WO2015090447A1 - Sulfur-containing polymers - Google Patents
Sulfur-containing polymers Download PDFInfo
- Publication number
- WO2015090447A1 WO2015090447A1 PCT/EP2013/077700 EP2013077700W WO2015090447A1 WO 2015090447 A1 WO2015090447 A1 WO 2015090447A1 EP 2013077700 W EP2013077700 W EP 2013077700W WO 2015090447 A1 WO2015090447 A1 WO 2015090447A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- sulfur
- polymer
- elastomeric
- containing polymer
- styrene
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 152
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 54
- 239000011593 sulfur Substances 0.000 title claims abstract description 52
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 17
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 59
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 49
- 238000006116 polymerization reaction Methods 0.000 claims description 33
- PXJJSXABGXMUSU-UHFFFAOYSA-N disulfur dichloride Chemical compound ClSSCl PXJJSXABGXMUSU-UHFFFAOYSA-N 0.000 claims description 30
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 29
- 125000000129 anionic group Chemical group 0.000 claims description 17
- 239000000178 monomer Substances 0.000 claims description 15
- 229920006318 anionic polymer Polymers 0.000 claims description 14
- 150000001993 dienes Chemical class 0.000 claims description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 239000000945 filler Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 8
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 8
- -1 1 -substituted styrene Chemical class 0.000 claims description 6
- 238000010539 anionic addition polymerization reaction Methods 0.000 claims description 6
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003921 oil Substances 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 239000003381 stabilizer Substances 0.000 claims description 5
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- 125000001979 organolithium group Chemical group 0.000 claims description 4
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 claims description 3
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- 239000012528 membrane Substances 0.000 claims description 3
- 150000002900 organolithium compounds Chemical group 0.000 claims description 3
- 229920003023 plastic Polymers 0.000 claims description 3
- 239000004033 plastic Substances 0.000 claims description 3
- 230000002787 reinforcement Effects 0.000 claims description 3
- AHAREKHAZNPPMI-AATRIKPKSA-N (3e)-hexa-1,3-diene Chemical compound CC\C=C\C=C AHAREKHAZNPPMI-AATRIKPKSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 claims description 2
- CORMBJOFDGICKF-UHFFFAOYSA-N 1,3,5-trimethoxy 2-vinyl benzene Natural products COC1=CC(OC)=C(C=C)C(OC)=C1 CORMBJOFDGICKF-UHFFFAOYSA-N 0.000 claims description 2
- QTYUSOHYEPOHLV-FNORWQNLSA-N 1,3-Octadiene Chemical compound CCCC\C=C\C=C QTYUSOHYEPOHLV-FNORWQNLSA-N 0.000 claims description 2
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 claims description 2
- NVZWEEGUWXZOKI-UHFFFAOYSA-N 1-ethenyl-2-methylbenzene Chemical compound CC1=CC=CC=C1C=C NVZWEEGUWXZOKI-UHFFFAOYSA-N 0.000 claims description 2
- JZHGRUMIRATHIU-UHFFFAOYSA-N 1-ethenyl-3-methylbenzene Chemical compound CC1=CC=CC(C=C)=C1 JZHGRUMIRATHIU-UHFFFAOYSA-N 0.000 claims description 2
- FXRQXYSJYZPGJZ-UHFFFAOYSA-N 2-[(2-methylpropan-2-yl)oxy]ethenylbenzene Chemical compound CC(C)(C)OC=CC1=CC=CC=C1 FXRQXYSJYZPGJZ-UHFFFAOYSA-N 0.000 claims description 2
- PDELBHCVXBSVPJ-UHFFFAOYSA-N 2-ethenyl-1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=C(C=C)C(C)=C1 PDELBHCVXBSVPJ-UHFFFAOYSA-N 0.000 claims description 2
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 2
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 claims description 2
- KJQMOGOKAYDMOR-UHFFFAOYSA-N CC(=C)C=C.CC(=C)C=C Chemical compound CC(=C)C=C.CC(=C)C=C KJQMOGOKAYDMOR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004606 Fillers/Extenders Substances 0.000 claims description 2
- PJANXHGTPQOBST-VAWYXSNFSA-N Stilbene Natural products C=1C=CC=CC=1/C=C/C1=CC=CC=C1 PJANXHGTPQOBST-VAWYXSNFSA-N 0.000 claims description 2
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- DZRKBPWATCKLKY-UHFFFAOYSA-N n-benzyl-n-methylprop-2-en-1-amine Chemical compound C=CCN(C)CC1=CC=CC=C1 DZRKBPWATCKLKY-UHFFFAOYSA-N 0.000 claims description 2
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 claims description 2
- PJANXHGTPQOBST-UHFFFAOYSA-N stilbene Chemical compound C=1C=CC=CC=1C=CC1=CC=CC=C1 PJANXHGTPQOBST-UHFFFAOYSA-N 0.000 claims description 2
- 235000021286 stilbenes Nutrition 0.000 claims description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 claims 1
- OEVVKKAVYQFQNV-UHFFFAOYSA-N 1-ethenyl-2,4-dimethylbenzene Chemical compound CC1=CC=C(C=C)C(C)=C1 OEVVKKAVYQFQNV-UHFFFAOYSA-N 0.000 claims 1
- QEDJMOONZLUIMC-UHFFFAOYSA-N 1-tert-butyl-4-ethenylbenzene Chemical compound CC(C)(C)C1=CC=C(C=C)C=C1 QEDJMOONZLUIMC-UHFFFAOYSA-N 0.000 claims 1
- MPMBRWOOISTHJV-UHFFFAOYSA-N but-1-enylbenzene Chemical compound CCC=CC1=CC=CC=C1 MPMBRWOOISTHJV-UHFFFAOYSA-N 0.000 claims 1
- UBHHTPOLMACCDD-UHFFFAOYSA-N n,n-dimethyl-4-phenylbut-3-en-1-amine Chemical compound CN(C)CCC=CC1=CC=CC=C1 UBHHTPOLMACCDD-UHFFFAOYSA-N 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 abstract description 2
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 abstract 1
- 229920001971 elastomer Polymers 0.000 description 20
- 239000005060 rubber Substances 0.000 description 20
- 239000003999 initiator Substances 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000005299 abrasion Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 229920002554 vinyl polymer Polymers 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 6
- 238000005859 coupling reaction Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000004073 vulcanization Methods 0.000 description 5
- 238000004566 IR spectroscopy Methods 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229920005669 high impact polystyrene Polymers 0.000 description 4
- 239000004797 high-impact polystyrene Substances 0.000 description 4
- 229920002223 polystyrene Polymers 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- 238000004846 x-ray emission Methods 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 3
- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 3
- 239000004636 vulcanized rubber Substances 0.000 description 3
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 2
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- 239000002879 Lewis base Substances 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- 239000006057 Non-nutritive feed additive Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000011326 mechanical measurement Methods 0.000 description 2
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 2
- 229920002589 poly(vinylethylene) polymer Polymers 0.000 description 2
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Polymers C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 description 2
- 230000008961 swelling Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- OGQVROWWFUXRST-FNORWQNLSA-N (3e)-hepta-1,3-diene Chemical compound CCC\C=C\C=C OGQVROWWFUXRST-FNORWQNLSA-N 0.000 description 1
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- VPBZZPOGZPKYKX-UHFFFAOYSA-N 1,2-diethoxypropane Chemical compound CCOCC(C)OCC VPBZZPOGZPKYKX-UHFFFAOYSA-N 0.000 description 1
- LEEANUDEDHYDTG-UHFFFAOYSA-N 1,2-dimethoxypropane Chemical compound COCC(C)OC LEEANUDEDHYDTG-UHFFFAOYSA-N 0.000 description 1
- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 description 1
- QMGJMGFZLXYHCR-UHFFFAOYSA-N 1-(2-butoxypropoxy)butane Chemical compound CCCCOCC(C)OCCCC QMGJMGFZLXYHCR-UHFFFAOYSA-N 0.000 description 1
- OUSXYCTXXLYBGJ-UHFFFAOYSA-N 1-ethenyl-2,4-di(propan-2-yl)benzene Chemical compound CC(C)C1=CC=C(C=C)C(C(C)C)=C1 OUSXYCTXXLYBGJ-UHFFFAOYSA-N 0.000 description 1
- CBXRMKZFYQISIV-UHFFFAOYSA-N 1-n,1-n,1-n',1-n',2-n,2-n,2-n',2-n'-octamethylethene-1,1,2,2-tetramine Chemical compound CN(C)C(N(C)C)=C(N(C)C)N(C)C CBXRMKZFYQISIV-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- NUMXHEUHHRTBQT-AATRIKPKSA-N 2,4-dimethoxy-1-[(e)-2-nitroethenyl]benzene Chemical compound COC1=CC=C(\C=C\[N+]([O-])=O)C(OC)=C1 NUMXHEUHHRTBQT-AATRIKPKSA-N 0.000 description 1
- MATDIXOGHXOZDW-UHFFFAOYSA-N 2-butoxyoxolane Chemical compound CCCCOC1CCCO1 MATDIXOGHXOZDW-UHFFFAOYSA-N 0.000 description 1
- GDQKLNXQGUDPKS-UHFFFAOYSA-N 2-hexoxyoxolane Chemical compound CCCCCCOC1CCCO1 GDQKLNXQGUDPKS-UHFFFAOYSA-N 0.000 description 1
- OKAMTPRCXVGTND-UHFFFAOYSA-N 2-methoxyoxolane Chemical compound COC1CCCO1 OKAMTPRCXVGTND-UHFFFAOYSA-N 0.000 description 1
- GAODDBNJCKQQDY-UHFFFAOYSA-N 2-methyl-4,6-bis(octylsulfanylmethyl)phenol Chemical compound CCCCCCCCSCC1=CC(C)=C(O)C(CSCCCCCCCC)=C1 GAODDBNJCKQQDY-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
- OHNPPRNQKABHPI-UHFFFAOYSA-N 2-propoxyoxolane Chemical compound CCCOC1CCCO1 OHNPPRNQKABHPI-UHFFFAOYSA-N 0.000 description 1
- VSAWBBYYMBQKIK-UHFFFAOYSA-N 4-[[3,5-bis[(3,5-ditert-butyl-4-hydroxyphenyl)methyl]-2,4,6-trimethylphenyl]methyl]-2,6-ditert-butylphenol Chemical compound CC1=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C(CC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)C(C)=C1CC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 VSAWBBYYMBQKIK-UHFFFAOYSA-N 0.000 description 1
- CJSBUWDGPXGFGA-UHFFFAOYSA-N 4-methylpenta-1,3-diene Chemical compound CC(C)=CC=C CJSBUWDGPXGFGA-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- STUSTWKEFDQFFZ-UHFFFAOYSA-N Chlordimeform Chemical compound CN(C)C=NC1=CC=C(Cl)C=C1C STUSTWKEFDQFFZ-UHFFFAOYSA-N 0.000 description 1
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241001441571 Hiodontidae Species 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZEZSORUWZUMNU-UHFFFAOYSA-N [Li]CCCC[Li] Chemical compound [Li]CCCC[Li] BZEZSORUWZUMNU-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 125000002897 diene group Chemical group 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- BLHLJVCOVBYQQS-UHFFFAOYSA-N ethyllithium Chemical compound [Li]CC BLHLJVCOVBYQQS-UHFFFAOYSA-N 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 150000007527 lewis bases Chemical class 0.000 description 1
- 229920005610 lignin Polymers 0.000 description 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- CETVQRFGPOGIQJ-UHFFFAOYSA-N lithium;hexane Chemical compound [Li+].CCCCC[CH2-] CETVQRFGPOGIQJ-UHFFFAOYSA-N 0.000 description 1
- XBEREOHJDYAKDA-UHFFFAOYSA-N lithium;propane Chemical compound [Li+].CC[CH2-] XBEREOHJDYAKDA-UHFFFAOYSA-N 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 239000012802 nanoclay Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- LGOPTUPXVVNJFH-UHFFFAOYSA-N pentadecanethioic s-acid Chemical compound CCCCCCCCCCCCCCC(O)=S LGOPTUPXVVNJFH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- NHKJPPKXDNZFBJ-UHFFFAOYSA-N phenyllithium Chemical compound [Li]C1=CC=CC=C1 NHKJPPKXDNZFBJ-UHFFFAOYSA-N 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920005604 random copolymer Polymers 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000009877 rendering Methods 0.000 description 1
- 229910000077 silane Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FWMUJAIKEJWSSY-UHFFFAOYSA-N sulfur dichloride Chemical class ClSCl FWMUJAIKEJWSSY-UHFFFAOYSA-N 0.000 description 1
- 125000004354 sulfur functional group Chemical group 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000007970 thio esters Chemical class 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- ABDKAPXRBAPSQN-UHFFFAOYSA-N veratrole Chemical compound COC1=CC=CC=C1OC ABDKAPXRBAPSQN-UHFFFAOYSA-N 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
-
- 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
- C08C19/20—Incorporating sulfur atoms into the molecule
-
- 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
- C08F236/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F236/02—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F236/04—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F236/10—Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated with vinyl-aromatic monomers
-
- 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
- C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
- C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated
- C08F36/06—Butadiene
Definitions
- the present invention is directed to novel sulfur-containing polymers, specifically elastomeric polymers containing one or more polysulfide (i.e. di-, tri-, tetra- or higher sulfide) bridges within the linear polymer chain.
