DE2615953C2 - Verfahren zur Herstellung von festem kautschukartigem Polybutadien mit einem hohen Gehalt von mehr als 95 % der Butadieneinheiten in cis-1,4-Konfiguration - Google Patents
Verfahren zur Herstellung von festem kautschukartigem Polybutadien mit einem hohen Gehalt von mehr als 95 % der Butadieneinheiten in cis-1,4-KonfigurationInfo
- Publication number
- DE2615953C2 DE2615953C2 DE2615953A DE2615953A DE2615953C2 DE 2615953 C2 DE2615953 C2 DE 2615953C2 DE 2615953 A DE2615953 A DE 2615953A DE 2615953 A DE2615953 A DE 2615953A DE 2615953 C2 DE2615953 C2 DE 2615953C2
- Authority
- DE
- Germany
- Prior art keywords
- catalyst
- butadiene
- boron trifluoride
- nickel
- mixture
- 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
Links
- 238000000034 method Methods 0.000 title claims description 40
- KAKZBPTYRLMSJV-UHFFFAOYSA-N butadiene group Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 title claims description 39
- 229920002857 polybutadiene Polymers 0.000 title claims description 11
- 239000005062 Polybutadiene Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title claims description 4
- 239000007787 solid Substances 0.000 title claims 2
- 239000003054 catalyst Substances 0.000 claims description 51
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims description 36
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 21
- 229910015900 BF3 Inorganic materials 0.000 claims description 20
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 9
- 125000001931 aliphatic group Chemical group 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- -1 nickel carboxylic acid salt Chemical class 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003849 aromatic solvent Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 239000012442 inert solvent Substances 0.000 claims description 3
- 238000010924 continuous production Methods 0.000 claims description 2
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims 5
- 150000001735 carboxylic acids Chemical class 0.000 claims 2
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 125000002947 alkylene group Chemical group 0.000 claims 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 claims 1
- 150000001734 carboxylic acid salts Chemical class 0.000 claims 1
- 150000001993 dienes Chemical class 0.000 claims 1
- DPDXVBIWZBJGSX-XUTVFYLZSA-N isoboonein Chemical compound C1C(=O)OC[C@@H]2[C@@H](C)[C@@H](O)C[C@@H]21 DPDXVBIWZBJGSX-XUTVFYLZSA-N 0.000 claims 1
- 239000002244 precipitate Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 239000003381 stabilizer Substances 0.000 claims 1
- 238000003860 storage Methods 0.000 claims 1
- 239000000243 solution Substances 0.000 description 7
- DVTHIMLUHWEZOM-UHFFFAOYSA-L nickel(2+);octanoate Chemical compound [Ni+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O DVTHIMLUHWEZOM-UHFFFAOYSA-L 0.000 description 3
- 239000011877 solvent mixture Substances 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- UIEKYBOPAVTZKW-UHFFFAOYSA-L naphthalene-2-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=CC2=CC(C(=O)[O-])=CC=C21.C1=CC=CC2=CC(C(=O)[O-])=CC=C21 UIEKYBOPAVTZKW-UHFFFAOYSA-L 0.000 description 2
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 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
