GB2156377A - Co-oligomerization of olefins - Google Patents
Co-oligomerization of olefins Download PDFInfo
- Publication number
- GB2156377A GB2156377A GB08407787A GB8407787A GB2156377A GB 2156377 A GB2156377 A GB 2156377A GB 08407787 A GB08407787 A GB 08407787A GB 8407787 A GB8407787 A GB 8407787A GB 2156377 A GB2156377 A GB 2156377A
- Authority
- GB
- United Kingdom
- Prior art keywords
- olefins
- branched
- chain
- psig
- oligomerization
- 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.)
- Granted
Links
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 30
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052796 boron Inorganic materials 0.000 claims abstract description 7
- GGQQNYXPYWCUHG-RMTFUQJTSA-N (3e,6e)-deca-3,6-diene Chemical compound CCC\C=C\C\C=C\CC GGQQNYXPYWCUHG-RMTFUQJTSA-N 0.000 claims abstract description 6
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 14
- 229910015900 BF3 Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 5
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 4
- 239000004711 α-olefin Substances 0.000 description 4
- CRSBERNSMYQZNG-UHFFFAOYSA-N 1-dodecene Chemical compound CCCCCCCCCCC=C CRSBERNSMYQZNG-UHFFFAOYSA-N 0.000 description 2
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000013638 trimer Substances 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- -1 aluminum alkyl halide Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- 229940069096 dodecene Drugs 0.000 description 1
- 238000004508 fractional distillation Methods 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 230000003606 oligomerizing effect Effects 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
- C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2527/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- C07C2527/06—Halogens; Compounds thereof
- C07C2527/08—Halides
- C07C2527/12—Fluorides
- C07C2527/1213—Boron fluoride
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- C07C2531/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
C20-C40 branched-chain olefins are prepared by the co-oligomerization of C12-C18 branched-chain internal olefins with C5-C6 olefins by a process comprising (a) contacting a propylene oligomer feedstock having from 12 to 18 carbon atoms with a C5-C6 olefin feedstock in a reaction zone in the presence of a boron trifluoride-alkanol catalyst; (b) maintaining the temperature in the reaction zone between 0 DEG C and 80 DEG C; and (c) maintaining the pressure in the reaction zone in the range of 0 psig to 200 psig (1 to 15 kg/cm<2>).
Description
SPECIFICATION
Co-oligomerization of olefins
The present invention relates to a process for the preparation of C20-C40 branched-chain olefins by the co-oligomerization of C12-Cl8 branched-chain internal olefins with Cs-C6 olefins in the presence of a boron trifluoride-alkanol catalyst.
The oligomerization of alpha olefins is well known in the art. Thus, U.S. Patent No. 3,932,553 describes the oligomerization of propylene in the presence of a boron trifluoride catalyst and a small amount of an olefinic diene to provide oligomers having about 15 to 21 carbon atoms.
U.S. Patent No. 4,024,203 describes the oligomerization of lower molecular weight mono alpha olefins utilizing a catalyst composition containing a Bronsted acid, a sulfone, and optionally, a Lewis acid, to provide predominantly dimers and trimers.
U.S. Patent No. 4,041,098 describes a method of oligomerizing straight-chain alpha olefins having from 3 to 14 carbon atoms with a soluble catalyst system consisting of an aluminum alkyl halide and an organo halide.
U.S. Patent Nos. 4,045,507 and 5,045,508 describe the oligomerization of alpha olefins having about 5 to 14 carbon atoms, particularly 1-decene and mixtures of 1-decene with 1-octene andlor 1-dodecene, in the presence of a boron trifluoride catalyst and co-catalyst that complexes with boron trifluoride to provide an oligomer mixture including trimer and tetramer.
It has now been found, in accordance with the invention, that the production of C20-C < o branchedchain olefins is successfully achieved by the co-oligomerization of C,2-C,8 branched-chain internal olefins with C5-C6 olefins by a process which comprises
(a) contacting a propylene oligomer feedstock having from 12 to 18 carbon atoms with a Cs-C6 olefin feedstock in a reaction zone in the presence of a boron trifluoride-alkanol catalyst;
(b) maintaining the temperature in the reaction zone in the range from 0 C to 800C; and
(c) maintaining the pressure in the reaction zone in the range from 0 psig to 200 psig (1 to 15 kg/ cm2).
Among other factors, the present invention is based on the discovery that C,2-C,6 internal olefins which are also highly branched can be co-oligomerization with C5-C6 olefins to provide high molecular weight branched-chain olefins in high yield and conversions.
The process of the present invention is suitable for the production of C20-C40 branched-chain olefins.
