 공액디엔 단위의 불포화 이중결합을 극히 선택적으로 수소화 할 수 있는 새로운 방법이다.The present invention relates to a method of selectively adding hydrogen to an unsaturated double bond of a conjugated diene unit of a homopolymer or copolymer, using a novel homogeneous phase organic titanium catalyst having high activity represented by the following Chemical Formula 1 as a catalyst, Lithium hydride (LiH) used as a reducing agent is brought into contact with an organoalkyl lithium and hydrogen in a solution to be mixed and used to show very high hydrogenation rate and hydrogenation reproducibility, as well as conjugated diene polymer, conjugated diene monomer and vinyl substitution. It is a new method which can extremely selectively hydrogenate the unsaturated double bond of the conjugated diene unit in the copolymer with an aromatic monomer.
상기 식에서, Cp는 사이클로펜타디에닐기(C5H5)이고,In the above formula, Cp is a cyclopentadienyl group (C 5 H 5 ),
R1, R2, R3및 R4는 서로 같거나 다른 것으로서, 수소원자, 탄소원자수 1∼12의 알킬기 또는 알콕시기, 탄소원자수 6∼20의 아릴기, 아릴록시기 또는 사이클로알킬기이며,R 1 , R 2 , R 3 and R 4 are the same as or different from each other, and are a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, an aryl group having 6 to 20 carbon atoms, an aryloxy group or a cycloalkyl group,
R5와 R6는 서로 같거나 다른 것으로서, 할로겐 원자로부터 선택된 것이다.R 5 and R 6 are the same as or different from each other, and are selected from halogen atoms.
Description
본 발명은 공액디엔 중합체의 수소화 방법에 관한 것으로서, 개질제 등으로 사용되는 공중합체의 내구성과 내산화성 등을 향상시키기 위하여 공액디엔 단위의 불포화이중결합에 선택적으로 수소를 첨가하는 데 있어서 고활성을 갖는 새로운 균일상 유기티타늄촉매를 용액 중에서 만들어진 고활성의 리튬하이드라이드(LiH)와 혼합 사용하여 매우 높은 수율의 수소 첨가율과 수소화 재현성을 나타낼 수 있는 공액디엔 중합체의 이중결합에 수소를 첨가하는 방법에 관한 것이다.The present invention relates to a hydrogenation method of a conjugated diene polymer, and has high activity in selectively adding hydrogen to an unsaturated double bond of a conjugated diene unit in order to improve durability and oxidation resistance of a copolymer used as a modifier or the like. A method for adding hydrogen to a double bond of a conjugated diene polymer that can be used in combination with a highly active lithium hydride (LiH) made in solution in a novel homogeneous organic titanium catalyst can exhibit very high hydrogenation and hydrogenation reproducibility. will be.
1,3-부타디엔이나 이소프렌과 같은 공액디엔(conjugated diene)의 중합체 또는 공액디엔류 및 이들과 공중합가능한 스티렌과 같은 비닐방향족 모노머와의 공중합체 등은 엘라스토머(elastomer)로 널리 사용되고 있다.Polymers of conjugated dienes such as 1,3-butadiene and isoprene or conjugated dienes and copolymers of vinylaromatic monomers such as styrene copolymerizable with these are widely used as elastomers.
이러한 중합체들은 중합체 내부 사슬에 이중결합들을 가지고 있어 가황( vulcanization)이 가능하나 내구성과 내산화성이 떨어진다.These polymers have double bonds in the polymer's inner chain, which allows vulcanization but lacks durability and oxidation resistance.
한편, 공액디엔과 비닐방향족 모노머와의 블록 공중합체들은 가황하지 않고 열가소성 엘라스토머로서 내충격성 투명수지 또는 폴리올레핀 및 폴리스티렌 수지의 개질제로 사용된다.On the other hand, block copolymers of conjugated dienes and vinylaromatic monomers are not vulcanized and are used as impact modifiers of impact resistant transparent resins or polyolefins and polystyrene resins as thermoplastic elastomers.
그러나, 올레핀성 불포화 이중결합을 함유하는 중합체는 불포화 이중결합이 가류과정을 거쳐 유리하게 이용되는 반면 이러한 이중결합이 내열성, 내산성 및 내후성 등의 안정성에 문제를 일으킨다.However, polymers containing olefinic unsaturated double bonds are advantageously used through the vulcanization process while unsaturated double bonds cause problems in stability such as heat resistance, acid resistance and weather resistance.
따라서 이러한 중합체는 외부에 노출되지 않는 제한된 범위에서 적용할 수밖에 없었다.Therefore, such a polymer was forced to apply in a limited range that is not exposed to the outside.
일반적으로 불포화 이중결합을 갖는 중합체의 내구성과 내산화성을 개선하기 위해서는 중합체 내의 이중결합들에 수소를 첨가하여 부분 또는 완전 포화시키는 방법을 사용할 수 있다.In general, in order to improve durability and oxidation resistance of a polymer having an unsaturated double bond, a method of partially or completely saturating by adding hydrogen to the double bonds in the polymer may be used.
올레핀성 이중결합을 가진 중합체를 수소화시키는 방법에 대해서는 여러 방법들이 보고되어 있는 바, 크게 두 가지로 나뉜다.As a method of hydrogenating a polymer having an olefinic double bond has been reported, there are two main methods.
첫 번째 방법은 불균일계 촉매를 사용한 방법이고, 두 번째 방법은 지글러성 촉매 또는 로듐이나 티타늄과 같은 유기금속화합물의 균일계 촉매를 사용하는 방법이다.The first method uses a heterogeneous catalyst, and the second method uses a Ziegler catalyst or a homogeneous catalyst of an organometallic compound such as rhodium or titanium.
이 중 불균일계 촉매를 사용한 수소화 반응은 올레핀성 중합체를 적절한 용매에 녹인 다음 불균일 촉매의 존재 하에 수소를 접촉시키는 방법으로, 중합체의 입체장애와 상대적으로 높은 점도 등의 영향으로 반응물과 촉매간의 접촉이 쉽지 않다. 또한 중합체가 촉매표면에 강하게 흡착하여 한번 수소가 첨가되면 떨어지지 않아 수소화되지 않은 다른 중합체가 활성점에 접근하기가 매우 어렵다. 이러한 경우 이중결합들에 완전히 수소를 첨가시키기 위해서는 많은 양의 촉매와 고온, 고압의 가혹한 반응조건이 요구되는데, 그 결과 종종 중합체의 분해와 겔화를 일으킨다.Among these, the hydrogenation reaction using heterogeneous catalyst is a method of dissolving an olefinic polymer in a suitable solvent and then contacting hydrogen in the presence of a heterogeneous catalyst. The reaction between the reactant and the catalyst is prevented due to the steric hindrance of the polymer and the relatively high viscosity. Uneasy. In addition, the polymer is strongly adsorbed on the catalyst surface, and once hydrogen is added, it does not fall off, which makes it very difficult for other non-hydrogenated polymers to approach the active site. In this case, the complete addition of hydrogen to the double bonds requires a large amount of catalyst and harsh reaction conditions at high temperatures and pressures, often resulting in polymer degradation and gelation.
특히, 이러한 가혹한 반응조건은 공액디엔과 비닐방향족 모노머와의 공중합체의 경우에 있어서는 방향족의 이중결합의 포화가 동시에 진행되어 올레핀성 중합체를 선택적으로 수소화시키기 매우 어렵다.In particular, in such a severe reaction condition, in the case of a copolymer of a conjugated diene and a vinyl aromatic monomer, the saturation of an aromatic double bond proceeds simultaneously and it is very difficult to selectively hydrogenate an olefinic polymer.
뿐만 아니라 수소화된 중합체 용액으로부터 촉매를 물리적으로 분리하기가 극히 어렵고, 어떤 불균일계 촉매는 중합체와 강하게 흡착하기 때문에 이를 완전히 제거하기가 불가능하다.In addition, it is extremely difficult to physically separate the catalyst from the hydrogenated polymer solution, and some heterogeneous catalysts are strongly adsorbed with the polymer, making it impossible to remove them completely.
반면에 균일계 촉매를 사용하는 수소화 반응은 불균일계 촉매를 사용한 경우에 비하여 활성이 높고, 적은 양으로도 저온 저압의 온화한 조건에서 고수율을 기대할 수 있다.On the other hand, the hydrogenation reaction using a homogeneous catalyst is higher in activity than in the case of using a heterogeneous catalyst, and high yield can be expected under mild conditions at low temperature and low pressure even with a small amount.
