DE60226270T2 - Verfahren zur herstellung von butadien/isopren-copolymeren und dabei erhaltene copolymere - Google Patents
Verfahren zur herstellung von butadien/isopren-copolymeren und dabei erhaltene copolymere Download PDFInfo
- Publication number
- DE60226270T2 DE60226270T2 DE60226270T DE60226270T DE60226270T2 DE 60226270 T2 DE60226270 T2 DE 60226270T2 DE 60226270 T DE60226270 T DE 60226270T DE 60226270 T DE60226270 T DE 60226270T DE 60226270 T2 DE60226270 T2 DE 60226270T2
- Authority
- DE
- Germany
- Prior art keywords
- butadiene
- isoprene
- catalytic system
- random copolymer
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims abstract description 135
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Natural products CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 229920001577 copolymer Polymers 0.000 title claims abstract description 28
- 238000004519 manufacturing process Methods 0.000 title 1
- 238000000034 method Methods 0.000 claims abstract description 52
- 230000003197 catalytic effect Effects 0.000 claims abstract description 48
- 239000002904 solvent Substances 0.000 claims abstract description 31
- -1 alkylaluminium halide Chemical class 0.000 claims abstract description 22
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 22
- 150000003839 salts Chemical class 0.000 claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 20
- 229920005604 random copolymer Polymers 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 17
- 229940100198 alkylating agent Drugs 0.000 claims abstract description 15
- 239000002168 alkylating agent Substances 0.000 claims abstract description 15
- 239000000725 suspension Substances 0.000 claims abstract description 13
- 150000001993 dienes Chemical class 0.000 claims abstract description 9
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 9
- 150000002367 halogens Chemical class 0.000 claims abstract description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 8
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 8
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 6
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 5
- 125000005234 alkyl aluminium group Chemical group 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 20
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 19
- 238000006116 polymerization reaction Methods 0.000 claims description 18
- 230000009477 glass transition Effects 0.000 claims description 12
- 238000005259 measurement Methods 0.000 claims description 12
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 11
- 239000005062 Polybutadiene Substances 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000004455 differential thermal analysis Methods 0.000 claims description 8
- 238000005481 NMR spectroscopy Methods 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 6
- OKTJSMMVPCPJKN-OUBTZVSYSA-N Carbon-13 Chemical compound [13C] OKTJSMMVPCPJKN-OUBTZVSYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 5
- 239000007983 Tris buffer Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 3
- YNLAOSYQHBDIKW-UHFFFAOYSA-M diethylaluminium chloride Chemical compound CC[Al](Cl)CC YNLAOSYQHBDIKW-UHFFFAOYSA-M 0.000 claims description 3
- 229920002857 polybutadiene Polymers 0.000 claims description 3
- 229920001195 polyisoprene Polymers 0.000 claims description 3
- 229930195734 saturated hydrocarbon Natural products 0.000 claims description 2
- 229920006301 statistical copolymer Polymers 0.000 claims 3
- 150000003016 phosphoric acids Chemical class 0.000 abstract 1
- 229920006395 saturated elastomer Polymers 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 19
- 239000000243 solution Substances 0.000 description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 11
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 10
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 10
- 238000003786 synthesis reaction Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000000203 mixture Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 150000001206 Neodymium Chemical class 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000000806 elastomer Substances 0.000 description 5
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 4