- the invention is also directed to a method of making the sulfur-containing polymer.
- the invention further relates to an uncured, i.e. non-crosslinked, polymer composition comprising the sulfur-containing polymer of the invention.
- the invention relates to the use of the sulfur-containing polymer or uncured polymer composition in selected applications, i.e. for preparing selected cured (crosslinked or vulcanized) elastomeric polymer compositions or rubber goods.
- composition of a cured rubber compound as being part of automobile tires, especially of tire threads, very much influences the running characteristics of such tires.
- various additives may be added and/or special elastomeric polymers can be used. Additives include, for example, processing aids, fillers (such as carbon black), plasticizers, antioxidants, vulcanizing agents, accelerators and activators,
- Crosslinking of the polymer chains by means of a vulcanization system produces a three- dimensional, wide-meshed chemical network, thus rendering the resulting rubber more rigid and tear-resistant, in. particular resistant to tear propagation, depending on the crosslinking density.
- the crosslinking process forms crosslinks between the polymer chains, usually by means of bridges such as sulfur bridges upon sulfur-vulcanized diene rubbers.
- the length of the sulfur bridges will depend on the ratio of sulfur to accelerator, distinguishing between conventional networks (ratio of sulfur/accelerator of 10: 1 to 2: 1 ), semi-efficient networks (2: 1 to 1 :2), and efficient networks (1 :2 to 1 : 10).
- EP 0 316 857 describes an anionic polymerization process using an initiator mixture comprising a di-iithium compound and an organic diamine or triamine.
- the resultmg polymer preferably triblock styrene-isoprene-styrene polymers, are said to exhibit a narrow molecular weight distribution, resulting in increased tensile rupture strength properties of adhesive formulations.
- an elastomeric polymer having, when used in vulcanized rubber composition, improved abrasion resistance and/or rolling resistance, while maintaining or even improving other relevant rubber properties;, including wet grip.
- the invention provides an elastomeric sulfur-containing polymer represented by the following Formula 1 :
- S is a sulfur atom
- P is an elastomeric polymer chain obtained by anionic polymerization of at least one conjugated diene and optionally a vinylaromatic compound in the presence of a diinitiator
- Y is the dicarbanion group derived from the diinitiator
- x is, independently for each group S x , an integer selected from 1 and higher, with the proviso that x is selected from 2, 3 and 4 for at least one group S x ,
- z is an integer selected from 1 to 160, and
- F is independently a terminal group selected from H, -SH, -SOH, -SCI, -SSCi, -S0 2 H and -SO . 3H,
- the invention provides a method of making the e!astomcric sulfur- containing polymer of Formula 1 comprising the steps of:
- step (ii) reacting the anionic living polymer chains of step (i) with sulfur monochloride (S2CI 2 ).
- the invention provides a non-cured polymer composition
- a non-cured polymer composition comprising the elastomeric sulfur-containing polymer of Formula 1 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for preparation of the anionic living polymer chains and (ii) components which remain after solvent removal from the polymerization process.
- the invention provides for the use of the elastomeric sulfur-containing polymer of Formula 1 according to the first aspect of the invention or of the polymer composition according to the third aspect of the invention in (i) footwear, (ii) golf balls, (iii) membranes that do not contain reinforcements (such as but not limited to fibers or fabrics), (iv) adhesives, (v) modified plastics, including polybutadiene-modified acrylonitrile-styrene copolymers (ABS) and high impact polystyrene (polybutadiene-modified polystyrene, HIPS), and (vi) films that are not for automotive interiors or aircraft interiors.
- footwear elastomeric sulfur-containing polymer of Formula 1 according to the first aspect of the invention or of the polymer composition according to the third aspect of the invention
- reinforcements such as but not limited to fibers or fabrics
- adhesives such as but not limited to fibers or fabrics
- modified plastics including polybutadiene-modified acrylonitrile
- the elastomeric sulfur-containing polymer and compositions thereof have beneficial properties especially when used in the manufacture of tires. Specifically, it was surprisingly found that cured polymer compositions ("cured rubber compounds") produced from the elastomeric sulfur-containing polymer of Formula 1 exhibit improved abrasion resistance and roiling resistance, while maintaining or even improving other rubber properties, including wet grip and tensile properties.