- RSWGJHLUYNHPMX-UHFFFAOYSA-N 1,4a-dimethyl-7-propan-2-yl-2,3,4,4b,5,6,10,10a-octahydrophenanthrene-1-carboxylic acid Chemical compound C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- SFXNZFATUMWBHR-UHFFFAOYSA-N 2-morpholin-4-yl-2-pyridin-3-ylacetonitrile Chemical compound C=1C=CN=CC=1C(C#N)N1CCOCC1 SFXNZFATUMWBHR-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000002716 delivery method Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- LXHKZDOLHOQBTR-UHFFFAOYSA-L hexadecanoate;nickel(2+) Chemical compound [Ni+2].CCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCC([O-])=O LXHKZDOLHOQBTR-UHFFFAOYSA-L 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- JMWUYEFBFUCSAK-UHFFFAOYSA-L nickel(2+);octadecanoate Chemical compound [Ni+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O JMWUYEFBFUCSAK-UHFFFAOYSA-L 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- SQBBHCOIQXKPHL-UHFFFAOYSA-N tributylalumane Chemical compound CCCC[Al](CCCC)CCCC SQBBHCOIQXKPHL-UHFFFAOYSA-N 0.000 description 1
- FQMMZTDQJFUYSA-UHFFFAOYSA-N triheptylalumane Chemical compound CCCCCCC[Al](CCCCCCC)CCCCCCC FQMMZTDQJFUYSA-UHFFFAOYSA-N 0.000 description 1
- ORYGRKHDLWYTKX-UHFFFAOYSA-N trihexylalumane Chemical compound CCCCCC[Al](CCCCCC)CCCCCC ORYGRKHDLWYTKX-UHFFFAOYSA-N 0.000 description 1
- JOJQVUCWSDRWJE-UHFFFAOYSA-N tripentylalumane Chemical compound CCCCC[Al](CCCCC)CCCCC JOJQVUCWSDRWJE-UHFFFAOYSA-N 0.000 description 1
- CNWZYDSEVLFSMS-UHFFFAOYSA-N tripropylalumane Chemical compound CCC[Al](CCC)CCC CNWZYDSEVLFSMS-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
- C08F136/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
- C08F136/02—Homopolymers 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
- C08F136/04—Homopolymers 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
- C08F136/06—Butadiene
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/575,311 US4020255A (en) | 1975-05-07 | 1975-05-07 | Continuous insitu catalyst addition for polybutadiene polymerization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| DE2615953A1 DE2615953A1 (de) | 1976-11-18 |
| DE2615953C2 true DE2615953C2 (de) | 1984-07-26 |
Family
ID=24299794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| DE2615953A Expired DE2615953C2 (de) | 1975-05-07 | 1976-04-12 | Verfahren zur Herstellung von festem kautschukartigem Polybutadien mit einem hohen Gehalt von mehr als 95 % der Butadieneinheiten in cis-1,4-Konfiguration |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4020255A (enExample) |
| JP (1) | JPS51136772A (enExample) |
| AU (1) | AU498320B2 (enExample) |
| BR (1) | BR7602588A (enExample) |
| CA (1) | CA1061944A (enExample) |
| DD (1) | DD124994A5 (enExample) |
| DE (1) | DE2615953C2 (enExample) |
| FR (1) | FR2310362A1 (enExample) |
| GB (1) | GB1499638A (enExample) |
| IT (1) | IT1058180B (enExample) |
| ZA (1) | ZA762144B (enExample) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4383097A (en) * | 1981-08-21 | 1983-05-10 | The Goodyear Tire & Rubber Company | Molecular weight regulation of cis-1,4-polybutadiene |
| CA1236647A (en) * | 1982-04-26 | 1988-05-10 | Anthony J. Puccio | Preparation of high cis-1,4-polybutadiene |
| US4562171A (en) * | 1984-06-04 | 1985-12-31 | The Firestone Tire & Rubber Company | Method of preparing high cis-1,4 diene polymers having good green strength and tack using a catalyst composition containing a carboxylated metal oxy aluminate component |
| US4522988A (en) * | 1984-06-04 | 1985-06-11 | The Firestone Tire & Rubber Company | Method of preparing high cis-1,4 diene polymers having good green strength and tack |
| US4562172A (en) * | 1984-06-04 | 1985-12-31 | The Firestone Tire & Rubber Company | Method of preparing high cis-1,4 diene polymers having good green strength and tack |
| US4522989A (en) * | 1984-06-04 | 1985-06-11 | The Firestone Tire & Rubber Company | Method of preparing high cis-1,4 diene polymers having good green strength and tack using a catalyst composition containing a carboxylated metal oxy aluminate component |
