Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
  • C07C209/60—Preparation of compounds containing amino groups bound to a carbon skeleton by condensation or addition reactions, e.g. Mannich reaction, addition of ammonia or amines to alkenes or to alkynes or addition of compounds containing an active hydrogen atom to Schiff's bases, quinone imines, or aziranes

Definitions

• the present invention relates to an aminomethylation process for making long chain internal fatty tertiary amine, quaternized amines and the corresponding amine oxides.
• Linear tertiary amines with chain lengths between 8 and 24 carbon atoms are com- monly referred to as fatty tertiary amines. According to Ullman's Encyclopedia of Chemical Technology, 5* edition, Volume Al, these materials, and their derivatives such as the corresponding quaternary ammonium compounds, are widely used in ap ⁇ plications such as fabric softeners, drilling muds, surfactants, asphalt emulsifiers, and bactericides/disinfectants.
• the fatty quaternary ammonium compounds dialkyldimethyl ammonium chloride or the corresponding methyl sulfate are useful.
• methyl or benzyl quaternary ammonium chlorides produced from dialkyl methyl amine are useful.
• C 12 or C 14 based dimethylalkyl amine oxide is commonly used.
• alkyl(benzyl)dimethyl and alky trimethyl compounds in which the fatty alkyl group contains 12 to 14 carbon atoms are most effective against a broad range of organisms.
• the dialkyl di ⁇ methyl compounds are most effective when the fatty alkyl group contains 8-10 carbon atoms.
• Fatty amines are commonly produced from natural fats and oils or from conventional petrochemical raw materials. Three primary feedstocks are used to make fatty tertiary amines: fatty nitriles, fatty alcohols or aldehydes, and long chain olefins.
• Fatty nitriles which are formed from fatty acids and ammonia over dehydrating cata ⁇ lysts in liquid phase reactors or liquid and vapor-phase reactors at 280 to 360° C, are reacted either with dimethylamine or with formaldehyde and formic acid to produce N,N-dimethylalkylamines (see US 4,248,801 to Lion Fat & Oil Co. and US 3,444,205 to Hoechst).
• Fatty alcohols and aldehydes can be converted into the same product via direct amina- tion in the presence of dimethylamine or other primary or secondary amines at 230° C at atmospheric pressure (0.1 - 0.5 MPa) using copper chromite catalysts (for alcohol feedstocks) or noble metal, copper chelate, or copper carboxylate catalysts (for alde- hydes) (see US 4,251,465 to Gulf Research and Development Co., US 4,138,437 to Hoechst, and both US 4,254,060 and US 4,210,605 to Kao).
• terminal amines means that the amine moiety is connected on a ⁇ or ⁇ carbon of the long chain alkyl chain of the amine.
• amine oxide surfactants For the case of amine oxide surfactants, this is done to provide good cleaning with high suds stability. However, sometimes it is desirable to produce with a high content (10 wt% or more) of internal amine. This would be useful for branched chain surfac- tants with improved cold water cleaning, moderate suds stability, and improved wet ⁇ ting properties.
• the present invention relates to a process comprising the steps of (a) providing a long chain internal olefin source selected from the group consisting of oligomerized C 2 to C 11 olefins, metathesized C 5 to C 10 olefins, Fischer-Tropsch ole ⁇ fins, dehydrogenated long chain paraffin hydrocarbons, thermally cracked hydrocar ⁇ bon waxes, or dimerized vinyl olefins and mixtures thereof;
• a long chain internal olefin source selected from the group consisting of oligomerized C 2 to C 11 olefins, metathesized C 5 to C 10 olefins, Fischer-Tropsch ole ⁇ fins, dehydrogenated long chain paraffin hydrocarbons, thermally cracked hydrocar ⁇ bon waxes, or dimerized vinyl olefins and mixtures thereof;
• step (d) optionally (with or without step (c)) oxidizing the long chain fatty tertiary amine to the corresponding amine oxide, and (e) optionally (with or without step (c) and/or (d)) quaternizing the long chain fatty tertiary amine into a quaternary long chain internal fatty tertiary amine product.
• long chain internal olefin means an olefin with 8 to 22 carbon atoms and greater than 10% of the carbon-carbon double bonds being in a position other than the terminal ( ⁇ and/or ⁇ carbon) position on the olefin. Preferably more than 50%, 70%, 90% and up to 100% of the carbon-carbon double bonds are in a position other than the terminal ( ⁇ and/or ⁇ carbon) positions on the olefin.
• the long chain internal olefin may be linear or branched. If the long chain internal olefin is branched, a C 1 -C 5 carbon branch is preferred.