- the beneficial properties were in particular found when using and curing ( vulcanizing) a polymer composition of the invention containing both the elastomeric sulfur-containing polymer and additionally one or more inorganic fillers.
- vulcanization using a sulfur-containing vulcanizing agent can be carried out at a reduced level of the vulcanizing agent.
- the elastomeric sulfur-containing polymer of the present invention is generally represented by Formula 1 as defined above.
- the elastomeric polymer chains P contained in the polymer of the invention are obtained by carrying out an anionic polymerization of at least one conjugated die e and optionally a vinylaromatic compound in the presence of a diinitiator.
- the living anionic polymer chains P are subsequently reacted with sulfur monochloride (S2CI2) and, thus, form the elastomeric sulfur-containing polymer of the invention.
- Exemplary conjugated dienes useful in preparing the living anionic polymer chains include 1 ,3 -butadiene, 2-(Ci-Cj alkyl)- 1,3 -butadiene such as isoprene (2- methyl- 1,3 -butadiene), 2,3- dimethyl- 1 ,3 -butadiene, 1 ,3-pentadiene, 2,4-hexadiene, 1 ,3-hexadiene, 1 ,3-heptadiene, 1 ,3- octadiene, 2-methyl-2,4-pentadiene f cyclopentadiene, 2,4-hexadiene and 1 ,3-cyc!ooctadiene.
- 2-(Ci-Cj alkyl)- 1,3 -butadiene such as isoprene (2- methyl- 1,3 -butadiene), 2,3- dimethyl- 1 ,3 -butadiene, 1 ,3-
- conjugated dienes include 1 ,3 -butadiene and isoprene. In one embodiment, the conjugated diene is 1,3- butadiene.
- the vinylaromatic compound includes monoviiiylaromatic compounds, i.e. compounds having only one vinyl group attached to an aromatic group, and di- or higher vinylaromatic compounds which have two or more vinyl groups attached to an aromatic group.
- exemplary vinylaromatic compounds optionally used together with the at least one conjugated diene include styrene, C j.4 alkyl-substituted styrene such as 2-methylstyrene, 3-methylstyrene, 4- methylstyrene, 2,4-dimethylstyreiie, 2,4,6-trimethylstyrene, a-methylstyrene, 2,4- diisopropylstyrene and 4-tert-butyIstyrene, stilbene, vinyl benzyl dimethylamine, (4- vinylbenzyl)dimethy] aminoefhyJ ether, ⁇ , ⁇ -dimethylaminoethyl styrene,
- vinylpyridine and di vinylaromatic compounds such as 1,2-divinylbenzene, 1,3- divinylbenzene and 1,4-divinylbenzene.
- a mixture of two or more vinylaromatic compounds may be used.
- a preferred vinylaromatic compound is a monovinylaromatic compound, more preferably styrene.
- the monovinylaromatic compound(s) may be used in total amounts of up to 70 wt,%, preferably up to 60 wt.% and more preferably up to 50 wt.%, based on the total weight of monomers used in the polymerization reaction for preparing the living anionic polymer ehains.
- the di- or higher vinylaromatic compounds such as divinylbenzene, including 1,2-divinylbenzene, 1 ,3 -divinylbenzene and 1 ,4-divinylben.zene, may be used in total amount of 1 wt.% or less (based on the total molar weight of the monomers used to make the polymer).
- the living anionic polymer chains are obtained from a random copoiymerization of 1,3 -butadiene as the conjugated diene and styrene as the vinylaromatic compound, preferably using styrene in an amount of from 5 to 70 wt.%.
- the diinitiator used in the preparation of the living anionic polymer chains can be any initiator compound known in the art and effecting initiation of the polymerization reaction by providing at least two carbanions in a single initiator molecule. Two or more different diinitiators may be used in combination. Organolithium di initiators are preferred for use in the present invention. Diinitiators useful in the present invention are those disclosed in EP 0 316 857, EP 0 413 294, US 4,182,818, US 4,196,153, US 5,561 ,210, US 5,521 ,255 and WO 2011/047220, each being incorporated herein by reference in its entirety.
- the amount of diinitiator used (total amount) will be selected on the basis of the monomers to be polymerized and the target molecular weight of the living anionic polymer chains. However, the amount is typically 0.05 to 20 mmol, preferably 0.1 to 10 mmol per 100 grams of monomer (total amount of polymerizable monomer).
- the diinitiator may be used in combination with one or more further initiator compounds not falling within, the characterization of a diinitiator.
- Such further initiator compounds include organometal compounds, especially organolithium compounds, such as ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, hexyllithium, 1 ,4-dilithio-n-butane, i ,3-di(2-lithio-2-hexyl)benzene and l,3-di(2-lithio-2- propyl)benzene.
- organolithium compounds such as ethyllithium, propyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, hexyllithium, 1 ,4-dilithio-n-
- n-butyllithium and sec-butyllithium are preferred. If a combination of diinitiator and further initiator compound is used, the amount of the diinitiator is at least 25 mol% 5 based on the total amount of initiator compounds (including diinitiator).
- Polar coordinator compounds as known in the art may optionally be added to the monomer mixture or polymerization reaction, in order to adjust the microstructiire (i.e. the content of vinyl bonds) of the conjugated diene part of the living anionic polymer chains, or to adjust the composition distribution of any viny!aromatic compound in the living anionic polymer chains (thus acting as a randomizer compound), A combination of two or more polar coordinator compounds may be used.
- Polar coordinator compounds useful in the invention are generally exemplified by Lewis base compounds.
- Suitable Lewis bases for use in the present invention are, for example, ether compounds such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, (Cj-Cg alkyl)tetrahydrofurylethers (including methyltetrahydrofurylether.