뿐만 아니라 적절한 수소화 조건에서 비닐방향족 탄화수소와 공액디엔의 공중합체 사슬 중에서 방향족 탄화수소부분을 제외한 이중결합에만 선택적으로 수소를 첨가할 수 있다.In addition, hydrogen may be selectively added only to the double bond excluding the aromatic hydrocarbon moiety in the copolymer chain of the vinylaromatic hydrocarbon and the conjugated diene under appropriate hydrogenation conditions.
그럼에도 불구하고 균일계 촉매를 사용하여 공액디엔 중합체의 이중결합을 수소화하는 방법은 촉매자체의 안정성이 낮고, 수소화된 중합체로부터 분해된 촉매를 분리해내는 것이 매우 어려운 단점이 있다.Nevertheless, the method of hydrogenating a double bond of a conjugated diene polymer using a homogeneous catalyst has a disadvantage of low stability of the catalyst itself and very difficult to separate the decomposed catalyst from the hydrogenated polymer.
한편, 공액디엔 중합체의 불포화 이중결합을 수소화 또는 선택적 수소화하는 몇 가지 방법이 있는 바, 예를 들면 미합중국 특허 제3,494,942호; 제3,670,054호; 및 제3,700,633호 등에는 에틸렌성 불포화 이중결합을 함유하는 중합체 및 방향족과 에틸렌성 불포화 이중결합을 갖는 중합체를 수소화 또는 선택적으로 수소화하기 위해 선행기술에 공지된 적합한 촉매, 특히 8, 9, 10족 금속을 함유하는 촉매 또는 촉매선구 물질을 사용하는 방법에 대해 기술되어 있다.On the other hand, there are several methods for hydrogenating or selectively hydrogenating unsaturated double bonds of conjugated diene polymers, for example US Pat. No. 3,494,942; 3,670,054; And 3,700,633 and the like are suitable catalysts known in the prior art, in particular Group 8, 9, 10 metals for the hydrogenation or optionally hydrogenation of polymers containing ethylenically unsaturated double bonds and polymers having aromatic and ethylenically unsaturated double bonds. A method of using catalysts or catalyst precursors containing is described.
상기 특허에 기술된 방법에서, 촉매는 9, 10족 금속, 특히 니켈 또는 코발트 화합물을 알루미늄 알킬과 같은 적합한 환원제와 조합하여 제조된 것이다. 또한 알루미늄 알킬이 바람직한 환원제이나, 이외에도 원소 주기율표의 1족, 2족 및 13족 금속, 특히 리튬, 마그네슘 및 알루미늄 알킬 또는 수소화물이 효과적인 환원제라고 선행기술에 공지되어 있다. 이때, 1족, 2족 및 13족 금속과 8, 9 및 10족 금속은 0.1:1∼20:1 몰비, 바람직하게는 1:1∼10:1 몰비의 범위에서 조합된다.In the process described in this patent, the catalyst is prepared by combining a Group 9, 10 metal, in particular a nickel or cobalt compound with a suitable reducing agent such as aluminum alkyl. It is also known in the prior art that aluminum alkyl is the preferred reducing agent, but in addition the Group 1, 2 and 13 metals of the periodic table of the elements, in particular lithium, magnesium and aluminum alkyl or hydrides, are effective reducing agents. At this time, the Group 1, Group 2 and Group 13 metals and Group 8, 9 and 10 metals are combined in a range of 0.1: 1 to 20: 1 molar ratio, preferably 1: 1 to 10: 1 molar ratio.
미합중국 특허 제4,501,857호에는 적어도 하나의 비스(사이클로펜타디에닐)티타늄 화합물 및 적어도 하나의 탄화수소 리튬화합물의 존재 하에 공액디엔 중합체를 수소화함으로써 상기 중합체내 이중결합을 선택적으로 수소화할 수 있음을 밝혔다.U.S. Patent 4,501,857 discloses that the double bonds in the polymer can be selectively hydrogenated by hydrogenating the conjugated diene polymer in the presence of at least one bis (cyclopentadienyl) titanium compound and at least one hydrocarbon lithium compound.
그리고, 미합중국 특허 제4,980,421호에는 직접 첨가되거나 유기리튬화합물과 알콜성 또는 페놀성 화합물과 반응혼합물로서 첨가될 수 있는 알콕시 리튬화합물과 비스(사이클로펜타디에닐)티타늄 화합물을 조합하여 사용하므로써 유사 수소화 활성을 갖게 할 수 있음을 밝혔다. 여기서는 촉매가 수소화 중합체의 안정성에 역으로 영향을 주지 않을 만큼 소량 사용하더라도 효과적일 만큼 활성이고, 탈회단계를 요하지 않는 것으로 언급되었다.In addition, U.S. Patent No. 4,980,421 describes similar hydrogenation activity by using a combination of an alkoxy lithium compound and a bis (cyclopentadienyl) titanium compound which can be added directly or as an organic lithium compound and an alcoholic or phenolic compound as a reaction mixture. Revealed that you can have. It has been mentioned here that the catalyst is active enough to be effective and does not require a deliming step even if the catalyst is used in small amounts so as not to adversely affect the stability of the hydrogenated polymer.
미합중국 특허 제4,673,714호에서는 비스(사이클로펜타디에닐)티타늄화합물이 바람직하게 공액디엔의 이중결합을 수소화하며, 이때 알킬리튬의 사용을 요하지 않음을 밝혔다. 이러한 티타늄화합물의 구체적인 예는 비스(사이클로펜타디에닐)티타늄 디아릴 화합물이며, 탄화수소 리튬화합물을 사용하지 않는 것을 이 촉매 시스템의 장점으로 언급하였다.U.S. Patent 4,673,714 discloses that bis (cyclopentadienyl) titanium compounds preferably hydrogenate double bonds of conjugated dienes, which do not require the use of alkyllithium. A specific example of such a titanium compound is a bis (cyclopentadienyl) titanium diaryl compound, which mentions the use of a hydrocarbon lithium compound as an advantage of this catalyst system.
또한, 미합중국 특허 제5,039,755호에는 적합한 용매에서 공액디엔 단량체를 유기알칼리 금속 중합개시제로 중합 또는 공중합하여 리빙 중합체를 생성시키는 것을 포함하는 공액디엔 중합체의 수소화 방법에 대해 제시되어 있다. 이때, 생성된 리빙중합체(living polymer)는 수소의 첨가로 중합이 종결된다. 종결된 중합체의 공액디엔 단위에서 이중결합의 선택적 수소화는 (C5H5)2TiR2(R=아릴알킬기) 촉매 존재 하에에서 수행되었다.U.S. Patent 5,039,755 also discloses a process for hydrogenating conjugated diene polymers comprising polymerizing or copolymerizing conjugated diene monomers with organic alkali metal polymerization initiators in a suitable solvent to produce living polymers. At this time, the resulting living polymer (living polymer) is terminated by the addition of hydrogen. Selective hydrogenation of the double bond in the conjugated diene unit of the terminated polymer was carried out in the presence of a (C 5 H 5 ) 2 TiR 2 (R = arylalkyl group) catalyst.
미합중국 특허 제5,243,986호에서는 스티렌-부타디엔-이소프렌의 공중합체를 특정의 티타노센 화합물과 환원제의 사용에 의해서 공액디엔의 이중결합만을 선택적으로 수소화함을 밝혔다.US Pat. No. 5,243,986 discloses that the copolymer of styrene-butadiene-isoprene selectively hydrogenates only double bonds of conjugated dienes by the use of certain titanocene compounds and reducing agents.
그리고, 미합중국 특허 제5,583,185호에는 균일계 촉매로서 Cp2Ti(PhOR)2(단, 여기서 Cp는 사이클로펜타디에닐이며, OR은 탄소원자수 1∼4인 알콕시화합물이다.) 또는 Cp2TiR2(단, 여기서 R은 CH2PPh2이다)를 사용하여 공액디엔의 이중결합을 수소화하는 방법에 대해 기술되어 있다.And, U.S. Patent No. 5,583,185 discloses a homogeneous catalyst Cp 2 Ti (PhOR) 2 (However, where Cp is cyclopentadienyl and cyclopentadienyl, OR is an alkoxy compound of 1 to 4 carbon atoms) or Cp 2 TiR 2 ( Provided that R is CH 2 PPh 2 ) for the hydrogenation of double bonds of conjugated dienes.