• internal amine mean an amine having the amine moiety attached to the alkyl moiety in greater than 10%, 50%, 70%, 90% and up to 100% in a position other than the terminal ( ⁇ and/or ⁇ carbon) position on the alkyl moiety.
• Long chain internal olefin sources can be obtained from a variety of different proc- esses, including C 2 to Ci ⁇ olefin oligomerization processes, C 5 to C 1 Q olefin metathesis - A -
• the long chain internal olefins from any of the above described processes are then re ⁇ acted with primary or secondary amines to produce long chain fatty tertiary amines using commercially feasible processes such as aminomethylation. Any unconverted hydrocarbons and color or odor bodies are subsequently separated from the long chain internal fatty tertiary amines using distillation or other commercial techniques.
• the long chain internal fatty tertiary amines are converted into the corresponding amine oxide via oxidation.
• the present process relates to converting long chain internal olefins to long chain in ⁇ ternal fatty tertiary amines and optionally, long chain internal amine oxides.
• Oligomerized ethylene is available from suppliers such as Shell Chemicals, Exxon Chemicals, BP Amoco and Chevron Phillips.
• the oligomerized C 2 to C 11 olefins may be derived from C 2 to C 11 olefins in the pres ⁇ ence of either organoaluminum compounds, transition metal catalysts or acidic zeo- lites to produce a wide range of chainlengths that is further purified by various known means, preferably distillation (see US 3,647,906, 4,727,203, and 4,895,997 to Shell Oil Co., US 5,849,974 to Amoco Corp., and US 6,281,404 to Chevron Chemicals which disclose suitable catalysts and processing conditions for ethylene oligomeriza- tion).
• Oligomerization includes the production of dimers, trimers, or tetramers using cata ⁇ lysts such as acidic zeolites, nickel oxides, or metallocene cataylsts.
• cata ⁇ lysts such as acidic zeolites, nickel oxides, or metallocene cataylsts.
• US 5,026,933 discloses the use of ZSM-23 zeolite for propylene oligomerization.
• AMBERLYST 36® and acidic zeolites including mordenite, offretite and H-ZSM- 12 in at least partially acidic form (see also Comprehensive Or ⁇ ganic Transformation, 2 nd Edition, Larock, Richard C, pages 633-636; and Vogel's Textbook of Practical Organic Chemistry, 5 th Edition, Furniss, Brian S., Hannaford, Antony J., Smith, Peter W.G., and Tatchell, Austin R., pages 574- 579).
• ⁇ -olefins or internal olefins are generated from the oligomerization processes.
• an isomerization step is required to gen ⁇ erate the desired long chain internal olefins.
• the isomerization step results in random placement of the double bond along the carbon chain.
• Suitable isomerization catalysts include homogeneous or heterogeneous acidic catalysts, supported metal oxides such as cobalt oxide, iron oxide, or manganese oxide, and metal carbonyls such as cobalt carbonyl and iron carbonyl, see US 3,647,906, US 4,727,203, and US 4,895,997 to Shell Oil Co., US 5,849,974 to Amoco Corp., and US 6,281,404 to Chevron Chemi ⁇ cals which disclose suitable catalysts and processing conditions for double bond isom- erization.
• Cross-metathesis of C 5 -C 10 olefins with other olefins or even with oleochemicals can be used to produce suitable long chain internal olefins for the present process.
• two octene molecules can be reacted to form tetradecene and ethylene.
• the methyl ester of oleic acid can be reacted with hexene to form dodecene and the methyl ester of lauric acid.
• Common homogeneous catalysts include the ruthenium based Grubb's catalyst as well as the Schrock catalyst.
• Cross metathesis is further described in the text Olefin Metathesis and Metathesis Polymerization by Mn and MoI (1997), and also the journal Chemical and Engineering News, vol. 80, no. 51, Dec 23, 2002, pp. 29-33.
• olefins are from the isomerization/disproportionation olefin process and/or SHOP® process from Shell Chemical. These are commercially avail ⁇ able materials under the tradename NEODENE®. Fischer-Tropsch Olefins and Paraffins
• Long chain internal olefin sources from Fischer-Tropsch involves converting a source of carbon such as coal, methane, or natural gas to a wide distribution of carbon chainlengths and then isolating a narrow hydrocarbon fraction, using techniques such as distillation or liquid-liquid extraction.
• Two different catalysts are commercially used: iron and cobalt, with iron generally producing a higher yield of olefins and cobalt producing a higher yield of paraffins.
• Hydrocarbons recovered from the Fischer-Tropsch reaction may be a mixture of linear and branched chains, olefins and paraffins, having both terminal and internal double bonds.