- ether compounds such as diethyl ether, di-n-butyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dibutyl ether, (Cj-Cg alkyl)tetrahydrofurylethers (including methyltetrahydrofurylether
- ethyltetrahydrofiirylether propyltetrahydrofurylether, butyltetrahydrofurylether, hexyltetrahydrofurylether and octyltetrahydrofurylether
- tetrahydrofuran 2,2-(bistetrahydrofurfuryl)propane
- bistetrahydrofurfurylformal methyl ether of tetrahydrofurfuryl alcohol, ethyl ether of tetrahydrofurfuryl alcohol, butyl ether of tetrahydrofurfuryl alcohol, a- methoxytetrahydrofuran, dimethoxybenzene and dimethoxyethane
- tertiary amines such as triethylamine, pyridine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethyl ethylenediamine, dipiperidinoethane, methyl ether of ⁇ , ⁇ -die
- the polar coordinator compound will typically be added at a molar ratio of polar coordinator compound to initiator compound of from 0.012:1 to 10: 1 , preferably from 0.1 : 1 to 8: 1 and more preferably from 0.25: 1 to about 6:1.
- the polymerization process used for preparing the living anionic polymer chains is preferably conducted as a solution polymerization, wherein the formed polymer is substantially soluble in the reaction mixture, or as a suspension slurry polymerization, wherein, the formed polymer is substantially insoluble in the reaction medium. More preferably, the living anionic polymer chains are obtained in a solution polymerization.
- the solution polymerization normally is carried out at a pressure of not more than 10 MPa (absolute pressure), preferably in a temperature range of from 0 to 120°C.
- the polymerization can be conducted under batch, continuous or semi-continuous polymerization conditions.
- the living anionic polymer chains are reacted with sulfur monochloride (S2CI2) to provide the sulfur-containing elastomeric polymer of Formula 1.
- sulfur monochloride acts as a coupling agent to link two living anionic polymer molecules end-to-end and to produce a linear polymer (as opposed to the S- crosslinked network obtain in a conventional vulcanization reaction using elemental sulfur).
- Sulfur monochloride may be added intermittently (at regular or irregular intervals) or continuously during the polymerization reaction. When asymmetrical coupling is desired, it is preferable to add sulfur monochloride continuously during the polymerization reaction. Such continuous addition is normally effected in a reaction zone separate from the zone where the bulk of the polymerization is taking place. Sulfur monochloride is preferably added to the polymerization reaction at a time when a high degree of conversion of monomer has already been achieved. For example, the coupling agent will normally be added when at least 80% of the monomer has been polymerized. In a preferred embodiment, sulfur chloride is not added until at least 90% of the monomer has been polymerized.
- a substantial amount of the chain ends of the polymer produced in the polymerization process is not terminated when sulfur monochloride is added. That is, living polymer chain ends are present and capable of reacting with the sulfur monochloride in a polymer chain, coupling reaction.
- the coupling reaction may be carried out in a temperature range of from 0°C to 150°C, preferably from 15°C to 120°C and even more preferably from 40°C to 1 (X)°C. There is no limitation for the duration of the coupling reaction. However, with respect to an economical polymerization, process, for example in the case of a batch polymerization process, the coupling reaction is usually stopped at about 1 to 60 minutes after the addition of the sulfur monochloride.
- Sulfur monochloride can be added to the polymerization reaction in the form of a solution in a hydrocarbon solvent, for example in cyclohexane, with suitable mixing for distribution and reaction.
- sulfur monochloride is used in an amount of from 0.01 to 10 mol, preferably from 0.05 to 8 mol and more preferably from 0,2 to 5 mol for every 10 moles of living anionic polymer chain, ends.
- reaction mixture typically involves removal of polymerization and/or reaction, solvent by steam stripping or vacuum evaporation techniques and will determine the type of the terminal groups F of the elastomeric sulfur-containing polymer of Formula 1.
- an anionic chain end may not have reacted with sulfur monochloride and is protonated during work-up, resulting in F being hydrogen, or is may have reacted with sulfur monochloride, without further linkage to another anionic living polymer chain, so that sulfur monochloride or a derivative thereof acts as an end-capping agent.
- the elastomeric sulfur-containing polymer of the invention is represented by Formula 1 as defined herein.
- z is an integer selected from 1 to 80, more preferably from 1 to 40, In one embodiment, z is at least 2.
- x is an integer selected from 1 to 8, more preferably from 1 to 6, even more preferably from 1 to 4, with the proviso that x is an integer selected from 2, 3 and 4 for at least one group S x .
- z is an integer selected from 1 to 40 and x is an integer selected from 1 to 4, with the proviso as above.
- the elastomeric sulfur-containing polymer of the invention is a styrene-butadtene copolymer represented by the following Formula 2:
- SBR is an elastomeric polymer chain obtained by anionic polymerization of 1,3-butadiene and styrene in the presence of a diinitiator
- styrene typically constitutes from 5 to 70 % by weight, preferably from 5 to 60% by weight and more preferably from 5 to 50 % by weight, based on the total weight of the polymer.
- An amount of less than 5 % by weight of styrene may result in a deteriorated balance of rolling resistance, wet skid and abrasion resistance, and in reduced tensile strength, whereas an amount of more than 70 % by weight may lead to increased hysteresis loss.
- the elastomeric sulfur containing polymer of Formula 2 may be a block or random copolymer. Preferably 40 % by weight or more of the styrene repeating units are linked singly, and 10 % by weight or less are "blocks" of eight or more styrene monomers linked successively. A polymer falling outside these limits may exhibit increased hysteresis loss.
- the length of successively linked vinyl aromatic units, including styrene repeating units, can be determined by an ozonolysis-gel permeation chromatography method developed by Tanaka et al. (Polymer, Vol. 22, Pages 1721 -1723 (1981)).
- the elastomeric sulfur-containing polymer of Formula 1 of the present invention usually contains sulfur in a total amount of from 0.10 to 30 g/kg of polymer, preferably from 0.1 to 10 g/kg and more preferably from 0.5 to 3 g/kg.
- sulfur in a total amount of from 0.10 to 30 g/kg of polymer, preferably from 0.1 to 10 g/kg and more preferably from 0.5 to 3 g/kg.