- CQQUWTMMFMJEFE-UHFFFAOYSA-N 2-chloro-n,n-diethylacetamide Chemical compound CCN(CC)C(=O)CCl CQQUWTMMFMJEFE-UHFFFAOYSA-N 0.000 description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 4
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 229910052740 iodine Inorganic materials 0.000 description 4
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 238000009417 prefabrication Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 229910017493 Nd 2 O 3 Inorganic materials 0.000 description 3
- 238000005804 alkylation reaction Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000004448 titration Methods 0.000 description 3
- SDJHPPZKZZWAKF-UHFFFAOYSA-N 2,3-dimethylbuta-1,3-diene Chemical compound CC(=C)C(C)=C SDJHPPZKZZWAKF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 239000005662 Paraffin oil Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000029936 alkylation Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001805 chlorine compounds Chemical class 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000007614 solvation Methods 0.000 description 2
- 239000011550 stock solution Substances 0.000 description 2
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-UHFFFAOYSA-N 0.000 description 2
- NLSXASIDNWDYMI-UHFFFAOYSA-N triphenylsilanol Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(O)C1=CC=CC=C1 NLSXASIDNWDYMI-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- APPOKADJQUIAHP-GGWOSOGESA-N (2e,4e)-hexa-2,4-diene Chemical compound C\C=C\C=C\C APPOKADJQUIAHP-GGWOSOGESA-N 0.000 description 1
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- PJXJBPMWCKMWLS-UHFFFAOYSA-N 2-methyl-3-methylidenepent-1-ene Chemical compound CCC(=C)C(C)=C PJXJBPMWCKMWLS-UHFFFAOYSA-N 0.000 description 1
- OAOZZYBUAWEDRA-UHFFFAOYSA-N 3,4-dimethylidenehexane Chemical compound CCC(=C)C(=C)CC OAOZZYBUAWEDRA-UHFFFAOYSA-N 0.000 description 1
- ZZMVLMVFYMGSMY-UHFFFAOYSA-N 4-n-(4-methylpentan-2-yl)-1-n-phenylbenzene-1,4-diamine Chemical compound C1=CC(NC(C)CC(C)C)=CC=C1NC1=CC=CC=C1 ZZMVLMVFYMGSMY-UHFFFAOYSA-N 0.000 description 1
- UZGARMTXYXKNQR-UHFFFAOYSA-K 7,7-dimethyloctanoate;neodymium(3+) Chemical compound [Nd+3].CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O.CC(C)(C)CCCCCC([O-])=O UZGARMTXYXKNQR-UHFFFAOYSA-K 0.000 description 1
- BDDLHHRCDSJVKV-UHFFFAOYSA-N 7028-40-2 Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O BDDLHHRCDSJVKV-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 description 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 description 1
- 235000010703 Modiola caroliniana Nutrition 0.000 description 1
- 244000038561 Modiola caroliniana Species 0.000 description 1
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- IRYSNLPWOIOTED-UHFFFAOYSA-N acetic acid ethane-1,2-diamine Chemical compound CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O.NCCN.NCCN IRYSNLPWOIOTED-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- AZWXAPCAJCYGIA-UHFFFAOYSA-N bis(2-methylpropyl)alumane Chemical compound CC(C)C[AlH]CC(C)C AZWXAPCAJCYGIA-UHFFFAOYSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- XZKRXPZXQLARHH-UHFFFAOYSA-N buta-1,3-dienylbenzene Chemical compound C=CC=CC1=CC=CC=C1 XZKRXPZXQLARHH-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 230000009918 complex formation Effects 0.000 description 1
- 238000003926 complexometric titration Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 235000014510 cooky Nutrition 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000005281 excited state Effects 0.000 description 1
- 238000000556 factor analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 1
- 238000013178 mathematical model Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- XRVMAUGYKFDXKO-UHFFFAOYSA-K octanoate;praseodymium(3+) Chemical compound [Pr+3].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O.CCCCCCCC([O-])=O XRVMAUGYKFDXKO-UHFFFAOYSA-K 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000010238 partial least squares regression Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920002587 poly(1,3-butadiene) polymer Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000003223 protective agent Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229940099259 vaseline Drugs 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 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
- 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