| US4501866A (en) * | 1984-07-23 | 1985-02-26 | The Firestone Tire & Rubber Company | Continuous method for preparing high cis-1,4 polybutadiene |
| IN173082B (enExample) * | 1986-02-19 | 1994-02-05 | Goodyear Tire & Rubber | |
| US5412045A (en) * | 1994-09-16 | 1995-05-02 | Polysar Rubber Corporation | Preparation of high cis-1,4-polybutadiene with reduced gel |
| US5955553A (en) * | 1998-08-19 | 1999-09-21 | Bridgestone Corporation | Molecular weight regulation of cis-1,4-polybutadiene using carboxylates |
| US6596825B1 (en) | 2002-07-30 | 2003-07-22 | Firestone Polymers, Llc | Low gel high cis polydiene |
| US6727330B1 (en) * | 2003-02-07 | 2004-04-27 | Firestone Polymers, Llc | Termination and reduced gel in high cis polybutadiene |
| EP2658886B1 (en) | 2010-12-31 | 2017-03-08 | Bridgestone Corporation | Bulk polymerization of conjugated dienes using a nickel-based catalyst system |
| JP5810172B2 (ja) | 2010-12-31 | 2015-11-11 | 株式会社ブリヂストン | ニッケル系触媒系を使用する共役ジエンのバルク重合 |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3170907A (en) * | 1959-12-31 | 1965-02-23 | Bridgestone Tire Co Ltd | Production of cis-1, 4 polybutadiene with a nickel carboxylic acid salt-boron trifluoride etherate-aluminum trialkyl catalyst |
| GB1035796A (en) * | 1964-10-22 | 1966-07-13 | Japan Synthetic Rubber Co Ltd | Method for producing polybutadiene |
| US3464965A (en) * | 1965-10-08 | 1969-09-02 | Japan Synthetic Rubber Co Ltd | Process for producing polybutadienes having reduced cold flow tendency |
| US3528957A (en) * | 1967-07-10 | 1970-09-15 | Goodyear Tire & Rubber | Method of producing polybutadiene |
| US3513149A (en) * | 1967-12-11 | 1970-05-19 | Phillips Petroleum Co | Gel reduction in cis-polybutadiene process |
| US3844974A (en) * | 1970-07-08 | 1974-10-29 | Goodyear Tire & Rubber | Catalyst for the polymerization of conjugated diolefins |
| US3845029A (en) * | 1972-10-27 | 1974-10-29 | Goodyear Tire & Rubber | Polymerization of butadiene with stabilized catalyst system |
| US3985677A (en) * | 1972-10-27 | 1976-10-12 | The Goodyear Tire & Rubber Company | Preparation of polymerization catalyst and polymerization therewith |
| US3985941A (en) * | 1975-05-12 | 1976-10-12 | The Goodyear Tire & Rubber Company | Method of polymerization |
-
1975
- 1975-05-07 US US05/575,311 patent/US4020255A/en not_active Expired - Lifetime
-
1976
- 1976-04-05 CA CA249,533A patent/CA1061944A/en not_active Expired
- 1976-04-09 ZA ZA762144A patent/ZA762144B/xx unknown
- 1976-04-09 AU AU12883/76A patent/AU498320B2/en not_active Expired
- 1976-04-12 DE DE2615953A patent/DE2615953C2/de not_active Expired
- 1976-04-13 GB GB15062/76A patent/GB1499638A/en not_active Expired
- 1976-04-21 IT IT49116/76A patent/IT1058180B/it active
- 1976-04-28 BR BR2588/76A patent/BR7602588A/pt unknown
- 1976-04-29 FR FR7612769A patent/FR2310362A1/fr active Granted
- 1976-04-30 JP JP51049821A patent/JPS51136772A/ja active Granted
- 1976-05-05 DD DD192690A patent/DD124994A5/xx unknown
Also Published As
| Publication number | Publication date |
|---|---|
| DE2615953A1 (de) | 1976-11-18 |
| FR2310362A1 (fr) | 1976-12-03 |
| ZA762144B (en) | 1977-04-27 |
| AU498320B2 (en) | 1979-03-01 |
| FR2310362B1 (enExample) | 1978-05-19 |
| US4020255A (en) | 1977-04-26 |
| CA1061944A (en) | 1979-09-04 |
| BR7602588A (pt) | 1976-11-16 |
| JPS5740846B2 (enExample) | 1982-08-31 |
| IT1058180B (it) | 1982-04-10 |
| JPS51136772A (en) | 1976-11-26 |
| AU1288376A (en) | 1977-10-13 |
| GB1499638A (en) | 1978-02-01 |
| DD124994A5 (enExample) | 1977-03-23 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| 8110 | Request for examination paragraph 44 | ||
| D2 | Grant after examination | ||
| 8364 | No opposition during term of opposition |