- the content of 1 ,2-bonds (vinyl bond content") in the butadiene part of the polymer, it is preferably from 2 to 90 % by weight, particularly preferably from 5 to 75 % by weight for most applications, based on the total weight of the polymer.
- a vulcanized rubber compound obtained from the polymer may have an inferior balance of wet skid resistance, roiling resistance and abrasion resistance.
- a vulcanized rubber compound obtained from the polymer may exhibit inferior tensile strength and abrasion resistance and a relatively high hysteresis loss.
- the elastomeric sulfur- containing polymer of the present invention preferably has a Mooney viscosity of up to 150 MU, preferably up to 120 MU and more preferably from 20 to 120 MU (ML 1+4, 100°C; determined in accordance with ASTM D 1646 (2004) using a Monsanto MV2000 instrument). If the Mooney viscosity of the elastomeric sulfur-containing polymer is more than.
- the processability as reflected by filler incorporation and heat build-up in the internal mixer, banding on the roll mill, extrusion rate, extrudate die swell and smoothness, is likely to be negatively affected because the compounding machinery used by the tire manufacturers are not designed to handle such high Mooney rubber grades, and the time and costs of processing increases.
- a Mooney viscosity of less than 20 may not be preferred due to increased tack and cold flow of the uncross! inked elastomeric polymer, resulting in difficult handling, poor green strength and poor dimensional stability during storage.
- a Mooney viscosity of less than 20 may be preferred.
- the number average molecular weight of the elastomeric sulfor-containing polymer of the invention is usually in the range of 5 to 2000 kg/mol, preferably from. 10 to 1500 kg/mol and more preferably from 15 to 1.000 kg mol.
- the elastomeric sulfur-containing polymer of Formula 1 is prepared in a method comprising the steps of:
- step (ii) reacting the anionic living polymer chains of step (i) with sulfur monochloride (S 2 G 2 ).
- the method provides an elastomeric sulfur-containing polymer of Formula 2, as defined herein, and comprises the steps of;
- step (ii) reacting the anionic living styrene-butadiene copolymer chains of step (i) with sulfur monochloride (S2CI.2).
- the non-cured polymer composition of the present invention comprises the elastomeric sulfur-containing polymer of Formula 1 and one or more further components selected from (i) components which are added to or formed as a result of the polymerization process used for preparation of the anionic living polymer chains and (ii) components which remain after solvent removal from, the polymerization process.
- the elastomeric sulfur- containing polymer contained in the polymer composition is represented by Formula 2 as defined herein.
- the non-cured (non-crosslinked or unvulcanized) polymer composition is typically obtained by conventional work-up of the reaction mixture obtained after reaction of the anionic living polymer chains with sulfur monochloride. Work-up means the removal of the solvent using steam stripping or vacuum evaporation techniques.
- Components which are added to or formed as a result of the polymerization process include, in particular, oils (extender oils), stabilizers, fillers and further polymers.
- oils can be added to the polymer prior to or after the termination of the polymerization process.
- oils see WO 2009/148932 and US 2005/0159513, each of which is incorporated herein by reference in its entirety.
- One or more stabilizers can optionally be added to the polymer prior to or after the termination of the polymerization process to prevent the degradation of the elastomeric polymer by molecular oxygen.
- Antioxidants based on sterically hindered phenols such as 2,6-di-tert-bntyl-4-methylphenoI 5 6 > 6'-methyIenebis(2-tert-butyI-4-methylphenol) > Iso- octyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, hexamethylenebis[3-(3 s 5 ⁇ di ⁇ tert- butyl-4-hydroxyphenyl)propionate] , octadecyl-3 -(3 ,5-di-tert-butyl-4-hydroxyphenyl) propionate, isotridecyi-3-(3,5-di-tert-buty -hydroxypheny])
- One or more fillers can be added to the polymer prior to or after the termination of the polymerization process.
- suitable fillers include carbon black (including electroconductive carbon black),, carbon nanotubes (CNT) (including discrete CNT, hollow carbon fibers (HCF) and modified CNT carrying one or more functional groups, such as hydroxy!, car boxy I and earbonyl groups), graphite, graphene (including discrete graphene platelets), silica, carbon-silica dual-phase filler, clays (layered silicates, including exfoliated nanoclay and organoclay), calcium carbonate, magnesium carbonate, lignin, amorphous fillers, such as glass particle-based fillers, starch-based fillers, and combinations thereof. Further examples of suitable fillers are described in WO 2009/148932 which is fully incorporated herein by reference.
- polymers as part of the polymer composition of the invention are, in particular, polymers which are formed in the polymerization process but which are not in accordance with Formula 1 of the present invention.
- the elastomcric sulfur-containing polymer of Formula 1 of the invention, including the polymer of Formula 2, and the respective polymer composition comprising such polymer are beneficially used in and for preparing (i) footwear, (ii) golf balls, (iii) membranes that do not contain reinforcements (such as but not limited to fibers or fabrics), (iv) adhesives, (v) modified plastics, including polybutadiene-modified acrylonitrile-styrene copolymers (ABS) and high impact polystyrene (polybutadiene-modified polystyrene, HIPS), and (vi) films that are not for automotive interiors or aircraft interiors.
- ABS polybutadiene-modified acrylonitrile-styrene copolymers
- HIPS high impact polystyren
- Root temperature refers to a temperature of about 20-25°C, or to 20°C when the measurement of a specific parameter is concerned,
- the vinyl bond content in the butadiene part of the (co)polymer was determined by IR absorption spectrometry (Morello method, I S 66 FT-IR spectrometer, Bruker Analytic GmbH).
- the IR samples were prepared using CS 2 as a swelling agent.