또한 문헌 Journal of Organometallic Chemistry, 382 (1990) 69-76에서는 촉매로서 Cp2TiCl2또는 (C6H10(p-CH3OC6H4)C5H4)2TiCl2를 용액 중에서 만든 고활성의알칼리금속하이드라이드(MH)와 혼합하여 사용하여 올레핀성 모노머의 수소화 방법에 대해 기술했다.See also the Journal of Organometallic Chemistry, 382 (1990) 69-76, where Cp 2 TiCl 2 or (C 6 H 10 (p-CH 3 OC 6 H 4 ) C 5 H 4 ) 2 TiCl 2 was prepared as a catalyst. A method for hydrogenation of olefinic monomers has been described using a mixture of active alkali metal hydrides (MH).
그러나, 상기와 같은 균일계 촉매는 일반적으로 외부의 환경에 매우 민감하여 공기중 또는 수분이 있는 경우 쉽게 촉매가 변질되며, 수소화 활성이 촉매의 환원상태에 따라 크게 변화하는 문제가 있다. 결국 수소화 반응의 재현성이 떨어지는 양상을 보이므로 고수소화율과 높은 재현성을 동시에 만족하는 수소화된 중합체를 얻는데 어려움이 있다.However, such a homogeneous catalyst is generally very sensitive to the external environment, so that the catalyst easily deteriorates when there is air or moisture in the air, and there is a problem in that the hydrogenation activity is greatly changed depending on the reduction state of the catalyst. As a result, since the reproducibility of the hydrogenation reaction is poor, it is difficult to obtain a hydrogenated polymer that satisfies both high hydrogenation rate and high reproducibility at the same time.
또한 촉매 활성성분이 반응이 진행됨에 따라서 비활성의 물질로 변하는 경향이 있고, 결국 이로 인해 수소화 활성이 저하되어 반응 재현성을 떨어뜨리는 원인으로 작용한다. 이러한 경향성은 중합체의 내구성과 내산화성를 향상시키기 위한 중합체 수소화 반응에 심각한 장애를 일으킨다. 뿐만 아니라 균일계 촉매에서는 수소화 반응 중의 촉매의 안전성에 따라 수소 첨가율이 많은 영향을 받는다.In addition, the catalytically active component tends to change into an inert material as the reaction proceeds, which in turn causes a decrease in hydrogenation activity, thereby reducing the reproducibility of the reaction. This tendency causes serious obstacles to the polymer hydrogenation reaction to improve the durability and oxidation resistance of the polymer. In addition, in the homogeneous catalyst, the hydrogenation rate is greatly influenced by the safety of the catalyst during the hydrogenation reaction.
따라서 균일계 촉매에 의한 중합체의 수소화 반응공정을 공업적으로 적용하는 데에는 상기한 문제점들이 있는 바, 이러한 문제점들이 개선된 안정하고 재현성이 있는 고활성의 수소화 촉매의 개발이 강력히 요구되고 있다.Therefore, the above-mentioned problems are required to industrially apply a hydrogenation reaction process of a polymer by a homogeneous catalyst. Therefore, there is a strong demand for the development of a stable and reproducible high activity hydrogenation catalyst having improved these problems.
본 발명의 목적은 상기와 같은 균일계 촉매를 사용한 공액디엔 중합체의 불포화 이중결합을 수소화시키는 데 있어서의 문제점을 해결하기 위한 것으로서, 일반적인 균일계 수소화 촉매가 가진 문제점들을 나타내지 않으면서도 고수소화율과 높은 재현성으로 수소화된 중합체를 생산할 수 있는 새로운 촉매를 사용한 수소화방법을 제공하는 데 있다.An object of the present invention is to solve the problem of hydrogenating unsaturated double bonds of conjugated diene polymers using the homogeneous catalyst as described above, high hydrogenation rate and high reproducibility without showing the problems with the general homogeneous hydrogenation catalyst It is to provide a hydrogenation method using a new catalyst that can produce a hydrogenated polymer.
상기와 같은 목적을 달성하기 위해 공액디엔 모노머의 단독 중합체 또는 공액디엔 모노머와 방향족 비닐모노머와의 공중합체 중에서 선택된 중합체를 공액디엔만을 선택적으로 수소화하는 공정으로서, 1)적어도 하나의 공액디엔을 유기 알칼리금속을 개시제로 하여 단독중합 또는 공중합하여 리빙중합체(living polymer)를 만들고, 2) 형성된 리빙중합체를 동일 당량의 말단 변성물질을 사용하여 처리한 다음, 3) 말단 처리된 고분자에 유기 알칼리금속과 수소를 반응시켜 만든 알칼리금속 하이드라이드(MH)와 다음 화학식 1로 표시되는 모노사이클로펜타디에닐(피롤릴) 티타늄화합물을 수소와 함께 가하여 선택적으로 공액디엔을 수소화시키는 데 그 특징이 있다.In order to achieve the above object, a process of selectively hydrogenating a conjugated diene of a polymer selected from a homopolymer of a conjugated diene monomer or a copolymer of a conjugated diene monomer and an aromatic vinyl monomer, comprising: 1) at least one conjugated diene Using a metal as an initiator, homopolymerization or copolymerization to form a living polymer, 2) treating the formed living polymer with the same equivalent of a denaturing material, and 3) terminating the polymer to an organic alkali metal and hydrogen. An alkali metal hydride (MH) prepared by reacting with a monocyclopentadienyl (pyrrolyl) titanium compound represented by the following Chemical Formula 1 is added with hydrogen to selectively hydrogenate the conjugated diene.
화학식 1Formula 1
상기 식에서, Cp는 사이클로펜타디에닐기(C5H5)이고, R1, R2, R3및 R4는 서로 같거나 다른 것으로서, 수소원자, 탄소원자수 1∼12의 알킬기 또는 알콕시기, 탄소원자수 6∼20의 아릴기, 아릴록시기 또는 사이클로알킬기이고, R5와 R6는 서로 같거나 다른 것으로서, 할로겐 원자로부터 선택된 것이다.In the above formula, Cp is a cyclopentadienyl group (C 5 H 5 ), R 1 , R 2 , R 3 and R 4 are the same as or different from each other, a hydrogen atom, an alkyl group having 1 to 12 carbon atoms or an alkoxy group, a carbon source It is an aryl group, an aryloxy group, or a cycloalkyl group of 6-6 embroidery, and R <5> and R <6> are the same or different from each other, and they are selected from a halogen atom.
이와같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명의 수소화 반응에서 사용되는 촉매는 모노사이클로펜타디에닐티타늄 화합물과 용액 중에서 유기알칼리금속과 수소와의 반응에 의해 만들어진 알칼리금속하이드라이드(MH)의 혼합에 의해 만들어진다.The catalyst used in the hydrogenation reaction of the present invention is made by mixing a monocyclopentadienyl titanium compound and an alkali metal hydride (MH) produced by the reaction of an organic alkali metal and hydrogen in a solution.
상기 화학식 1로 표시되는 촉매의 구체적인 모노사이클로펜타디에닐(피롤릴)티타늄화합물의 예들은, 모노사이클로펜타디에닐(피롤릴)티타늄디플루오라이드, 모노사이클로펜타디에닐(피롤릴)티타늄디클로라이드, 모노사이클로펜타디에닐(피롤릴)티타늄디아이오다이드, 모노사이클로펜타디에닐(피롤릴)티타늄디브로마이드, 모노사이클로펜타디에닐(2,4-디메틸피롤릴)티타늄디플루오라이드, 모노사이클로펜타디에닐(2,4-디메틸피롤릴)티타늄디클로라이드, 모노사이클로펜타디에닐(2,4-디메틸피롤릴)티타늄디아이오다이드, 모노사이클로펜타디에닐(2,4-디메틸피롤릴)티타늄디브로마이드, 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디플루오라이드, 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디클로라이드, 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디아이오다이드 및 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디브로마이드 중에서 선택된 것이며, 단독 또는 혼합으로 사용될 수 있다.Examples of specific monocyclopentadienyl (pyrrolyl) titanium compounds of the catalyst represented by the formula (1) include monocyclopentadienyl (pyrrolyl) titanium difluoride and monocyclopentadienyl (pyrrolyl) titanium dichloride , Monocyclopentadienyl (pyrrolyl) titanium dioxide, monocyclopentadienyl (pyrrolyl) titanium dibromide, monocyclopentadienyl (2,4-dimethylpyrrolyl) titanium difluoride, monocyclopenta Dienyl (2,4-dimethylpyrrolyl) titanium dichloride, monocyclopentadienyl (2,4-dimethylpyrrolyl) titanium diiodide, monocyclopentadienyl (2,4-dimethylpyrrolyl) titaniumdi Bromide, monocyclopentadienyl (2,5-dimethylpyrrolyl) titanium difluoride, monocyclopentadienyl (2,5-dimethylpyrrolyl) titaniumdichloride, monocyclopentadienyl (2,5-di Tilpi pyrrolyl) titanium DI iodide and mono- cyclopentadienyl (2,5-dimethyl-pyrrolyl) titanium di-will selected from the group consisting of bromide, it can be used alone or in combination.
