KR20040098437A - 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체 및 그제조방법 - Google Patents
고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체 및 그제조방법 Download PDFInfo
- Publication number
- KR20040098437A KR20040098437A KR1020030030805A KR20030030805A KR20040098437A KR 20040098437 A KR20040098437 A KR 20040098437A KR 1020030030805 A KR1020030030805 A KR 1020030030805A KR 20030030805 A KR20030030805 A KR 20030030805A KR 20040098437 A KR20040098437 A KR 20040098437A
- Authority
- KR
- South Korea
- Prior art keywords
- compound
- cis polybutadiene
- polybutadiene
- polyurethane copolymer
- cis
- Prior art date
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 57
- 239000004814 polyurethane Substances 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title claims description 20
- -1 isocyanate compound Chemical class 0.000 claims abstract description 68
- 239000005062 Polybutadiene Substances 0.000 claims abstract description 59
- 229920002857 polybutadiene Polymers 0.000 claims abstract description 59
- 239000003054 catalyst Substances 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 39
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 32
- 125000000524 functional group Chemical group 0.000 claims abstract description 29
- 239000012948 isocyanate Substances 0.000 claims abstract description 28
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 27
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 23
- 238000000034 method Methods 0.000 claims abstract description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 16
- 150000002367 halogens Chemical class 0.000 claims abstract description 16
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 13
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims abstract description 9
- 229920001577 copolymer Polymers 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract 3
- 238000006116 polymerization reaction Methods 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 10
- 125000003118 aryl group Chemical group 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 150000002910 rare earth metals Chemical group 0.000 claims description 8
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 7
- 239000004305 biphenyl Substances 0.000 claims description 7
- SIPUZPBQZHNSDW-UHFFFAOYSA-N bis(2-methylpropyl)aluminum Chemical compound CC(C)C[Al]CC(C)C SIPUZPBQZHNSDW-UHFFFAOYSA-N 0.000 claims description 7
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002841 Lewis acid Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 150000007517 lewis acids Chemical class 0.000 claims description 5
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical group CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 claims description 5
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 claims description 4
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- UAHWPYUMFXYFJY-UHFFFAOYSA-N beta-myrcene Chemical compound CC(C)=CCCC(=C)C=C UAHWPYUMFXYFJY-UHFFFAOYSA-N 0.000 claims description 4
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethylcyclohexane Chemical compound CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 4
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 claims description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 4
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims description 4
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 4
- 125000005474 octanoate group Chemical group 0.000 claims description 4
- 150000002896 organic halogen compounds Chemical class 0.000 claims description 4
- 150000001735 carboxylic acids Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005234 alkyl aluminium group Chemical group 0.000 claims description 2