- Bonded styrene content A calibration curve was prepared by IR absorption spectrometry (IFS 66 FT-IR spectrometer). The IR samples were prepared using CS 2 as a swelling agent. For the IR determination of bonded styrene in styrene-butadiene copolymers, four bands were assessed: a) for trans- 1 ,4-pol butadiene units at 966 cm "1 , b) for cis- 1 ,4-polybutadiene units at 730 cm “1 , c) for 1 ,2-polybutadiene units at 910 cm 4 , and d) for bonded styrene (styrene aromatic bond) at 700 cm "5 .
- the band heights are normalized according to the appropriate extinction coefficients and added to a total of 100%.
- the normalization is done via ⁇ - and ,3 C-NMR.
- Sulfur content was determined by X-ray fluorescence spectrometry (XRF) on an Axios spectrometer (PANalyticai). Data analysis were done with the software PCFPW from Fundex. Samples were prepared in a hot press and measured immediately,
- GPC-Method SEC calibrated with narrow distributed polystyrene standard.
- each GPC device 3 columns of 300 mm length each were used in a connected mode (Column Type 7991 1 GP- MXB, Pigel 10 pm MIXED-B GPC/SEC Columns, Agilent Technologies)
- GPC Standards EasiCai PS-1 Polystyrene Standards, Spatula A F B
- Mw/Mn PolydispersitY
- the Mpl -Mp4 values correspond to the molecular weight measured at the first, second, third or fourth peaks of the GPC curve [the first peak M l (lowest molecular weight) is located on the right side of the curve, and the last peak (highest molecular weight) is located on the left side of the curve], respectively.
- Tg glass transition
- Polymerizations and the synthesis of the initiator II were performed in a nitrogen atmosphere under exclusion of moisture and oxygen.
- S 2 CI 2 Sulfur monochloride
- the copolymerizations were performed in a double wall, 10 liter steel reactor, which was first purged with nitrogen, before adding of organic solvent, monomers, polar coordinator compound, initiator compound and other components. The following components were then added, in this order: cyclohexane solvent (4600 grams); butadiene monomer, styrene monomer, tetramethylethylene diamine (TMEDA) and the mixture was heated to 40°C, followed by titration with n-butyl lithium to remove traces of moisture or other impurities, The polymerization initiator compound (II or n-BuLi) was added into the polymerization reactor to initiate the polymerization reaction.
- cyclohexane solvent 4600 grams
- butadiene monomer styrene monomer
- TMEDA tetramethylethylene diamine
- the polymerization was performed for 80 minutes, not allowing the polymerization temperature to exceed 60°C. Next, 2.3% (Examples 1-3, 5, 6) or 0.5% (Example 4) of the total butadiene monomer amount was added, followed by the addition of the coupling agent, unless stated otherwise. After 5 minutes (Examples 2, 3) or 10 minutes (Examples 1 , 4-6), the polymerization was terminated by the addition of methanol (one equivalent based on initiator). 0.25 wt% IRGANOX 1520 based on the total monomer weight was added as a stabilizer to the polymer solution. This mixture was stirred for 10 minutes.
- vinyl content is that of the 1 ,2-polybutadiene unit content of the final copolymer, and is determined by IR Spectroscopy
- Polymer compositions were prepared from the polymers of Examples 2 and 4.
- the polymer of Example 2 is an. e!astomeric sulfur-containing polymer according to the invention, whereas the polymer of Example 4 is a comparative polymer not in accordance with the invention. All indications of amounts are based on weight, relative to 100 parts by weight of total rubber (phr), or relative to 100 parts by weight of silica (phf).
- compositions were prepared in the conventional manner in two stages in a lab tangential blender.
- Rubber compound El contains 100 phr of the polymer of Example 2.
- Rubber compound VI uses the polymer of Example 4 instead, which has a similar molecular weight and contains SBR polymer segments, yet linked via silicon atoms instead of the di-, tri or tetrasulfide units according to the present invention. As a result, the polymer segments of Example 4 do not contain sulfur- ulcanizable groups.
- a similar hardness (Shore A at room temperature) was established by adjusting the amounts of sulfur and accelerator.
- Test pieces were prepared from each composition by vulcanization, and tested for typical physical properties in the rubber industry, using the following test methods:
- Tg Glass transition temperature (Tg) derived from loss factor tan ⁇ obtained from dynamic- mechanical measurement according to DIN 53 513 (temperature sweep)
- rubber compound El made with a polymer of the invention has, at almost identical Tg. a substantially higher impact resilience at 70 °C than the comparative rubber compound VI, indicating a much improved (reduced) rolling resistance of El versus VI .