이와 같은 수소화 촉매의 사용량은 중합체 100g 당 0.01∼20mmol이 적당하며, 더욱 바람직하게는 중합체 100g 당 0.05∼2mmol이 적절하다.The amount of the hydrogenation catalyst used is suitably 0.01 to 20 mmol per 100 g of polymer, more preferably 0.05 to 2 mmol per 100 g of polymer.
상기의 수소화 촉매로부터 분자량 500∼1,000,000인 공액디엔 중합체 또는 공액디엔과 공중합가능한 비닐치환 방향족 모노머와의 공중합체로서 랜덤, 테이퍼드 또는 블록 공중합체의 공액디엔단위의 불포화이중결합에의 수소 첨가가 가능하다.From the hydrogenation catalyst, a copolymer of a conjugated diene polymer having a molecular weight of 500 to 1,000,000 or a conjugated diene and a vinyl-substituted aromatic monomer copolymerizable with the conjugated diene enables hydrogenation to a unsaturated double bond of a conjugated diene unit of a random, tapered or block copolymer. Do.
잘 알려진 바와 같이 에틸렌 불포화 이중결합 및 임의의 방향족 불포화 이중결합을 함유하는 중합체는 하나 이상의 폴리올레핀, 특히 디올레핀을 단독 중합하거나 하나 이상의 알케닐 방향족 탄화수소 단량체와 공중합하여 제조될 수 있다.As is well known, polymers containing ethylenically unsaturated double bonds and any aromatic unsaturated double bonds can be prepared by homopolymerizing one or more polyolefins, in particular diolefins, or copolymerizing with one or more alkenyl aromatic hydrocarbon monomers.
공중합체는 선형, 성상 또는 방사상 뿐만 아니라 랜덤, 테이퍼드, 블록 또는 이들의 조합일 수 있다.The copolymer can be linear, constellation or radial as well as random, tapered, block or combinations thereof.
에틸렌 불포화 이중결합 또는 방향족 및 에틸렌 불포화 이중결합 둘 다를 함유하는 공중합체는 유기리튬 화합물과 같은 음이온성 개시제 또는 지글러 나타 중합촉매를 사용하여 제조될 수 있다. 상기 중합체 제조시 그 방법은 통상의 방법, 즉 벌크, 용액 또는 유탁액 기술을 사용할 수 있다.Copolymers containing ethylenically unsaturated double bonds or both aromatic and ethylenically unsaturated double bonds can be prepared using anionic initiators such as organolithium compounds or Ziegler Natta polymerization catalysts. In the preparation of the polymers, the process may employ conventional methods, ie bulk, solution or emulsion techniques.
여기서, 음이온형으로 중합될 수 있는 공액디엔은 1,3-부타디엔, 이소프렌, 피페릴렌, 페닐부타디엔, 3,4-디메틸-1,3-헥사디엔, 4,5-디에틸-1,3-옥타디엔 등과 같은 4∼12개의 탄소원자를 함유한 공액디엔계 화합물을 사용할 수 있고, 바람직하기로는 탄소원자수 4∼9인 공역 디올레핀을 사용하는 것이다.Here, the conjugated diene which can be polymerized in the anionic form is 1,3-butadiene, isoprene, piperylene, phenylbutadiene, 3,4-dimethyl-1,3-hexadiene, 4,5-diethyl-1,3- A conjugated diene compound containing 4 to 12 carbon atoms such as octadiene can be used, and preferably a conjugated diolefin having 4 to 9 carbon atoms is used.
그리고, 상기 공액디엔계 화합물과 공중합 가능한 알케닐 방향족 탄화수소는 스티렌, 각종 알킬기로 치환된 스티렌, 알콕시기로 치환된 스티렌, 2-비닐 피리딘, 4-비닐 피리딘, 비닐 나프탈렌, 알킬기로 치환된 비닐 나프탈렌 등과 같은 비닐 아릴 화합물을 포함한다.The alkenyl aromatic hydrocarbon copolymerizable with the conjugated diene-based compound may include styrene, styrene substituted with various alkyl groups, styrene substituted with alkoxy groups, 2-vinyl pyridine, 4-vinyl pyridine, vinyl naphthalene, vinyl naphthalene substituted with alkyl groups, and the like. Such vinyl aryl compounds.
상기와 같은 공액디엔 화합물이나 공액디엔 화합물과 공중합 가능한 비닐 방향족 화합물 중 적어도 하나 이상의 화합물을 유기 알칼리금속을 개시제로 하여 단독중합 또는 공중합하여 리빙중합체(living polymer)를 만든다.A living polymer is formed by homopolymerizing or copolymerizing at least one or more compounds of the above-described conjugated diene compound or a vinyl aromatic compound copolymerizable with the conjugated diene compound using an organic alkali metal as an initiator.
이때, 방향족 비닐계 모노머와 공액디엔 모노머를 혼용할 경우 그 중량비는 1:9∼9:1인 것이 바람직하다.In this case, when the aromatic vinyl monomer and the conjugated diene monomer are mixed, the weight ratio thereof is preferably 1: 9 to 9: 1.
그리고, 개시제로 첨가되는 유기 알칼리금속으로는 유기 리튬화합물, 구체적으로는 n-부틸리튬이나 sec-부틸리튬 등을 사용할 수 있다.As the organic alkali metal added as the initiator, an organolithium compound, specifically n-butyllithium, sec-butyllithium or the like can be used.
그 다음, 형성된 리빙중합체를 동일 당량의 말단 변성물질을 사용하여 말단을 비활성시키는 바, 이때 말단 변성물질로는 아민류, 알콜류, 에스테르류, 케톤류, 할로겐류 화합물 중에서 선택하여 사용할 수 있다. 보다 구체적으로는 벤질클로라이드, 벤질브로마이드, 벤질아이오다이드, 메틸클로라이드, 메틸브로마이드, 메틸아이오다이드, 에틸클로라이드, 에틸브로마이드, 에틸아이오다이드, 부틸클로라이드, 부틸브로마이드, 부틸아이오다이드, 아세톤, 메틸이소부틸케톤, 디페닐케톤, 메탄올, 에탄올, 이소프로필알콜, 부탄올, 페놀, 크레졸, 2,6-디-t-부틸 4-메틸 페놀, 에틸아세테이트, 부틸아세테이트, 트리메틸실릴플로라이드, 트리메틸실릴클로라이드, 트리메틸실릴브로마이드, 트리메틸실릴아이오다이드, 트리에틸실릴플로라이드, 트리에틸실릴클로라이드, 트리에틸실릴브로마이드, 트리에틸실릴아이오다이드, 트리부틸실릴플로라이드, 트리부틸실릴클로라이드, 트리부틸실릴브로마이드, 트리부틸실릴아이오다이드, 트리페닐실릴플로라이드, 트리페닐실릴클로라이드, 트리페닐실릴브로마이드, 트리페닐실릴아이오다이드에서 선택된 것이다.Thereafter, the formed living polymer is inactivated at the terminal using the same amount of the terminal modified material. In this case, the terminal modified material may be selected from amines, alcohols, esters, ketones, and halogen compounds. More specifically, benzyl chloride, benzyl bromide, benzyl iodide, methyl chloride, methyl bromide, methyl iodide, ethyl chloride, ethyl bromide, ethyl iodide, butyl chloride, butyl bromide, butyl iodide, acetone, Methyl isobutyl ketone, diphenyl ketone, methanol, ethanol, isopropyl alcohol, butanol, phenol, cresol, 2,6-di- t -butyl 4-methyl phenol, ethyl acetate, butyl acetate, trimethylsilyl fluoride, trimethylsilyl Chloride, trimethylsilyl bromide, trimethylsilyl iodide, triethylsilyl fluoride, triethylsilyl chloride, triethylsilyl bromide, triethylsilyl iodide, tributylsilyl fluoride, tributylsilyl chloride, tributylsilyl bromide , Tributylsilyl iodide, triphenylsilyl fluoride, tripe Silyl chloride, is selected from triphenylsilyl bromide, triphenylsilyl iodide.
말단 처리된 고분자에 용액 중에서 유기 리튬화합물과 수소를 접촉시켜 만든 리튬 하이드라이드와 상기 화학식 1로 표시되는 모노사이클로펜타디에닐(피롤릴) 티타늄 화합물을 수소와 함께 가하여 수소화 공정을 수행한다.A hydrogenation process is performed by adding a lithium hydride made by contacting an organic lithium compound with hydrogen in a solution and a monocyclopentadienyl (pyrrolyl) titanium compound represented by Formula 1 together with hydrogen.