- VYBREYKSZAROCT-UHFFFAOYSA-N alpha-myrcene Natural products CC(=C)CCCC(=C)C=C VYBREYKSZAROCT-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 239000001273 butane Substances 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000004122 cyclic group Chemical group 0.000 claims description 2
- AFABGHUZZDYHJO-UHFFFAOYSA-N dimethyl butane Natural products CCCC(C)C AFABGHUZZDYHJO-UHFFFAOYSA-N 0.000 claims description 2
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical group CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims description 2
- 125000005609 naphthenate group Chemical group 0.000 claims description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- 229920006395 saturated elastomer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 claims description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 2
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 claims description 2
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 2
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019354 vermiculite Nutrition 0.000 claims description 2
- 229910052902 vermiculite Inorganic materials 0.000 claims description 2
- 239000010455 vermiculite Substances 0.000 claims description 2
- 239000008096 xylene Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 235000021355 Stearic acid Nutrition 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 125000005608 naphthenic acid group Chemical group 0.000 claims 1
- 229920001296 polysiloxane Polymers 0.000 claims 1
- 150000003609 titanium compounds Chemical class 0.000 claims 1
- 238000005299 abrasion Methods 0.000 abstract description 4
- 230000000379 polymerizing effect Effects 0.000 abstract description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000006229 carbon black Substances 0.000 abstract 1
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000003963 antioxidant agent Substances 0.000 description 8
- 230000003078 antioxidant effect Effects 0.000 description 8
- 125000003368 amide group Chemical group 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000032683 aging Effects 0.000 description 6
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000004593 Epoxy Substances 0.000 description 4
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 4
- 239000002685 polymerization catalyst Substances 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- ZMZGFLUUZLELNE-UHFFFAOYSA-N 2,3,5-triiodobenzoic acid Chemical compound OC(=O)C1=CC(I)=CC(I)=C1I ZMZGFLUUZLELNE-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 125000003545 alkoxy group Chemical group 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- IQPQWNKOIGAROB-UHFFFAOYSA-N isocyanate group Chemical group [N-]=C=O IQPQWNKOIGAROB-UHFFFAOYSA-N 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- OAOABCKPVCUNKO-UHFFFAOYSA-N 8-methyl Nonanoic acid Chemical compound CC(C)CCCCCCC(O)=O OAOABCKPVCUNKO-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000004386 Erythritol Substances 0.000 description 1
- UNXHWFMMPAWVPI-UHFFFAOYSA-N Erythritol Natural products OCC(O)C(O)CO UNXHWFMMPAWVPI-UHFFFAOYSA-N 0.000 description 1
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 239000002879 Lewis base Substances 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- GTTSNKDQDACYLV-UHFFFAOYSA-N Trihydroxybutane Chemical compound CCCC(O)(O)O GTTSNKDQDACYLV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000011952 anionic catalyst Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- UNXHWFMMPAWVPI-ZXZARUISSA-N erythritol Chemical compound OC[C@H](O)[C@H](O)CO UNXHWFMMPAWVPI-ZXZARUISSA-N 0.000 description 1
- 229940009714 erythritol Drugs 0.000 description 1
- 235000019414 erythritol Nutrition 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000020169 heat generation Effects 0.000 description 1