-
- 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
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/54—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with other compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerization Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR0115888 | 2001-12-07 | ||
| FR0115888 | 2001-12-07 | ||
| PCT/EP2002/013709 WO2003048221A1 (fr) | 2001-12-07 | 2002-12-04 | Procede de preparation de copolymeres butadiene/isoprene et ces copolymeres |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE60226270D1 DE60226270D1 (de) | 2008-06-05 |
| DE60226270T2 true DE60226270T2 (de) | 2009-07-16 |
Family
ID=8870258
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE60226270T Expired - Lifetime DE60226270T2 (de) | 2001-12-07 | 2002-12-04 | Verfahren zur herstellung von butadien/isopren-copolymeren und dabei erhaltene copolymere |
Country Status (12)
| Country | Link |
|---|---|
| US (2) | US7115693B2 (https=) |
| EP (1) | EP1456260B1 (https=) |
| JP (2) | JP4741185B2 (https=) |
| KR (2) | KR100939651B1 (https=) |
| CN (1) | CN1273508C (https=) |
| AT (1) | ATE393176T1 (https=) |
| AU (1) | AU2002361972A1 (https=) |
| BR (1) | BR0214685B1 (https=) |
| DE (1) | DE60226270T2 (https=) |
| ES (1) | ES2305339T3 (https=) |
| RU (1) | RU2301236C2 (https=) |
| WO (1) | WO2003048221A1 (https=) |
Families Citing this family (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5111101B2 (ja) * | 2004-03-02 | 2012-12-26 | 株式会社ブリヂストン | バルク重合プロセス |
| DE102004022676A1 (de) * | 2004-05-07 | 2005-12-15 | Bayer Ag | Hydrierte Copolymerisate aus nicht substituierten und substituierten konjugierten Dienen |
| FR2886937B1 (fr) * | 2005-06-14 | 2007-08-10 | Michelin Soc Tech | Procede de preparation d'un elastomere dienique, tel qu'un polybutadiene |
| US20080090852A1 (en) * | 2006-10-13 | 2008-04-17 | Colin Andrew Leach | Bicyclic Heteroaromatic Compounds |
| US7705005B2 (en) * | 2006-10-13 | 2010-04-27 | Glaxo Group Limited | Bicyclic heteroaromatic compounds |
| US20080090851A1 (en) * | 2006-10-13 | 2008-04-17 | Colin Andrew Leach | Bicyclic Heteroaromatic Compounds |
| DE102007050119A1 (de) * | 2007-10-19 | 2009-04-23 | Robert Bosch Gmbh | Speichervorrichtung, Sensorelement und Verfahren zur qualitativen und/oder quantitativen Bestimmung mindestens einer Gaskomponente, insbesondere von Stickoxiden, in einem Gas |
| US7820580B2 (en) | 2007-11-15 | 2010-10-26 | Bridgestone Corporation | Nickel-based catalysts for preparing high cis 1,4-polydienes |
| RU2515980C2 (ru) * | 2007-12-31 | 2014-05-20 | Бриджстоун Корпорейшн | Способ получения полидиенов полимеризацией в объеме |
| US8394901B2 (en) | 2008-04-29 | 2013-03-12 | Changchun Institute Of Applied Chemistry Chinese Academy Of Sciences | Bi-component catalyst system for isoprene or butadiene cis 1, 4-polymerization and polymerization process |
| EP2291415B1 (en) | 2008-06-20 | 2016-07-20 | Bridgestone Corporation | Catalysts for preparing cis 1,4-polydienes |
| EP2470574B1 (en) * | 2009-08-24 | 2014-09-17 | Bridgestone Corporation | Process and catalyst system for polydiene production |
| CN102234356B (zh) * | 2010-04-30 | 2013-03-06 | 青岛伊科思新材料股份有限公司 | 稀土戊丁橡胶的生产方法 |
| CN101831032B (zh) * | 2010-05-19 | 2012-05-02 | 中国科学院长春应用化学研究所 | 一种丁二烯异戊二烯共聚物的制备方法 |
| WO2014010249A1 (ja) * | 2012-07-12 | 2014-01-16 | 株式会社ブリヂストン | 重合体組成物の製造方法及び重合体組成物 |
| CN104428332B (zh) * | 2012-07-12 | 2016-09-14 | 株式会社普利司通 | 异戊二烯共聚物及其制造方法 |
| CN103626926B (zh) * | 2012-08-21 | 2016-03-30 | 中国石油化工股份有限公司 | 一种聚丁二烯接枝异戊橡胶及其制备方法和硫化胶及混炼胶 |
| CN103665197B (zh) * | 2012-09-18 | 2015-12-02 | 中国石油天然气股份有限公司 | 一种均相稀土催化剂及其在共轭二烯烃聚合中的应用 |
| CN104130350B (zh) * | 2013-05-02 | 2017-08-22 | 中国石油化工股份有限公司 | 一种丁二烯‑异戊二烯共聚物橡胶及其制备方法 |
| TWI522378B (zh) * | 2013-12-13 | 2016-02-21 | 奇美實業股份有限公司 | 改質的高順式丁二烯－異戊二烯系共聚物、其製造方法及含有前述聚合物的輪胎 |
| CN103980425B (zh) * | 2014-06-09 | 2019-03-12 | 华宇橡胶有限责任公司 | 高顺式含量丁二烯-异戊二烯共聚物的制备方法 |
| US20170335032A1 (en) * | 2014-11-17 | 2017-11-23 | Bridgestone Corporation | Bulk polymerization of polyisoprene with preformed catalyst |
| IT201800005841A1 (it) * | 2018-05-30 | 2019-11-30 | Procedimento per la preparazione di copolimeri random butadiene-isoprene ad elevato contenuto di unita’ 1,4-cis | |
| CN112552451B (zh) * | 2019-09-25 | 2022-08-19 | 中国石油化工股份有限公司 | 无规丁二烯-异戊二烯共聚物及其合成方法和低滚阻汽车轮胎胎面胶 |