이 때, 리튬 하이드라이드의 첨가량은 화학식 1로 표시되는 모노사이클로펜타디에닐(피롤릴) 티타늄 화합물에 대하여 2∼30 몰비로 사용하는 것이 바람직하며, 리튬 하이드라이드는 유기 리튬화합물과 기체상태인 수소와의 용액중 반응을 통해 제조된 것이다.At this time, the amount of lithium hydride added is preferably used in a molar ratio of 2 to 30 with respect to the monocyclopentadienyl (pyrrolyl) titanium compound represented by Formula 1, and lithium hydride is an organic lithium compound and a gaseous hydrogen It was prepared through the reaction in solution with.
본 발명의 수소화 반응은 불활성 용매 중에서 공액디엔을 중합하여 얻어진 중합체를 사용하여 수행된다.The hydrogenation reaction of the present invention is carried out using a polymer obtained by polymerizing conjugated diene in an inert solvent.
여기서, 불활성 용매란 중합이나 수소화 반응의 어떠한 반응물과도 반응하지 않는 용매를 의미하며, 적합한 용매로는 n-펜탄, n-헥산, n-헵탄, n-옥탄 등의 지방족 탄화수소류; 사이클로헥산, 사이클로헵탄과 같은 지방족 고리 탄화수소류; 및 디에틸에테르, 테트라히드로퓨란과 같은 에테르류를 들 수 있으며, 이들 중에서 선택하여 단독 또는 혼합 사용할 수 있다.Here, an inert solvent means a solvent which does not react with any reactants of polymerization or hydrogenation reaction, and suitable solvents include aliphatic hydrocarbons such as n-pentane, n-hexane, n-heptane and n-octane; Aliphatic ring hydrocarbons such as cyclohexane and cycloheptane; And ethers, such as diethyl ether and tetrahydrofuran, These can be selected and can be used individually or in mixture.
또한 벤젠, 톨루엔, 자일렌, 에틸벤젠과 같은 방향족 탄화수소도 선택된 수소화 반응조건 하에서 방향족성 이중결합에 수소가 첨가되지 않는 범위 내에서 사용 가능하다.In addition, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene can also be used within the range where hydrogen is not added to the aromatic double bond under selected hydrogenation reaction conditions.
본 발명의 수소화 반응은 용매에 대해 중합체의 농도가 1∼50중량%, 바람직하게는 5∼25중량%에서 수행된다.The hydrogenation reaction of the present invention is carried out at a concentration of 1 to 50% by weight, preferably 5 to 25% by weight of the polymer relative to the solvent.
한편, 본 발명의 수소화 반응은 중합체 용액을 수소나 불활성 기체 분위기 하에서 일정온도로 유지한 후, 교반 또는 미교반상태에서 수소화 촉매를 첨가하고, 그 다음 수소 가스를 일정 압력으로 주입함으로써 수행된다.On the other hand, the hydrogenation reaction of the present invention is carried out by maintaining the polymer solution at a constant temperature under hydrogen or an inert gas atmosphere, then adding a hydrogenation catalyst in a stirred or unstirred state, and then injecting hydrogen gas at a constant pressure.
불활성 기체는 헬륨, 질소 및 아르곤 등으로서, 수소화 반응의 어떠한 반응물과도 반응하지 않는 가스분위기를 의미하며, 공기나 산소는 수소화 촉매를 산화 또는 분해시켜 촉매의 활성저하를 초래하므로 바람직하지 않다.The inert gas is helium, nitrogen, argon and the like, which means a gas atmosphere that does not react with any reactants of the hydrogenation reaction, and air or oxygen is not preferable because it causes oxidation or decomposition of the hydrogenation catalyst to cause deactivation of the catalyst.
수소화 반응은 일반적으로 0∼150℃의 온도범위에서 수행된다. 만일, 그 온도가 0℃ 보다 낮으면 촉매의 활성이 저하되고 동시에 수소 첨가속도도 떨어져 다량의 촉매를 필요로 하게 되므로 경제적이지 못할 뿐만 아니라 수소화된 중합체의 불용화로 중합체가 석출되기 쉽다. 반면, 그 반응온도가 150℃ 보다 높으면 촉매의 활성을 저하시키고 중합체의 겔화나 분해를 유발시키기 쉽고 또한 방향족성 이중결합에 수소화가 일어나기 쉽게 되어 수소 첨가의 선택성이 저하되는 경향이 있다. 더 바람직하게는 반응온도가 50∼140℃의 범위가 적당하다.The hydrogenation reaction is generally carried out in the temperature range of 0 to 150 ℃. If the temperature is lower than 0 ° C., the activity of the catalyst is lowered and at the same time, the addition rate of hydrogen is also lowered, so that a large amount of catalyst is required, which is not economical and the polymer is easily precipitated due to insolubilization of the hydrogenated polymer. On the other hand, when the reaction temperature is higher than 150 ° C., the activity of the catalyst is lowered, the polymer is easily gelatinized or decomposed, and the hydrogenation occurs easily in the aromatic double bond, and the selectivity of hydrogenation tends to be lowered. More preferably, the reaction temperature is in the range of 50 to 140 ° C.
또한, 수소화 반응에 사용되는 수소의 압력은 특별히 제한된 것은 아니나, 1∼100 kg/㎠가 적합하다. 만일, 수소의 압력이 1kg/㎠ 미만에서는 수소화 속도가 느려지고, 100kg/㎠를 초과한 압력에서는 실질적으로 불필요한 부반응인 겔화가 초래되므로 좋지 않다. 더욱 바람직하게는 수소압력이 2∼30 kg/㎠으로 촉매 첨가량 등 수소화 조건과의 관계에서 최적 수소압력이 선택되는 바, 실질적으로 수소화 촉매량이 적을 때는 수소압력은 고압을 택하는 것이 바람직하다.In addition, although the pressure of hydrogen used for a hydrogenation reaction is not specifically limited, 1-100 kg / cm <2> is suitable. If the pressure of hydrogen is less than 1 kg / cm 2, the rate of hydrogenation is slow, and at pressures exceeding 100 kg / cm 2, gelation, which is a substantially unnecessary side reaction, is caused. More preferably, the hydrogen pressure is 2 to 30 kg / cm 2, and the optimum hydrogen pressure is selected in relation to the hydrogenation conditions such as the addition amount of the catalyst. When the amount of the hydrogenation catalyst is substantially small, the hydrogen pressure is preferably high pressure.
그리고, 본 발명의 수소화 반응시간은 통상 수분 내지 1440분이다. 더 바람직하게는 30분 내지 360분이 적당하다. 다른 수소화 반응조건의 선택에 있어서 수소화 반응시간은 상기 범위 내에서 적절히 선택하여 실시된다. 본 발명의 수소화 반응은 배치식, 연속식 등 어떠한 방법을 사용해도 무방하다.The hydrogenation reaction time of the present invention is usually from minutes to 1440 minutes. More preferably 30 to 360 minutes are suitable. In the selection of other hydrogenation reaction conditions, the hydrogenation reaction time is appropriately selected within the above range and carried out. The hydrogenation reaction of this invention may use any method, such as a batch type and a continuous type.
수소화 반응의 진행은 수소 흡수량을 추적하는 것으로 파악할 수 있다.The progress of the hydrogenation reaction can be seen as tracking the hydrogen uptake.
본 발명에 있어서, 중합체의 공액디엔 단위의 불포화 이중결합이 50%이상 바람직하게는 90%이상 수첨되는 수소화된 중합체를 얻는 것이 가능하다. 더욱 바람직하게는 공액디엔과 비닐치환 방향족 탄화수소와의 공중합체를 수소화하는 경우 공액디엔 단위의 불포화 이중결합의 수첨율이 90%이상인 동시에 방향족성 이중결합의 수첨율이 5%미만으로 공액디엔 단위의 불포화 이중결합을 선택적으로 수소화된 공중합체를 얻는 것이 가능하다.In the present invention, it is possible to obtain a hydrogenated polymer wherein the unsaturated double bond of the conjugated diene unit of the polymer is hydrogenated at least 50%, preferably at least 90%. More preferably, when hydrogenating the copolymer of conjugated diene and vinyl-substituted aromatic hydrocarbon, the hydrogenation rate of the unsaturated double bond of the conjugated diene unit is 90% or more and the hydrogenation rate of the aromatic double bond is less than 5%. It is possible to obtain copolymers hydrogenated with unsaturated double bonds selectively.