- ACCCMOQWYVYDOT-UHFFFAOYSA-N hexane-1,1-diol Chemical compound CCCCCC(O)O ACCCMOQWYVYDOT-UHFFFAOYSA-N 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- TUQOTMZNTHZOKS-UHFFFAOYSA-N tributylphosphine Chemical compound CCCCP(CCCC)CCCC TUQOTMZNTHZOKS-UHFFFAOYSA-N 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
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L19/00—Compositions of rubbers not provided for in groups C08L7/00 - C08L17/00
- C08L19/006—Rubber characterised by functional groups, e.g. telechelic diene polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/22—Incorporating nitrogen atoms into the molecule
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08C—TREATMENT OR CHEMICAL MODIFICATION OF RUBBERS
- C08C19/00—Chemical modification of rubber
- C08C19/30—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule
- C08C19/42—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups
- C08C19/44—Addition of a reagent which reacts with a hetero atom or a group containing hetero atoms of the macromolecule reacting with metals or metal-containing groups of polymers containing metal atoms exclusively at one or both ends of the skeleton
-
- 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
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Abstract
Description
구분 | Nd촉매량(×0-4mol) | 촉매조성(mol ratio)(Nd/TIBA/DIBAL/DIEC) | 중합온도(℃) | 이소시아네이트투입량(phr) | 알코올투입량(phr) | |
실시예 | 1 | 1.0 | 1 / 20 / 4 / 2.5 | 70 | 0.3 | 0.3 |
2 | 1.0 | 1 / 20 / 5 / 2.5 | 70 | 0.3 | 0.3 | |
3 | 1.0 | 1 / 20 / 4 / 2.5 | 70 | 0.3 | 0.6 | |
4 | 1.2 | 1 / 20 / 7 / 2 | 70 | 0.3 | 1.2 | |
5 | 1.0 | 1 / 20 / 10 / 3 | 70 | 0.6 | 1.2 | |
6 | 1.5 | 1 / 30 / 4 / 3 | 70 | 0.3 | 0.6 | |
7 | 1.5 | 1 / 30 / 5 / 3 | 70 | 0.3 | 0.6 | |
Nd:니오디뮴 버스테이트[Nd(versatate)3(versatic acid)]DIEC:염화디에틸알루미늄(Et2AlCl)DIBAL:디이소부틸알루미늄하이드라이드(Al(iBu)2H)TIBA:트리이소부틸알루미늄(Al(iBu)3) |
구분 | cis함량a,b(%) | Mw a | Mw b | MWDa | MWDb | 무니점도a(ML1+4, 100℃) | 무니점도b(ML1+4, 100℃) | |
실시예 | 1 | 98.7 | 851,300 | 872,500 | 2.70 | 2.89 | 59.5 | 70.0 |
2 | 98.6 | 627,400 | 649,600 | 2.81 | 2.96 | 42.0 | 51.0 | |
3 | 98.6 | 652,700 | 695,900 | 2.93 | 3.10 | 49.5 | 61.0 | |
4 | 98.4 | 613,500 | 664,800 | 2.86 | 3.08 | 37.5 | 46.0 | |
5 | 98.5 | 302,000 | 321,400 | 2.42 | 2.65 | 27.5 | 33.5 | |
6 | 98.2 | 550,400 | 622,400 | 2.73 | 2.93 | 32.5 | 42.5 | |
7 | 98.3 | 583,600 | 620,600 | 2.64 | 2.84 | 35.5 | 43.0 | |
a:고 1,4-시스 폴리부타디엔b: 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체Mw: 중량평균분자량, MWD: 분자량 분포 |
니오디뮴촉매로 중합된 고 1,4-시스 폴리부타디엔 | 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체 | ||
MV | RAW(ML1+4, 100 ℃) | 47 | 50 |
Tensile | Hardness(shore-A/5sec) | 61.5 | 61.5 |
300% modulus(kg/㎠) | 111.5 | 116.2 | |
Tensile strength(kg/㎠) | 138.5 | 154 | |
Elongation at break(%) | 360 | 371.1 | |
H.B.U(℃) | 32.3 | 28.3 | |
Rebound(%) | 53.4 | 56.5 | |
Abrasion(mg) | 0.0183 | 0.0155 |
Claims (28)
- 다음 화학식 1로 표시되는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체.화학식 1상기 식에서, l, m, n 및 o는 반복단위의 수로서, l은 94∼99%, m은 0∼5%, n은 0∼5%, l+m+n=100% 및 l/(m+n)의 비율은 15∼100을 만족하며, o는 1∼100%이고, A와 Y는 탄소수가 1∼20인 알킬 또는 알릴이다.
- 제 1 항에 있어서, 고 1,4-시스 폴리부타디엔은 분자량이 100,000이상인 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체.
- 비극성 용매의 존재하에서 희토류 화합물, 할로겐을 함유하는 화합물, 그리고 유기알루미늄 화합물로 이루어지는 촉매를 이용하여 1,3-부타디엔 또는 부타디엔 유도체를 중합하여 95% 이상의 고 1,4-시스 함량을 갖는 폴리부타디엔을 제조하는 제 1 단계; 및여기에 관능기 2 이상의 이소시아네이트 화합물과 관능기 2 이상의 알코올을 반응시키는 제 2 단계를 포함하는 다음 화학식 1로 표시되는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.화학식 1상기 식에서, l, m, n 및 o는 반복단위의 수로서, l은 94∼99%, m은 0∼5%, n은 0∼5%, l+m+n=100% 및 l/(m+n)의 비율은 15∼100을 만족하며, o는 1∼100%이고, A와 Y는 탄소수가 1∼20인 알킬 또는 알릴이다.
- 제 3 항에 있어서, 관능기 2 이상의 이소시아네이트 화합물로는 다음 화학식 2로 표시되는 것을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.화학식 2R-(NCO)n상기 식에서, R은 탄소수가 1∼20인 알킬 또는 알릴그룹이며, n은 2~4의 정수이다.