| EP3838932B1 (en) | 2019-12-20 | 2022-08-10 | The Goodyear Tire & Rubber Company | Synthesis of isoprene-butadiene copolymer rubbers |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3541063A (en) * | 1967-12-29 | 1970-11-17 | Goodyear Tire & Rubber | Process for the polymerization of diolefins with a catalyst comprising alkylaluminum compounds,group iii-b organo metal compounds and organoaluminum fluoride compounds |
| JPS6023406A (ja) * | 1983-07-18 | 1985-02-06 | Asahi Chem Ind Co Ltd | ポリブタジエンの製造方法 |
| US5405815A (en) * | 1993-06-17 | 1995-04-11 | The Goodyear Tire & Rubber Company | Process for preparing a catalyst system useful in the synthesis of isoprene-butadiene rubber |
| RU2087488C1 (ru) * | 1994-03-16 | 1997-08-20 | Акционерное общество открытого типа "Ефремовский завод синтетического каучука" | Способ получения цис-1,4-полибутадиена и цис-1,4-сополимера бутадиена и изопрена |
| JP4067592B2 (ja) * | 1996-12-04 | 2008-03-26 | Ｊｓｒ株式会社 | 共役ジエン系重合体の製造方法 |
| RU2127281C1 (ru) * | 1997-03-11 | 1999-03-10 | Акционерное общество открытого типа "Ефремовский завод синтетического каучука" | Способ получения цис-1,4-полибутадиена и цис-1,4-сополимера бутадиена и изопрена |
| RU2127280C1 (ru) * | 1997-03-11 | 1999-03-10 | Акционерное общество открытого типа "Ефремовский завод синтетического каучука" | Способ получения цис-1,4-полибутадиена и цис-1,4-сополимера бутадиена и изопрена |
| JP2001048940A (ja) * | 1999-08-06 | 2001-02-20 | Nippon Zeon Co Ltd | ブタジエン系重合体及びその製造方法 |
| CA2427984A1 (fr) * | 2000-11-09 | 2002-05-16 | Michelin Recherche Et Technique S.A. | Systeme catalytique et procede de preparation d'elastomeres au moyen de ce systeme |
| US7022783B2 (en) * | 2001-12-31 | 2006-04-04 | The Goodyear Tire & Rubber Company | Group III-B metal catalyst system |
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2002
- 2002-12-04 KR KR1020097008323A patent/KR100939651B1/ko not_active Expired - Fee Related
- 2002-12-04 EP EP02796566A patent/EP1456260B1/fr not_active Expired - Lifetime
- 2002-12-04 KR KR1020047008774A patent/KR100904627B1/ko not_active Expired - Fee Related
- 2002-12-04 DE DE60226270T patent/DE60226270T2/de not_active Expired - Lifetime
- 2002-12-04 RU RU2004120699/04A patent/RU2301236C2/ru not_active IP Right Cessation
- 2002-12-04 AU AU2002361972A patent/AU2002361972A1/en not_active Abandoned
- 2002-12-04 CN CNB028243722A patent/CN1273508C/zh not_active Expired - Fee Related
- 2002-12-04 BR BRPI0214685-1A patent/BR0214685B1/pt not_active IP Right Cessation
- 2002-12-04 ES ES02796566T patent/ES2305339T3/es not_active Expired - Lifetime
- 2002-12-04 WO PCT/EP2002/013709 patent/WO2003048221A1/fr not_active Ceased
- 2002-12-04 JP JP2003549406A patent/JP4741185B2/ja not_active Expired - Fee Related
- 2002-12-04 AT AT02796566T patent/ATE393176T1/de not_active IP Right Cessation
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2004
- 2004-05-28 US US10/855,354 patent/US7115693B2/en not_active Expired - Lifetime
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2006
- 2006-05-03 US US11/416,188 patent/US7169870B2/en not_active Expired - Lifetime
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2011
- 2011-02-14 JP JP2011028442A patent/JP2011094157A/ja active Pending
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| Publication number | Publication date |
|---|---|
| WO2003048221A1 (fr) | 2003-06-12 |
| KR100904627B1 (ko) | 2009-06-25 |
| JP4741185B2 (ja) | 2011-08-03 |
| JP2005511806A (ja) | 2005-04-28 |
| DE60226270D1 (de) | 2008-06-05 |
| KR20090058577A (ko) | 2009-06-09 |
| EP1456260A1 (fr) | 2004-09-15 |
| US20050004333A1 (en) | 2005-01-06 |
| KR20040064298A (ko) | 2004-07-16 |
| CN1273508C (zh) | 2006-09-06 |
| US20060270817A1 (en) | 2006-11-30 |
| BR0214685A (pt) | 2004-12-07 |
| KR100939651B1 (ko) | 2010-02-03 |
| JP2011094157A (ja) | 2011-05-12 |
| CN1599762A (zh) | 2005-03-23 |
| ATE393176T1 (de) | 2008-05-15 |
| AU2002361972A1 (en) | 2003-06-17 |
| US7169870B2 (en) | 2007-01-30 |
| ES2305339T3 (es) | 2008-11-01 |
| EP1456260B1 (fr) | 2008-04-23 |
| RU2301236C2 (ru) | 2007-06-20 |
| BR0214685B1 (pt) | 2012-08-21 |
| RU2004120699A (ru) | 2005-03-27 |
| US7115693B2 (en) | 2006-10-03 |
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