이상과 같이 고활성의 새로운 촉매를 사용하여 공액디엔 중합체를 수소화하는 경우 온화한 조건으로 수소화를 수행할 수 있고, 특히 공액디엔과 비닐치환 방향족 탄화수소와의 공중합체에 있어서의 공액디엔단위의 불포화 이중결합을 극히 선택적으로 수소화할 수 있다. 특히 본 발명의 방법에 있어서 공액디엔중합체를 원료로 하므로 동일 반응기에서 연속적으로 수소화가 가능하며, 동시에 소량의 촉매첨가로 극히 높은 활성을 나타낼 수 있으므로 경제적이고 간편한 공정으로 공업상 유리하다.As described above, when the conjugated diene polymer is hydrogenated using a new catalyst having high activity, hydrogenation can be carried out under mild conditions, and in particular, unsaturated double bonds of conjugated diene units in copolymers of conjugated dienes and vinyl-substituted aromatic hydrocarbons. Can be hydrogenated extremely selectively. In particular, since the conjugated diene polymer is used as a raw material in the method of the present invention, it is possible to continuously hydrogenate in the same reactor, and at the same time, it can exhibit extremely high activity by adding a small amount of catalyst, which is industrially advantageous in an economical and simple process.
이하, 본 발명을 실시예에 의거하여 상세하게 설명하면 다음과 같은 바, 본 발명이 이에 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to the following Examples, but the present invention is not limited thereto.
제조예 1: 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디클로라이드Preparation Example 1 Monocyclopentadienyl (2,5-dimethylpyrrolyl) titanium dichloride
200㎖의 슈렝크(schlenk) 반응기에 불활성 기체 분위기 하에서 모노사이클로펜타디에닐티타늄트리클로라이드(0.35g, 1.6mmol)를 톨루엔 15㎖에 용해시킨 후 2,5-디메틸피롤(1.6mmol)과 n-부틸리튬(1.6mmol)을 톨루엔 10㎖에서 20분간 반응시킨 용액을 서서히 가하였다. 실온에서 12 시간 교반한 후 혼합물의 일부를 취하여 NMR 분석기를 이용하여 반응결과를 확인하였다.In a 200 ml Schlenk reactor, monocyclopentadienyltitanium trichloride (0.35 g, 1.6 mmol) was dissolved in 15 ml of toluene under an inert gas atmosphere, followed by 2,5-dimethylpyrrole (1.6 mmol) and n-. A solution of butyllithium (1.6 mmol) in 20 ml of toluene for 20 minutes was slowly added. After stirring for 12 hours at room temperature, a part of the mixture was taken and the reaction result was confirmed by using an NMR analyzer.
1H-NMR(CDCl3, ppm): δ(C5H5):6.627(s,5H), δ(-NC4H2): 5.741(d, 2H), 1 H-NMR (CDCl 3 , ppm): δ (C 5 H 5 ): 6.627 (s, 5H), δ (-NC 4 H 2 ): 5.741 (d, 2H),
δ(-CH3): 2.232(s, 6H)δ (-CH3): 2.232 (s, 6H)
제조예 2: 모노사이클로펜타디에닐(피롤릴)티타늄디클로라이드Preparation Example 2 Monocyclopentadienyl (pyrrolyl) Titanium Dichloride
200㎖의 슈렝크(schlenk) 반응기에 불활성 기체 분위기 하에서 모노사이클로펜타디에닐티타늄트리클로라이드(0.35g, 1.6mmol)를 톨루엔 15㎖에 용해시킨 후 피롤(1.6mmol)과 n-부틸리튬(1.6mmol)을 톨루엔 10㎖에서 20분간 반응시킨 용액을 서서히 가하였다. 실온에서 12 시간 교반한 후 혼합물의 일부를 취하여 NMR 분석기를 이용하여 반응결과를 확인하였다.In a 200 ml Schlenk reactor, monocyclopentadienyltitanium trichloride (0.35 g, 1.6 mmol) was dissolved in 15 ml of toluene in an inert gas atmosphere, followed by pyrrole (1.6 mmol) and n-butyllithium (1.6 mmol). ) Was slowly added to the solution in which 20 ml of toluene was reacted for 20 minutes. After stirring for 12 hours at room temperature, a part of the mixture was taken and the reaction result was confirmed by using an NMR analyzer.
1H-NMR(CDCl3,ppm): δ(C5H5): 6.18(s, 5H), δ(-NC4H4): 5.72(s, 2H), 1 H-NMR (CDCl 3, ppm): δ (C 5 H 5 ): 6.18 (s, 5H), δ (-NC 4 H 4 ): 5.72 (s, 2H),
4.67(s, 2H)4.67 (s, 2 H)
제조예 3: 리튬하이드라이드(LiH)의 합성Preparation Example 3 Synthesis of Lithium Hydride (LiH)
5ℓ의 오토클레이브 반응기 안에 불활성 기체 분위기에서 3.5리터의 n-부틸리튬 용액(0.2M 사이클로헥산 용액)을 넣고 500g의 테트라하이드로퓨란을 가하였다. 반응기 온도를 상온으로 유지하고 교반기를 500rpm으로 회전시키면서 기체상태의 수소를 가하여 10 kg/㎠의 압력을 유지하면서 1시간 동안 방치하였다. 한 시간 후 용액은 하얀 색의 현탁액으로 변하였다. 반응의 종말점은 용액의 일부를 취하여스티렌 모노머와 반응시켜 색깔변화가 없는 것을 육안으로 확인하면 된다. 만일 미반응 알킬 리튬이 용액 중에 남아 있으면 스티렌 모노머의 중합반응을 진행시켜 노란 색을 띄게 된다.In a 5 liter autoclave reactor, 3.5 liters of n-butyllithium solution (0.2 M cyclohexane solution) was added in an inert gas atmosphere and 500 g of tetrahydrofuran was added. The reactor temperature was maintained at room temperature, and while rotating the stirrer at 500 rpm, gaseous hydrogen was added and left for 1 hour while maintaining a pressure of 10 kg / cm 2. After an hour the solution turned to a white suspension. The end point of the reaction is to visually confirm that there is no change in color by taking part of the solution and reacting with the styrene monomer. If unreacted alkyl lithium remains in solution, the polymerization of styrene monomer proceeds to yellow.
제조예 4: 벤질클로라이드로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Preparation Example 4 Synthesis of Styrene-Butadiene-Styrene Block Copolymer Treated with Benzyl Chloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간 동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 2.0g의 벤질클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합 스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were polymerized, and then polymerized for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and then 2.0 g of benzyl chloride was added to inactivate the terminal of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block containing 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond (26.6% of all polymers) in a butadiene unit, and a number average molecular weight of about 50,000. Copolymer.
제조예 5:Preparation Example 5: tt -부틸클로라이드로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Synthesis of Styrene-Butadiene-Styrene Block Copolymers Treated with -Butylchloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 1.5g의t-부틸클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는결합 스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were added, followed by polymerization for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and 1.5 g of t -butyl chloride was added to inactivate the terminal of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block containing 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond (26.6% of a total polymer) of butadiene units, and a number average molecular weight of approximately 50,000. Copolymer.
제조예 6: 이소프로필알콜로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Preparation Example 6 Synthesis of Styrene-Butadiene-Styrene Block Copolymer Treated with Isopropyl Alcohol
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간 동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 1.0g의 이소프로필알콜을 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합 스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were polymerized, and then polymerized for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and then 1.0 g of isopropyl alcohol was added to inactivate the terminal of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block containing 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond (26.6% of all polymers) in a butadiene unit, and a number average molecular weight of about 50,000. Copolymer.
제조예 7: 아세톤으로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Preparation Example 7 Synthesis of Styrene-Butadiene-Styrene Block Copolymer Treated with Acetone
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌 모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간 동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 0.9g의 아세톤을 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합 스티렌함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were injected, followed by polymerization for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and then 0.9 g of acetone was added to inactivate the terminal of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block having a bound styrene content of 31.0% (block styrene content of 30.0%), a 1,2-vinyl bond content of butadiene units (38.5% (26.6% of all polymers)) and a number average molecular weight of about 50,000. Copolymer.
제조예 8: 알릴클로라이드로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Preparation Example 8 Synthesis of Styrene-Butadiene-Styrene Block Copolymer Treated with Allyl Chloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 1.2g의 알릴클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합 스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were added, followed by polymerization for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and 1.2 g of allyl chloride was added to inactivate the terminal of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block containing 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond (26.6% of all polymers) in a butadiene unit, and a number average molecular weight of about 50,000. Copolymer.