- 제 3 항 또는 제 4 항에 있어서, 관능기 2 이상의 이소시아네이트 화합물로는 탄소수 1∼20의 알킬 디이소시아네이트, 알킬 트리이소시아네이트, 알킬 테트라 이소시아네이트, 아로마틱 디이소시아네이트, 아로마틱 트리이소시아네이트 및 아로마틱 테트라이소시아네이트 화합물 중에서 선택하여 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항 또는 제 4 항에 있어서, 관능기 2 이상의 이소시아네이트 화합물로는 폴리메틸렌 디페닐디이소시아네이트를 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 관능기 2 이상의 이소시아네이트 화합물은 95% 이상의 고 1,4-시스 함량을 갖는 폴리부타디엔 100중량부에 대하여 0.01∼10.0중량부 되도록 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 관능기 2 이상의 알코올 화합물로는 다음 화학식 3으로표시되는 것을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.화학식 3R'-(OH)m상기 식에서, R'은 탄소수가 1∼20개인 알킬 또는 알릴그룹이며, m은 2~10의 정수이다.
- 제 3 항 또는 제 4 항에 있어서, 관능기 2 이상의 알코올 화합물로는 탄소수 1∼20의 알킬 디올, 알킬 트리올, 알킬 테트라올, 아로마틱 디올, 아로마틱 트리올 및 아로마틱 테트라올 화합물 중에서 선택하여 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항 또는 제 4 항에 있어서, 관능기 2 이상의 알코올 화합물로는 글리콜을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 관능기 2 이상의 알코올 화합물은 95% 이상의 고 1,4-시스 함량을 갖는 폴리부타디엔 100중량부에 대하여 0.01∼50.0중량부 되도록 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 부타디엔 유도체로는 이소프렌, 1,3-펜타디엔, 2,3-디메틸-1,3-부타디엔, 미르센, 이들의 혼합물 및 이들의 유도체를 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 희토류 화합물로는 희토류 유기산염 또는 희토류 무기산염을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 13 항에 있어서, 희토류 유기산염으로는 희토류 카르복실산염을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 14 항에 있어서, 희토류 카르복실산염으로는 탄소수 8∼20의 포화, 불포화, 환형 혹은 선형구조를 갖는 옥토에이트산, 나프턴산, 버스테에이트산 및 스티어에이트산 중에서 선택된 카르복실산의 염을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 15 항에 있어서, 희토류 카르복실산염으로는 니오디뮴버스테이트, 니오디뮴옥토에이트 및 니오디뮴 나프테네이트 중에서 선택하여 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 할로겐을 포함하는 화합물로는 할로겐을 함유하는 루이스산 또는 할로겐을 쉽게 내놓을 수 있는 유기할로겐 화합물을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 17 항에 있어서, 할로겐을 함유하는 루이스산으로는 AlXnR1 3-n(R1는 탄소원자수 1∼10인 알킬, 아릴, 또는 수소원자, n은 1 혹은 2)로 표시되는 알루미늄 화합물과 이에 상응하는 보론, 실리콘, 주석, 티타늄 화합물 중에서 선택하여 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 17 항에 있어서, 유기할로겐 화합물로는 t-알킬할로겐화합물을 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 유기알루미늄 화합물로는 AlR2 3(R2는 탄소원자수 1∼10인 알킬, 아릴, 또는 수소원자)로 표시되는 트리메틸알루미늄, 트리에틸알루미늄, 트리프로필알루미늄, 트리부틸알루미늄, 트리이소부틸알루미늄, 트리헥실알루미늄 및 디이소부틸알루미늄하이드라이드 중에서 선택하여 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 비극성 용매로는 부탄, 펜탄, 헥산, 이소펜탄, 헵탄, 옥탄, 이소옥탄, 시클로펜탄, 메틸시클로펜탄, 시클로헥산, 메틸시클로헥산, 에틸시클로헥산, 벤젠, 톨루엔, 에틸벤젠 및 크실렌 중에서 선택하여 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 촉매로는 희토류 원자 대 염소 원자의 몰비가 1:1 ∼ 1:20 되도록 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 촉매로는 희토류 원자 대 알킬알루미늄의 몰비가 1:20 ∼1:100 되도록 사용하는 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 용매 대 1,3-부타디엔 또는 부타디엔 유도체의 비율은 무게비로 10∼1인 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 제 1 단계 반응시간은 30분에서 3시간인 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 제 1 단계 반응온도는 -20℃ 내지 100℃ 사이인 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 제 2 단계 반응시간은 5분에서 2시간인 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
- 제 3 항에 있어서, 제 2 단계 반응온도는 20℃ 내지 150℃ 사이인 것을 특징으로 하는 고 1,4-시스 폴리부타디엔-폴리우레탄 공중합체의 제조방법.