• Straight run Fischer-Tropsch olefin and paraffins from jet and/or diesel frac ⁇ tions may be utilized in the present process.
• double bond isomerization catalysts can be employed to convert ⁇ -olef ⁇ ns to internal olefins. Paraffins present in the internal olefin feed stream may be left with the internal olefins until amination is complete.
• Oxygenates refer to carboxylic acids, alcohols, aldehydes, and ketones, which chainlengths from C 1 to C 18 . Oxygenates impart undesirable color, odor, and performance impurities to tertiary amines and must be removed from the hydrocarbons prior to amination or from the crude tertiary amine after amination.
• Liquid-liquid extraction is the preferred process for separating oxygenates from hydrocarbons. Liquid-liquid extraction is effective in removing both alcohols and carboxylic acids from hydrocarbons and can be achieved with more reasonable capital investment than distillation or adsorption. Caustic treatment, followed by cen- trifuging, water washing, or filtration is effective in neutralizing and separating car ⁇ boxylic acids, but has no effect on alcohols.
• liquid-liquid extraction to remove oxygenates can be done with a wide variety of solvents.
• diethylene glycol is reported to be a solvent for removal of aromatics from reformate
• propane is reported to be a solvent for removal of fatty acids from natural oils. See Packed Tower Design and Applications, 2 nd Ed., Strigle, page 294.
• Solvent polarity index is an important indicator of the solubility of the oxygenates as well as insolubility of the hydrocarbons.
• Extraction can be carried out in three classes of equipment: mixer-settlers, contacting columns, or centrifugal contactors.
• a mixer-settler When only one stage of separation is required for the extraction step, a mixer-settler may used. Spray columns may be used when the density difference between the phases is large. When more than three stages of separa ⁇ tion are needed, packed or tray columns with countercurrent flow are the preferred de ⁇ vices.
• Centrifugal contactors may also used if the liquid phases have small density dif ⁇ ference and a large number of equilibrium stages are needed. When ten to twelve equi- librium stages are required, a mechanical contactor with rotating disks or impellers is often used, as these have higher efficiencies than the packed contactors. The preferred number of equilibrium stages is one to twelve.
• distillation can be used to separate oxygenates from hydrocarbons, but the boiling points of oxygenates and hydrocarbons can overlap so that distillation is not preferred.
• Bulk separation by adsorption using molecular sieves is also possible, but expensive from a capital investment standpoint.
• Long chain internal olefin sources may also be obtained from the catalytic dehydroge ⁇ nation of long chain paraffins or paraff ⁇ n/olefm mixtures which yields long chain ole ⁇ fins with the same number of carbon atoms and with random locations of a double bond along the chain.
• double bond isomerization catalysts can be employed to convert ⁇ -olefins to internal olefins.
• Paraffins present in the internal ole- fin feed stream may be left with the internal olefins until amination is complete.
• Sources include the kerosene fraction from petroleum refineries and Fischer-Tropsch paraffins or paraffin/olefin mixtures.
• Thermally Cracked Hydrocarbon Waxes Long chain internal olefins may also be derived from thermal cracking of hydrocarbon waxes from either petroleum streams or the Fischer Tropsch reactions, including Fischer Tropsch paraffin waxes. The chainlength of these waxes is generally greater than C 22 .
• Thermal cracking is a non-catalytic, free radical process conducted at high temperatures in the presence of steam, followed by distillation to separate and recycle the unreacted wax to the cracking furnace.
• a tubular furnace is preferably used for the cracking reaction.
• the temperature for the thermal cracking ranges from 400 to 600°C. Selection of higher temperatures are not desired as higher temperatures results in the formation of shorter chain olefins (chainlength ⁇ C 5 ), higher levels of polyolef ⁇ ns, as well as more gas products. Selec ⁇ tion of lower temperatures are not desired as lower temperatures reduce the conver ⁇ sion of long chain internal olefins per pass, which is undesirable from a capital cost standpoint.
• the pressure in the thermal cracking reaction zone is 0.1 to 1 MPa. Higher pressure generally leads to an increase in the yield of liquid products, with a corresponding re ⁇ duction in ⁇ -olefin content. Space velocity is 1.25 to 5.0 volume of feed/volume of reactor/hour. This corresponds approximately to a vapor residence time in the reactor of 2.5 to 10 seconds. Higher residence time is undesirable as it leads to increased de- composition and secondary by-products verses the desired long chain internal olefins.
• the conversion per pass in the reaction is 10 to 25 wt %. Gas and liquid products from the thermal cracking reactor are separated by a distilla ⁇ tion step using a pressure of 10 to 2500 Pa and a temperature of 100° C- 280° C.