제조예 9: 트리메틸실릴클로라이드로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Preparation Example 9 Synthesis of Styrene-Butadiene-Styrene Block Copolymer Treated with Trimethylsilylchloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌 모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간 동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 1.7g의 트리메틸실릴클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합 스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were injected, followed by polymerization for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and 1.7 g of trimethylsilyl chloride was added to inactivate the terminal of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block containing 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond (26.6% of all polymers) in a butadiene unit, and a number average molecular weight of about 50,000. Copolymer.
제조예 10: 메틸브로마이드로 처리된 스티렌-부타디엔-스티렌형 블록 공중합체 합성Preparation Example 10 Synthesis of Styrene-Butadiene-Styrene Block Copolymer Treated with Methylbromide
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 1,3-부타디엔 모노머 552g을 반응기 내로 주입하여 1시간 동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 1.5g의 메틸브로마이드를 첨가하여 고분자의 말단을 비활성화시켰다. 이렇게 얻어진 고분자는 결합 스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 부타디엔 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-부타디엔-스티렌형 블록 공중합체이다.4800 g of cyclohexane was added to a 10-liter autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were polymerized, and then polymerized for 30 minutes. Then, 552 g of 1,3-butadiene monomer was injected into the reactor for 1 hour. Polymerized. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and 1.5 g of methyl bromide was added to inactivate the ends of the polymer. The polymer thus obtained had a styrene-butadiene-styrene block containing 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond (26.6% of all polymers) in a butadiene unit, and a number average molecular weight of about 50,000. Copolymer.
제조예 11:Preparation Example 11: tt -부틸클로라이드로 처리된 스티렌-이소프렌-스티렌형 블록 공중합체 합성Synthesis of Styrene-Isoprene-Styrene Block Copolymers Treated with -Butylchloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 4800g을 넣고 테트라하이드로퓨란 11g, 스티렌모노머 124g 및 n-부틸리튬 16mmol을 주입한 후 30분간 중합한 다음, 이소프렌 모노머 552g을 반응기 내로 주입하여 1시간 동안 중합시켰다. 마지막으로 스티렌 모노머 124g을 첨가하고 30분 동안 중합한 후 1.5g의 t-부틸클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합스티렌 함유율 31.0%(블록스티렌 함량 30.0%), 이소프렌 단위의 1,2-비닐 결합 함유율 38.5%(전 중합체 환산 26.6%), 수평균 분자량 약 50,000인 스티렌-이소프렌-스티렌형 블록 공중합체이다.4800 g of cyclohexane was charged in a 10 L autoclave reactor, 11 g of tetrahydrofuran, 124 g of styrene monomer, and 16 mmol of n-butyllithium were injected, followed by polymerization for 30 minutes, followed by injection of 552 g of isoprene monomer into the reactor for 1 hour. Finally, 124 g of styrene monomer was added and polymerized for 30 minutes, and 1.5 g of t-butyl chloride was added to inactivate the terminal of the polymer. The polymer thus obtained contained 31.0% of bound styrene (30.0% of block styrene), 38.5% of 1,2-vinyl bond of isoprene unit (26.6% of all polymers), and a styrene-isoprene-styrene block having a number average molecular weight of about 50,000. Copolymer.
제조예 12:Preparation Example 12: tt -부틸클로라이드로 처리된 스티렌-부타디엔 랜덤 공중합체 합성Synthesis of Styrene-Butadiene Copolymer Treated with -Butylchloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 5000g을 넣고 테트라하이드로퓨란 100g, 스티렌모노머 130g 및 부타디엔 모노머 870g을 넣은 후 n-부틸리튬 10mmol을 첨가하여 1시간 동안 중합한 후 0.9g의 t-부틸클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 결합 스티렌 함유율 13%, 부타디엔 단위의 1,2-비닐 결합 함유율 57%, 수평균 분자량 약 100,000인 스티렌-부타디엔 랜덤 공중합체이다.In a 10-liter autoclave reactor, 5000 g of cyclohexane was added, 100 g of tetrahydrofuran, 130 g of styrene monomer and 870 g of butadiene monomer were added, followed by polymerization of 1 mmol of n-butyllithium for 1 hour, followed by 0.9 g of t-butyl chloride. The terminal of the polymer was inactivated. The polymer thus obtained is a styrene-butadiene random copolymer having a combined styrene content of 13%, a 1,2-vinyl bond content of butadiene units of 57%, and a number average molecular weight of about 100,000.
제조예 13:Preparation Example 13: tt -부틸클로라이드로 처리된 부타디엔 단독중합체 합성Synthesis of Butadiene Homopolymer Treated with -Butylchloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 5000g을 넣고 부타디엔 모노머 1000g을 넣은 후 n-부틸리튬 10mmol을 첨가하여 2시간 동안 중합한 후 0.9g의 t-부틸클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 부타디엔 단위의 1,2-비닐 결합 함유율 10%, 시스 결합 함유율 35%, 수평균 분자량 약 100,000인 부타디엔 단독중합체이다.5000 g of cyclohexane was added in a 10 L autoclave reactor, 1000 g of butadiene monomer was added, n-butyllithium 10 mmol was added, polymerization was performed for 2 hours, and 0.9 g of t-butyl chloride was added to deactivate the terminal of the polymer. The polymer thus obtained is a butadiene homopolymer having a 1,2-vinyl bond content of butadiene units of 10%, a cis bond content of 35%, and a number average molecular weight of about 100,000.
제조예 14:Preparation Example 14 tt -부틸클로라이드로 처리된 이소프렌 단독중합체 합성Synthesis of Isoprene Homopolymers Treated with -Butylchloride
10ℓ의 오토클레이브 반응기 중에 사이클로헥산 5000g을 넣고 이소프렌 모노머 1000g을 넣은 후 n-부틸리튬 10mmol을 첨가하여 2시간 동안 중합한 후 0.9g의t-부틸클로라이드를 첨가하여 고분자의 말단을 비활성화 시켰다. 이렇게 얻어진 고분자는 이소프렌 단위의 1,2-비닐 결합 함유율 10%, 수평균 분자량 약 100,000인 이소프렌 단독중합체를 얻었다.5000 g of cyclohexane was added in a 10 L autoclave reactor, 1000 g of isoprene monomer was added, and 10 mmol of n-butyllithium was added to polymerize for 2 hours, and 0.9 g of t-butyl chloride was added to inactivate the terminal of the polymer. The thus obtained polymer obtained an isoprene homopolymer having a 1,2-vinyl bond content of 10% of isoprene units and a number average molecular weight of about 100,000.
실시예 1∼6Examples 1-6
상기 제조예 4∼9에서 얻어진 중합체 각각을 400g 포함하는 용액 2800g을 5ℓ 오토클레이브 반응기에 넣고 400rpm(분당회전수)에서 80℃로 가열하였다. 그 다음 상기 제조예 1에서 얻은 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디클로라이드 1.6mmol과 제조예 3에서 얻은 리튬하이드라이드 16mmol을 불활성 기체 하에서 30분간 혼합하여 중합체 용액에 첨가한 후 반응기를 10 kg/㎠의 수소로 가압하여 수소화 반응을 1시간 동안 계속하도록 하였다. 반응종료 후 반응기를 냉각시키고 압력을 상압으로 낮춘 후 반응용액을 메탄올에 투입하여 고분자를 침전시켰다.2800 g of a solution containing 400 g of each of the polymers obtained in Preparation Examples 4 to 9 was placed in a 5 L autoclave reactor and heated to 80 ° C. at 400 rpm (rpm). Then, 1.6 mmol of the monocyclopentadienyl (2,5-dimethylpyrrolyl) titanium dichloride obtained in Preparation Example 1 and 16 mmol of the lithium hydride obtained in Preparation Example 3 were mixed under an inert gas for 30 minutes, and added to the polymer solution. The reactor was then pressurized with 10 kg / cm 2 of hydrogen to continue the hydrogenation reaction for 1 hour. After completion of the reaction, the reactor was cooled, the pressure was reduced to normal pressure, and the reaction solution was added to methanol to precipitate the polymer.
얻어진 수소화된 폴리머의1H-NMR 분석결과, 최종 수소화율에 있어서 부타디엔 단위의 수소화율 및 스티렌단위의 수소 첨가율을 표 1에 나타내었다.As a result of 1 H-NMR analysis of the obtained hydrogenated polymer, the hydrogenation rate of butadiene units and the hydrogenation rate of styrene units in the final hydrogenation rate are shown in Table 1.
