CA1061944A - Continuous insitu catalyst addition for polybutadiene polymerization - Google Patents
Continuous insitu catalyst addition for polybutadiene polymerizationInfo
- Publication number
- CA1061944A CA1061944A CA249,533A CA249533A CA1061944A CA 1061944 A CA1061944 A CA 1061944A CA 249533 A CA249533 A CA 249533A CA 1061944 A CA1061944 A CA 1061944A
- Authority
- CA
- Canada
- Prior art keywords
- boron trifluoride
- butadiene
- catalyst
- mixture
- mole ratio
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 57
- 239000005062 Polybutadiene Substances 0.000 title claims abstract description 17
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 17
- 229920002857 polybutadiene Polymers 0.000 title abstract description 12
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims abstract description 52
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims abstract description 51
- 238000000034 method Methods 0.000 claims abstract description 32
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 29
- 239000002904 solvent Substances 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 19
- 150000002815 nickel Chemical class 0.000 claims abstract description 14
- 125000001931 aliphatic group Chemical group 0.000 claims abstract description 11
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract description 10
- 239000012442 inert solvent Substances 0.000 claims abstract description 6
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 150000002170 ethers Chemical class 0.000 claims abstract description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 3
- 230000000379 polymerizing effect Effects 0.000 claims abstract description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 7
- DVTHIMLUHWEZOM-UHFFFAOYSA-L nickel(2+);octanoate Chemical compound [Ni+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O DVTHIMLUHWEZOM-UHFFFAOYSA-L 0.000 claims description 5
- 241000746181 Therates Species 0.000 claims 1
- 229920003193 cis-1,4-polybutadiene polymer Polymers 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 27
- 235000010210 aluminium Nutrition 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- 230000008569 process Effects 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 7
- 229910052796 boron Inorganic materials 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 239000004568 cement Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 229930195733 hydrocarbon Natural products 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 239000003849 aromatic solvent Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- -1 butadiene Chemical class 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 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
- 239000002253 acid Substances 0.000 description 2
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-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
- 150000007513 acids Chemical class 0.000 description 1
- 238000012644 addition polymerization Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001734 carboxylic acid salts Chemical class 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 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
- 239000003701 inert diluent Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- WTQSPDBNCMUOKF-UHFFFAOYSA-L naphthalene-1-carboxylate;nickel(2+) Chemical compound [Ni+2].C1=CC=C2C(C(=O)[O-])=CC=CC2=C1.C1=CC=C2C(C(=O)[O-])=CC=CC2=C1 WTQSPDBNCMUOKF-UHFFFAOYSA-L 0.000 description 1
- 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 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- GAIQJSWQJOZOMI-UHFFFAOYSA-L nickel(2+);dibenzoate Chemical compound [Ni+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAIQJSWQJOZOMI-UHFFFAOYSA-L 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
- 230000037048 polymerization activity Effects 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 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
- MCULRUJILOGHCJ-UHFFFAOYSA-N triisobutylaluminium Chemical compound CC(C)C[Al](CC(C)C)CC(C)C MCULRUJILOGHCJ-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 (1)
| Publication Number | Publication Date |
|---|---|
| CA1061944A true CA1061944A (en) | 1979-09-04 |
Family
ID=24299794
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA249,533A Expired CA1061944A (en) | 1975-05-07 | 1976-04-05 | Continuous insitu catalyst addition for polybutadiene polymerization |
Country Status (11)
| Country | Link |
|---|---|
| US (1) | US4020255A (OSRAM) |
| JP (1) | JPS51136772A (OSRAM) |
| AU (1) | AU498320B2 (OSRAM) |
| BR (1) | BR7602588A (OSRAM) |
| CA (1) | CA1061944A (OSRAM) |
| DD (1) | DD124994A5 (OSRAM) |
| DE (1) | DE2615953C2 (OSRAM) |
| FR (1) | FR2310362A1 (OSRAM) |
| GB (1) | GB1499638A (OSRAM) |
| IT (1) | IT1058180B (OSRAM) |
| ZA (1) | ZA762144B (OSRAM) |
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 |
| 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 |
| 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 |
| US4501866A (en) * | 1984-07-23 | 1985-02-26 | The Firestone Tire & Rubber Company | Continuous method for preparing high cis-1,4 polybutadiene |
| IN173082B (OSRAM) * | 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 |
| KR101860969B1 (ko) | 2010-12-31 | 2018-05-24 | 가부시키가이샤 브리지스톤 | 니켈-기재 촉매시스템을 이용한 공액 디엔의 벌크중합 |
| JP5810171B2 (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 |
| US3985677A (en) * | 1972-10-27 | 1976-10-12 | The Goodyear Tire & Rubber Company | Preparation of polymerization catalyst and polymerization therewith |
| US3845029A (en) * | 1972-10-27 | 1974-10-29 | Goodyear Tire & Rubber | Polymerization of butadiene with stabilized catalyst system |
| 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 |
|---|---|
| ZA762144B (en) | 1977-04-27 |
| IT1058180B (it) | 1982-04-10 |
| FR2310362B1 (OSRAM) | 1978-05-19 |
| JPS5740846B2 (OSRAM) | 1982-08-31 |
| FR2310362A1 (fr) | 1976-12-03 |
| DE2615953A1 (de) | 1976-11-18 |
| BR7602588A (pt) | 1976-11-16 |
| DD124994A5 (OSRAM) | 1977-03-23 |
| DE2615953C2 (de) | 1984-07-26 |
| JPS51136772A (en) | 1976-11-26 |
| US4020255A (en) | 1977-04-26 |
| AU498320B2 (en) | 1979-03-01 |
| AU1288376A (en) | 1977-10-13 |
| GB1499638A (en) | 1978-02-01 |
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