The olefins thus prepared are highly branched compounds and the term "branched-chain is herein used to signify at least one carbon branch per every 5 carbon atoms in the olefin product.
A proplyene oligomer feedstock having from 12 to 18 carbon atoms and an internal double bond is used as a starting material. This feedstock may be obtained by the direct oligomerization of propylene in an acid medium.
The propylene oligomer feedstock is contacted with a C5-C6 olefin feedstock in the presence of a boron trifluoride-alkanol catalyst. The C5-C6 olefin may be obtained as a product of naphtha cracking and normally will contain a mixture of both straight-chain and branched-chain olefins. The reaction is carried out at a temperature of from 0 C to 80do, preferably from 10"C to 60"C. The reaction pressure is maintained at from 0 psig to 200 psig, (1 to 15 kg/cm2), preferably from 0 psig to 150 psig (1 to 11.5 kg/cm2).
The use of boron trifluoride-alkanol as the co-oligomerization catalyst has been found to be satisfactory for providing the olefin product in high yield.
The boron trifluoride catalyst is preferably utilized in combination with an alkanol. Suitable alkanols include straight-chain alkanols of 1 to 8 carbon atoms. A preferred alkanol is normal butanol. Generally, about 0.01 to 1, and preferably about 0.05 to 0.5, moles of boron trifluoride are utilized per mole of olefin feedstock. The boron trifluoride-alkanol catalyzed reaction proceeds to give order over 40% conversion to the olefin product.
The co-oligomerization branched-chain olefinic products may be separated from the reaction mixture by conventional procedures, such as fractional distillation.
The C20-C40 branched-chain olefins prepared by the process of the present invention are useful as precursors for surface-active products, lubricating compositions, and the like.
The following Example is provided to illustrate the invention.
Example
A 2-liter, 3-necked, round-bottom flask was equipped with a boron trifluoride bubbler, stirrer, dropping funnel, thermometer and condenser with ice trap and drierite tube. To this flask, 600ml (2.6 moles) of a propylene polymer having an averge molecular weight of about 200 and 960 ml (12.5 moles) of C6+Cs distilled FCC light gasoline was added and saturated with boron trifluoride. With stirring, 120 ml (1.6 moles) of n-butanol was added over a period of 180 minutes, while maintaining a temperature of 40"C. The pressure in the flask was atmospheric, i.e. 0 psig (1 kg/cm2). The reaction was run for 6 hours and the results are shown in Table 1.
TABLE 1
Time, hours Olefin Conversion
1 -
2 4%
3 25%
4 31%
5 36%
6 44%
Claims (6)
1. A process fo the preparation of C20-C40 branched-chain olefins by the co-oligomerization of C,2-C,8 branched-chain internal olefins with Cs-C6 olefins which comprises:
(a) contacting a propylene oligomer feestock having from 12 to 18 carbon atoms with a C5-C6 olefin feedstock in a reaction zone in the presence of a boron trifluoride-alkanol catalyst;
(b) maintaining the temperature in the reaction zone in the range from 0 C to 800C; and
(c) maintaining the pressure in the reaction zone in the range from 0 psig to 200 psig (1 to 15 kgl cm2).
2. A process according to Claim 1, wherein the alkanol is normal butanol.
3. A process according to Claim 1 or 2, wherein the reaction is carried out at a temperature in the range from 10"C to 60"C.
4. A process according to Claim 1, 2 or 3, wherein the reaction is carried out at a pressure in the range from 0 psig to 150 psig (1 to 11.5 kg/cm2).
5. A process according to Claim 1, 2, 3 or 4, wherein the reaction zone reaction conditions are maintained in a manner such as to yield at least 40% conversion of the olefin feedstock to the C20-C40 branched-chain olefins.