• double bond isomerization catalysts may be employed to convert any ⁇ -olefins present to long chain internal olefins.
• Internal vinylidenes may also be utilized as the long chain internal olefin source of the present process.
• Vinylidenes may be produced via a process involving dimerizing vi ⁇ nyl olefin with at least one trialkylaluminum compound. Further conditions may be found in US 5,625,105.
• Vinylidenes may also be produced via a process of dimerizing a vinyl-olefin monomer in the presence of a tri-alkyl aluminum catalyst as described in US 4,973,788.
• the long chain fatty tertiary amines desired in the present process are produced by the reaction between the long chain internal olefins as described above and either a pri ⁇ mary or secondary alkyl amine. If a primary alkyl amine such as monomethylamine is used, then two long chain internal olefin molecules are added to the primary alkyl amine to produce a di-long chain fatty tertiary monoalkyl amine product. If a secon ⁇ dary alkyl amine such as dimethylamine is used, then one long chain internal olefin molecule is added to the secondary alkyl amine to produce a mono-long chain fatty tertiary dialkyl amine product.
• Tertiary amine products that are produced by the process of the present invention have an internal amine content of from 10 wt% to 100 wt%, a linear olefin content of from about 1 wt% to 100 wt%, and a paraffin content of from 0 wt% to about 90 wt%.
• Examples of desirable tertiary amine products include but are not limited to trioc- tylamine, tridecylamine, tridodecylamine, didodecylmethylamine, ditetradecylmethyl- amine, dihexadecylmethylamine, dioctadecylmethylamine, decyldimethylamine, do- decyldimethylamine, tetradecyldimethylamine, hexadecyldimethylamine, and octade- cyldimethylamine.
• the amine moiety of these materials is located on the long chain alkyl in an internal position.
• An internal position refers to a carbon other than the ⁇ or ⁇ carbon of the long chain alkyl. Aminating the internal olefins for the present process includes hydrocarbonylation and is further described below.
• the aminomethylation reaction with an in- ternal long chain olefin such as those feedstocks described above produces a tertiary amine with the following structure:
• R 1 and R 2 are linear or semilinear hydrocarbons with a hydrocarbon content of chainlength of 1 to 19 carbon atoms.
• semilinear means that R 1 and/or R 2 comprise between 1 and 4 C 1 to C 3 alkyl branches randomly distributed or consistently distributed.
• the amine structure is such that an alkyl portion has a total sum of carbons from 8 to 22 carbon atoms.
• the alkyl portion is R 1 + R 2 + 2 carbon atoms between the nitrogen and R 1 and R 2 in the above referenced structure.
• the total sum of carbons in the alkyl portion is from 10 to 22 carbon atoms, preferably from 12 to 20, more preferably from 10 to 14.
• the number of carbon atoms for R 1 may be approximately the same number of carbon atoms for R 2 such that R 1 and R 2 are symmetric.
• symmetric means that for carbon atoms,
• asymmetric structure of the long chain fatty internal amine oxides improve surface wetting ability of the amine oxide that aids in the removal of grease deposits from surfaces at lower wash tempera ⁇ ture verses asymmetric branched amine oxides.
• asymmetric means
• mixtures contain non symmetric and symmetric structures of the long chain fatty internal amine oxides may also be de- sirable for the purpose but are not preferred.
• the process comprises the step of reacting the olefins with synthesis gas (H 2 and CO), preferably in a stoichiometric ratio, and a primary or secondary amine in the presence of a catalyst, preferably a heterogeneous catalyst, to form a tertiary amine product.
• synthesis gas H 2 and CO
• Preferred proc ⁇ ess conditions are a temperature of 60 to 200° C pressure of 2.8 to 21 MPa (400 to 3000 psig), H 2 :CO molar ratio of 0.5 to 3.0, and reaction time of 0.1 to 10.0 hours.
• the catalyst suitable for use in the present process include noble metal catalysts such as rhodium oxide, rhodium chloride, or ruthenium chloride, at a catalyst level of 50 to 1000 ppm by weight of the olefin.
• Ligands such as triphenylphosphine may optionally be used to stabilize the preferably heterogeneous noble metal catalyst. Preferred levels of triphenylphosphine are 100 to 5000 ppm by weight of the olefin.
• the process of the present invention further comprises the step of purifying the long chain internal fatty tertiary amine product from the previous step to form a purified long chain internal fatty tertiary amine product.
• Preferred purity of the purified long chain internal fatty tertiary amine product is from about 95 wt% or greater, more pref ⁇ erably from about 97 wt% or greater, most preferably from about 98 wt% to about 100 wt% by weight of the purified long chain internal fatty tertiary amine product after the purification step.