- rubber compound El exhibits improved abrasion resistance (reduced abrasion) and increased tensile strength over rubber compound VI , At the same, the remaining physical properties can be maintained at almost the same level.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2013/077700 WO2015090447A1 (en) | 2013-12-20 | 2013-12-20 | Sulfur-containing polymers |
EP13821106.5A EP3083270A1 (en) | 2013-12-20 | 2013-12-20 | Sulfur-containing polymers |
TW103137027A TW201525006A (zh) | 2013-12-20 | 2014-10-27 | 含硫聚合物 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/EP2013/077700 WO2015090447A1 (en) | 2013-12-20 | 2013-12-20 | Sulfur-containing polymers |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2015090447A1 true WO2015090447A1 (en) | 2015-06-25 |
Family
ID=49956147
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2013/077700 WO2015090447A1 (en) | 2013-12-20 | 2013-12-20 | Sulfur-containing polymers |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP3083270A1 (zh) |
TW (1) | TW201525006A (zh) |
WO (1) | WO2015090447A1 (zh) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160297948A1 (en) * | 2013-12-20 | 2016-10-13 | Continental Reifen Deutschland Gmbh | Rubber mixture and vehicle tire |
FR3068357A1 (fr) * | 2017-06-30 | 2019-01-04 | Compagnie Generale Des Etablissements Michelin | Compositions de caoutchouc ayant une bonne tenue au fluage |
WO2019115470A1 (fr) * | 2017-12-11 | 2019-06-20 | Compagnie Generale Des Etablissements Michelin | Procédé de synthèse d'un polymère fonctionnel ou non à structure particulière |
CN111978447A (zh) * | 2019-05-21 | 2020-11-24 | 中国石油化工股份有限公司 | 低顺式聚丁二烯橡胶及制备方法和应用以及芳族乙烯基树脂及制备方法 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1260794B (de) * | 1963-08-06 | 1968-02-08 | Bayer Ag | Verfahren zur Herstellung kautschukelastischer Dienpolymerer mit verbesserten Eigenschaften |
US5567784A (en) * | 1994-10-10 | 1996-10-22 | Bayer Ag | Process for producing diene rubbers polymerized by means of Nd catalysts and exhibiting reduced cold flow and low intrinsic odor |
WO2013127448A1 (en) * | 2012-02-29 | 2013-09-06 | Styron Europe Gmbh | Process for producing diene polymers |
-
2013
- 2013-12-20 WO PCT/EP2013/077700 patent/WO2015090447A1/en active Application Filing
- 2013-12-20 EP EP13821106.5A patent/EP3083270A1/en not_active Withdrawn
-
2014
- 2014-10-27 TW TW103137027A patent/TW201525006A/zh unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1260794B (de) * | 1963-08-06 | 1968-02-08 | Bayer Ag | Verfahren zur Herstellung kautschukelastischer Dienpolymerer mit verbesserten Eigenschaften |
US5567784A (en) * | 1994-10-10 | 1996-10-22 | Bayer Ag | Process for producing diene rubbers polymerized by means of Nd catalysts and exhibiting reduced cold flow and low intrinsic odor |
WO2013127448A1 (en) * | 2012-02-29 | 2013-09-06 | Styron Europe Gmbh | Process for producing diene polymers |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20160297948A1 (en) * | 2013-12-20 | 2016-10-13 | Continental Reifen Deutschland Gmbh | Rubber mixture and vehicle tire |
US9701809B2 (en) * | 2013-12-20 | 2017-07-11 | Continental Reifen Deutschland Gmbh | Rubber mixture and vehicle tire |
FR3068357A1 (fr) * | 2017-06-30 | 2019-01-04 | Compagnie Generale Des Etablissements Michelin | Compositions de caoutchouc ayant une bonne tenue au fluage |
WO2019115470A1 (fr) * | 2017-12-11 | 2019-06-20 | Compagnie Generale Des Etablissements Michelin | Procédé de synthèse d'un polymère fonctionnel ou non à structure particulière |
CN111978447A (zh) * | 2019-05-21 | 2020-11-24 | 中国石油化工股份有限公司 | 低顺式聚丁二烯橡胶及制备方法和应用以及芳族乙烯基树脂及制备方法 |
CN111978447B (zh) * | 2019-05-21 | 2023-04-11 | 中国石油化工股份有限公司 | 低顺式聚丁二烯橡胶及制备方法和应用以及芳族乙烯基树脂及制备方法 |
Also Published As
Publication number | Publication date |
---|---|
TW201525006A (zh) | 2015-07-01 |
EP3083270A1 (en) | 2016-10-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6796903B2 (ja) | 変性共役ジエン系重合体及びその製造方法、ゴム組成物、並びにタイヤ | |
CN102933613B (zh) | 改性聚合物组合物 | |
JP6769780B2 (ja) | 変性共役ジエン系重合体及びそのゴム組成物、並びにタイヤ | |
CN109563184B (zh) | 改性共轭二烯系聚合物、橡胶组合物以及轮胎 | |
JP6058013B2 (ja) | 変性共役ジエン重合体及びその製造方法 | |
JP5831461B2 (ja) | 共役ジエン系ゴム、ゴム組成物、ゴム架橋物、およびタイヤ | |
CN108699181B (zh) | 基于[双(三烃基硅烷基)氨基硅烷基]官能化苯乙烯的弹性体共聚物及其用于橡胶制备 | |
US11207918B2 (en) | Modified conjugated diene-based polymer and rubber composition thereof, and tire | |
CN111936536B (zh) | 共轭二烯系聚合物、支化剂、共轭二烯系聚合物的制造方法、充油共轭二烯系聚合物、橡胶组合物以及轮胎 | |
KR102471389B1 (ko) | 타이어용 작용기화 중합체 블렌드 | |
CN111201255B (zh) | 改性共轭二烯类聚合物和包含该改性共轭二烯类聚合物的橡胶组合物 | |
WO2015055252A1 (en) | Vinylsilanes for use in functionalized elastomeric polymers | |
CN115298225A (zh) | 氢化共轭二烯系聚合物、氢化共轭二烯系聚合物组合物和橡胶组合物以及氢化共轭二烯系聚合物的制造方法 | |
WO2015090447A1 (en) | Sulfur-containing polymers | |
JP6503075B2 (ja) | 変性共役ジエン系重合体、この製造方法及びこれを含むゴム組成物 | |
JP2004107384A (ja) | 共役ジエン系ゴム、ゴム組成物、及び共役ジエン系ゴムの製造方法 | |
CN108137715B (zh) | 用于制备官能化聚合物的方法 | |
EP3263605B1 (en) | Method for preparing modified conjugated diene rubber | |
JP2019094390A (ja) | 変性共役ジエン系重合体の製造方法、重合体組成物、架橋体及びタイヤ | |
JP6724018B2 (ja) | 機能化弾性ポリマー組成物、その製造方法及びその架橋ゴム組成物 | |
JPH0580503B2 (zh) | ||
EP4229099A1 (en) | Polymers with sulfur containing end groups | |
KR102121881B1 (ko) | 방사상 공액 디엔계 고무의 제조 방법 | |
CN108323168B (zh) | 改性单体、含有该改性单体的改性共轭二烯类聚合物及其制备方法 | |
KR20180080108A (ko) | 변성 공액디엔계 중합체 및 이를 포함하는 고무 조성물 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13821106 Country of ref document: EP Kind code of ref document: A1 |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REEP | Request for entry into the european phase |
Ref document number: 2013821106 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2013821106 Country of ref document: EP |