6. A process for the preparation of C20-C40 branched-chain olefins by the co-oligomerization of C12- C,8 branched-chain internal olefins with C > -C6 olefins, substantially as described in the foregoing Example.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08407787A GB2156377B (en) | 1984-03-26 | 1984-03-26 | Co-oligomerization of olefins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB08407787A GB2156377B (en) | 1984-03-26 | 1984-03-26 | Co-oligomerization of olefins |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8407787D0 GB8407787D0 (en) | 1984-05-02 |
| GB2156377A true GB2156377A (en) | 1985-10-09 |
| GB2156377B GB2156377B (en) | 1987-11-11 |
Family
ID=10558685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB08407787A Expired GB2156377B (en) | 1984-03-26 | 1984-03-26 | Co-oligomerization of olefins |
Country Status (1)
| Country | Link |
|---|---|
| GB (1) | GB2156377B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB453854A (en) * | 1934-12-08 | 1936-09-18 | Ig Farbenindustrie Ag | Process for the manufacture of polymerisation products from olefines |
| GB635576A (en) * | 1947-04-18 | 1950-04-12 | Standard Oil Dev Co | An improved manufacture of polymers of propylene |
| GB734498A (en) * | 1951-12-31 | 1955-08-03 | Exxon Research Engineering Co | Polymerisation of olefins |
| GB1011471A (en) * | 1961-07-11 | 1965-12-01 | Socony Mobil Oil Co Inc | Polymerized olefin synthetic lubricants |
| GB1121335A (en) * | 1965-04-23 | 1968-07-24 | Mobil Oil Corp | Polymerization of olefins with bf |
| GB1497524A (en) * | 1975-11-20 | 1978-01-12 | Gulf Research Development Co | Method of oligomerizing 1-olefins |
| EP0077113A1 (en) * | 1981-09-11 | 1983-04-20 | Gulf Research & Development Company | Olefin oligomerization using boron trifluoride and a three-component cocatalyst |
-
1984
- 1984-03-26 GB GB08407787A patent/GB2156377B/en not_active Expired
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB453854A (en) * | 1934-12-08 | 1936-09-18 | Ig Farbenindustrie Ag | Process for the manufacture of polymerisation products from olefines |
| GB635576A (en) * | 1947-04-18 | 1950-04-12 | Standard Oil Dev Co | An improved manufacture of polymers of propylene |
| GB734498A (en) * | 1951-12-31 | 1955-08-03 | Exxon Research Engineering Co | Polymerisation of olefins |
| GB1011471A (en) * | 1961-07-11 | 1965-12-01 | Socony Mobil Oil Co Inc | Polymerized olefin synthetic lubricants |
| GB1121335A (en) * | 1965-04-23 | 1968-07-24 | Mobil Oil Corp | Polymerization of olefins with bf |
| GB1497524A (en) * | 1975-11-20 | 1978-01-12 | Gulf Research Development Co | Method of oligomerizing 1-olefins |
| EP0077113A1 (en) * | 1981-09-11 | 1983-04-20 | Gulf Research & Development Company | Olefin oligomerization using boron trifluoride and a three-component cocatalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| GB8407787D0 (en) | 1984-05-02 |
| GB2156377B (en) | 1987-11-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4451684A (en) | Co-oligomerization of olefins | |
| US4413156A (en) | Manufacture of synthetic lubricant additives from low molecular weight olefins using boron trifluoride catalysts | |
| JP3178928B2 (en) | Production of Synthetic Oil from Vinylidene Olefin and α-Olefin | |
| NL194237C (en) | Process for isomerizing n-butenes to isobutene. | |
| CA2346902A1 (en) | Process for dimerizing olefinic hydrocarbon feedstock and producing a fuel component | |
| US3760026A (en) | Synthesis of di-tert-butylethylene using olefin disproportionation | |
| KR20010032041A (en) | Process for the Oligomerization of Isobutylene | |
| US4434309A (en) | Oligomerization of predominantly low molecular weight olefins over boron trifluoride in the presence of a protonic promoter | |
| US4417082A (en) | Thermal treatment of olefin oligomers via a boron trifluoride process to increase their molecular weight | |
| US4219686A (en) | Process for the preparation of alkylbenzenes | |
| US3483268A (en) | Dimerisation process | |
| EP0311310B1 (en) | Olefin oligomerization | |
| EP0424460B1 (en) | Heterogeneous isoparaffin/olefin alkylation process | |
| US4451689A (en) | Co-dimerization of olefins | |
| US4395578A (en) | Oligomerization of olefins over boron trifluoride in the presence of a transition metal cation-containing promoter | |
| GB2156377A (en) | Co-oligomerization of olefins | |
| CA1212965A (en) | Co-oligomerization of olefins | |
| US6930218B2 (en) | Process for the preparation of linear low molecular weight olefins by the oligomerization of ethylene | |
| US4167534A (en) | Process for the preparation of synthetic lubricating oils | |
| US2786036A (en) | Preparation of polymerization initiators | |
| JP2945134B2 (en) | New synthetic lubricant composition and method for producing the same | |
| US3322807A (en) | 1, 4-bis-and 2, 4-bis-di-(triorganosilyl) but-1-enes | |
| EP0634381A1 (en) | Olefin oligomerization process | |
| US4275249A (en) | Preparation of 2,4-Di-t-alkylphenol | |
| RU2452567C1 (en) | Catalyst and method for oligomerisation of alpha-olefins |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PCNP | Patent ceased through non-payment of renewal fee |
Effective date: 19940326 |