실시예 7∼11Examples 7-11
실시예 7∼11은 상기 제조예 10∼14에서 얻어진 각각의 중합체를 사용하여상기 실시예 1과 동일한 방법으로 수소화 반응을 실시하였다. 다만 제조예 13, 14의 중합체에는 실시예 1에서 사용하였던 모노사이클로펜타디에닐(2,5-디메틸피롤릴)티타늄디클로라이드와 리튬하이드라이드의 양을 각각 2배로 늘려 반응 시켰다. 그 결과를 다음 표 2에 나타내었다.Examples 7 to 11 were subjected to hydrogenation in the same manner as in Example 1 using the respective polymers obtained in Production Examples 10 to 14. However, the polymers of Preparation Examples 13 and 14 were reacted by doubling the amount of monocyclopentadienyl (2,5-dimethylpyrrolyl) titanium dichloride and lithium hydride used in Example 1, respectively. The results are shown in Table 2 below.
실시예 12∼16Examples 12-16
상기 제조예 9에서 얻어진 중합체 400g을 포함하는 용액 2800g을 5ℓ오토클레이브 반응기에 넣고 400rpm(분당회전수)에서 80℃로 가열하였다. 그 다음 상기 제조예 3에서 얻은 리튬하이드라이드와 상기 제조예 1에서 얻은 촉매량의 사용량과 몰 비율을 조절하여 중합체 용액에 첨가한 후 반응기를 10 kg/㎠의 수소로 가압하여 수소화 반응을 1시간 동안 계속하도록 하였다. 반응종료 후 반응기를 냉각시키고 압력을 상압으로 낮춘 후 반응용액을 메탄올에 투입하여 고분자를 침전시켰다.2800 g of a solution containing 400 g of the polymer obtained in Preparation Example 9 was placed in a 5 L autoclave reactor and heated to 80 ° C. at 400 rpm (rpm). Then, the amount and molar ratio of the lithium hydride obtained in Preparation Example 3 and the catalyst amount obtained in Preparation Example 1 were adjusted and added to the polymer solution, and then the reactor was pressurized with hydrogen of 10 kg / cm 2 for 1 hour. To continue. After completion of the reaction, the reactor was cooled, the pressure was reduced to normal pressure, and the reaction solution was added to methanol to precipitate the polymer.
얻어진 수소화된 폴리머의1H-NMR 분석결과, 최종 수소화율에 있어서 부타디엔 단위의 수소화율 및 스티렌단위의 수소 첨가율을 다음 표 3에 나타내었다.As a result of 1 H-NMR analysis of the obtained hydrogenated polymer, the hydrogenation rate of butadiene unit and hydrogenation rate of styrene unit in the final hydrogenation rate are shown in Table 3 below.
실시예 17∼20Examples 17-20
제조에 2에서 합성된 모노사이클로펜타디에닐(피롤릴)티타늄디클로라이드 와 제조예 4, 5, 6, 9에서 얻어진 중합체 각각을 사용한 것 이외에는 상기 실시예 1∼6에서와 같은 방법으로 수첨반응을 실시하였다. 얻어진 수소화된 폴리머의1H-NMR 분석결과, 최종 수소화율에 있어서 부타디엔 단위의 수소화율 및 스티렌단위의 수소 첨가율을 다음 표 4에 나타내었다.Hydrogenation reaction was carried out in the same manner as in Examples 1 to 6 except that monocyclopentadienyl (pyrrolyl) titanium dichloride synthesized in Preparation 2 and the polymers obtained in Preparation Examples 4, 5, 6, and 9 were used. Was carried out. As a result of 1 H-NMR analysis of the obtained hydrogenated polymer, the hydrogenation rate of butadiene units and the hydrogenation rate of styrene units in the final hydrogenation rate are shown in Table 4 below.
실시예 21∼25Examples 21-25
제조예 2에서 합성된 모노사이클로펜타디에닐(피롤릴)티타늄디클로라이드 를 사용한 것 이외에는 상기 실시예 12∼16에서와 같은 방법으로 수첨반응을 실시하였다. 얻어진 수소화된 폴리머의1H-NMR 분석결과, 최종 수소화율에 있어서 부타디엔 단위의 수소화율 및 스티렌단위의 수소 첨가율을 다음 표 5에 나타내었다.Hydrogenation reaction was carried out in the same manner as in Examples 12 to 16 except that monocyclopentadienyl (pyrrolyl) titanium dichloride synthesized in Preparation Example 2 was used. As a result of 1 H-NMR analysis of the obtained hydrogenated polymer, the hydrogenation rate of butadiene units and hydrogenation rate of styrene units in the final hydrogenation rate are shown in Table 5 below.
이상에서 상세히 설명한 바와 같이, 본 발명에서와 같이 상기 화학식 1로 표시되는 모노사이클로펜타디에닐(피롤릴) 티타늄화합물과, 용액 중에서 알킬리튬과 수소를 반응시켜 만든 리튬하이드라이드의 혼합으로 만들어지는 새로운 촉매는 공액디엔 중합체의 불포화 이중결합을 수소화시키는 경우 촉매 활성이 우수하여 온화한 조건 하에서 수소화가 가능하고, 특히 공액디엔계 화합물과 비닐치환 방향족 탄화수소와의 공중합체에 있어서 공액디엔 단위의 불포화 이중결합을 극히 선택적으로 수소화 할 수 있으며, 공액디엔 중합체를 원료로 사용하므로 동일 반응기에서 연속적으로 수소화가 가능하고, 동시에 소량의 촉매첨가로 극히 높은 활성을 나타낼 수 있는 경제적이고 단순한 공정이므로 공업적으로 특히 유용하게 사용할 수 있는 방법이다.As described in detail above, a new compound made of a mixture of a monocyclopentadienyl (pyrrolyl) titanium compound represented by Chemical Formula 1 and a lithium hydride made by reacting alkyl lithium and hydrogen in a solution as in the present invention The catalyst is excellent in catalytic activity when hydrogenating unsaturated double bonds of conjugated diene polymer, so that hydrogenation is possible under mild conditions. Especially, in the copolymer of conjugated diene-based compound with vinyl-substituted aromatic hydrocarbon, the unsaturated double bond of conjugated diene unit It is extremely selective and can be hydrogenated. Since conjugated diene polymer is used as raw material, it is possible to continuously hydrogenate in the same reactor, and at the same time, it is an economical and simple process that can show extremely high activity by adding a small amount of catalyst. This is the method you can use.
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| US5177155A (en) * | 1991-05-13 | 1993-01-05 | Shell Oil Company | Selective hydrogenation of conjugation diolefin polymers with rare earth catalysts |
| US5206307A (en) * | 1991-09-09 | 1993-04-27 | Shell Oil Company | Process for selective hydrogenation of conjugated diolefin polymers |
| WO1996018655A1 (en) * | 1994-12-12 | 1996-06-20 | The Dow Chemical Company | Hydrogenation of unsaturated polymers using monocyclopentadienyl group iv metal catalysts |
| US5539124A (en) * | 1994-12-19 | 1996-07-23 | Occidental Chemical Corporation | Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring |
| KR19980056208A (en) * | 1996-12-28 | 1998-09-25 | 김흥기 | Selective hydrogenation of olefinic double bonds in living polymers |
| US5886107A (en) * | 1996-05-29 | 1999-03-23 | Shell Oil Company | Process for hydrogenation of conjugated diene polymers and catalyst compositions suitable for use therein |
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| US5177155A (en) * | 1991-05-13 | 1993-01-05 | Shell Oil Company | Selective hydrogenation of conjugation diolefin polymers with rare earth catalysts |
| US5206307A (en) * | 1991-09-09 | 1993-04-27 | Shell Oil Company | Process for selective hydrogenation of conjugated diolefin polymers |
| WO1996018655A1 (en) * | 1994-12-12 | 1996-06-20 | The Dow Chemical Company | Hydrogenation of unsaturated polymers using monocyclopentadienyl group iv metal catalysts |
| US5539124A (en) * | 1994-12-19 | 1996-07-23 | Occidental Chemical Corporation | Polymerization catalysts based on transition metal complexes with ligands containing pyrrolyl ring |
| US5886107A (en) * | 1996-05-29 | 1999-03-23 | Shell Oil Company | Process for hydrogenation of conjugated diene polymers and catalyst compositions suitable for use therein |
| KR19980056208A (en) * | 1996-12-28 | 1998-09-25 | 김흥기 | Selective hydrogenation of olefinic double bonds in living polymers |
| KR100195581B1 (en) * | 1996-12-28 | 1999-06-15 | 박찬구 | Process for hydrogenating olefinic double bond in living polymers |
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