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KR100792414B1 (ko) * | 2006-07-20 | 2008-01-08 | 금호석유화학 주식회사 | 높은 1, 4-시스 함량을 지닌 폴리부타디엔 고무 나노복합재및 이의 제조방법 |
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ZA200904418B (en) * | 2006-12-27 | 2010-08-25 | Jsr Corp | Method for producing modified conjugated diene polymer, modified conjugated diene polymer, and rubber composition |
DE102007038442A1 (de) * | 2007-08-16 | 2009-02-19 | Lanxess Deutschland Gmbh | Modifizierte Polymere auf Basis von konjugierten Dienen oder von konjugierten Dienen und vinylaromatischen Verbindungen, ein Verfahren zu deren Herstellung sowie deren Verwendung |
BRPI0806170B1 (pt) * | 2007-10-22 | 2019-02-26 | Bridgestone Corporation | Polímero funcionalizado, método para preparar um polímero funcionalizado, e, composição compreendendo um polímero funcionalizado |
KR100970767B1 (ko) * | 2007-12-12 | 2010-07-16 | 금호석유화학 주식회사 | 방향족 유기황화합물로 기능화된 1,4-시스 폴리부타디엔 |
KR101194401B1 (ko) * | 2009-12-09 | 2012-10-25 | 금호석유화학 주식회사 | 골프공 코어의 제조용 방향족 유기황화합물로 기능화된 1,4-시스 폴리부타디엔 |
RU2627705C2 (ru) * | 2011-12-09 | 2017-08-10 | Бриджстоун Корпорейшн | Способ получения полидиенов и полидиеновых сополимеров с пониженной текучестью на холоде |
CN104098995B (zh) * | 2014-07-21 | 2016-05-04 | 广州市盛邦康体场地材料有限公司 | 一种阻燃与防水性水性聚氨酯涂料的制备方法 |
FR3044317B1 (fr) * | 2015-11-27 | 2017-12-08 | Michelin & Cie | Composition de caoutchouc renforcee comprenant un elastomere dienique fonctionnel |
CN107459596B (zh) * | 2017-09-26 | 2020-09-29 | 青岛瑞林材料科技有限公司 | 一种合成高顺式聚二烯烃的方法 |
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DE2830080A1 (de) * | 1978-07-08 | 1980-01-17 | Bayer Ag | Katalysator, dessen herstellung und verwendung zur loesungspolymerisation von butadien |
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IT1191614B (it) * | 1985-05-15 | 1988-03-23 | Enichem Elastomers | Procedimento migliorato per la polimerizzazione o copolimerizzazione del butadiene |
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GB8830007D0 (en) | 1988-12-22 | 1989-02-15 | Enichem Elastomers | Polymerization of butadiene |
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US5428119A (en) * | 1993-11-09 | 1995-06-27 | Polysar Rubber Corporation | Process for polybutadiene production using catalyst with high activity |
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CA2427659A1 (en) | 2000-10-30 | 2002-05-10 | William D. Huse | Methods for producing and improving therapeutic potency of binding polypeptides |
JP2004180801A (ja) * | 2002-11-29 | 2004-07-02 | Bridgestone Sports Co Ltd | マルチピースソリッドゴルフボール |
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KR100792414B1 (ko) * | 2006-07-20 | 2008-01-08 | 금호석유화학 주식회사 | 높은 1, 4-시스 함량을 지닌 폴리부타디엔 고무 나노복합재및 이의 제조방법 |
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