• the long chain internal fatty tertiary amine products may be mixed with paraffins, un- reacted olefins, color and odor bodies, and small quantities of oxygenates such as al ⁇ cohols or carboxylic acids among other impurities.
• a preferred purification step is via flash stills and/or topping columns.
• Equip ⁇ ment for the flash still and the topping column includes falling film evaporators, wiped film evaporators, reboiler flash units, and multistage distillation columns. All equipment is known to one of skill in the art and available from suppliers such as Pfaudler, Lewa, and Koch.
• Heavy impurities such as polyalkylamines, salts, and color bodies may be removed in a bottom stream of a flash still operating under a pressure of 10 to 2500 Pa (0.1 to 20 mm Hg) and a temperature of 90 to 205° C.
• Light impuri ⁇ ties such as residual hydrocarbons (olefin or paraffin) and color bodies may be re ⁇ moved in the overheads stream of a topping column operating under a pressure of 10 to 2500 Pa (0.1 to 20 mm Hg) and a temperature of 150 to 250° C.
• the process of the present invention further comprises the optional step of oxidizing the purified long chain internal fatty tertiary amine to give an oxidation product of the corresponding long chain internal fatty amine oxide.
• the purified long chain internal fatty tertiary amine may optionally be converted into using materials such as 5-70 wt% hydrogen peroxide.
• pu ⁇ rified long chain internal fatty tertiary amines are typically combined with 5 to 70 wt% hydrogen peroxide, 0.3 to 2.5% of a bicarbonate material such as sodium bicar ⁇ bonate or potassium bicarbonate, and optionally water, to result in an oxidation prod- uct which is 30-38 wt% by weight of the oxidation product of the corresponding long chain internal fatty amine.
• the amount of hydrogen peroxide is 100 to 115% of stoichiometric to the amount of amine present.
• the oxidation step target temperature is about 40 to 100° C (60 to 70° C preferred), and pressure is 0.1 MPa.
• the oxidation step is complete when the residual hydrogen peroxide level is below 1%, preferably below 0.1 wt% of the final product composition.
• Reaction time is gen ⁇ erally 4 to 24 hours.
• Residual hydrogen peroxide is typically decomposed by holding the material at reaction temperature. If necessary, 0.1 to 5 wt% by weight of the re ⁇ agents of platinum on alumina may be used as an adsorbent to remove residual hydro- gen peroxide from the oxidation product.
• the process of the present invention may further comprise the optional step of quater- nizing the purified long chain internal fatty tertiary amine to give a quaternary long chain internal fatty tertiary amine product.
• Quaternization may be achieved by a reac ⁇ tion of the purified long chain internal fatty tertiary amine with methyl chloride or di ⁇ methyl sulfate.
• Quaternization with methyl chloride is achieved by reaction with 1.0 to 1.3 mole equivalents of methyl chloride relative to the purified long chain internal fatty tertiary amine in an autoclave with temperature range of room temperature (20 0 C) to 8O 0 C under nitrogen pressure from 101 to 10100 kPa (1 to 100 atm).
• Dimethyl sulfate is reacted at 1.0 to 1.1 mole equivalents relative to the purified long chain internal fatty tertiary amine in a flask blanketed with nitrogen at 10 to 7O 0 C to form the desired quaternary long chain internal fatty tertiary amine product.
• Step 1 Melt a paraffin wax with a melt point range of 52 to 58° C and a linear hydrocarbon chainlength of C 21 to C 36 in an 800 niL glass beaker. Use the following equipment for the thermal cracking reaction:
• FMI piston pump (model QSY-I) to meter melted paraffin wax into a tubular reactor - 3.35 m (11 foot) long by 4.57 mm (0.18 inch) diameter stainless steel coil, heated in a muffle furnace (preheater)
• thermocouples before & after reac ⁇ tor coil
• the distillate composition was as follows:
• Step 2 Place 50 grams of Ci 0 to C 20 distillate composition from Step 1 above in a 300 ml Parr autoclave and combine with 0.025 grams of iron carbonyl, Fe 2 (CO) 9 to isomerize any double bonds present to result in internal olefins. Purge the reactor with 349.35 kPa (50 psig) nitrogen gas and then heat the distillate composition and iron carbonyl to 180° C for one hour with agitation.
• 349.35 kPa (50 psig) nitrogen gas Purge the reactor with 349.35 kPa (50 psig) nitrogen gas and then heat the distillate composition and iron carbonyl to 180° C for one hour with agitation.
• NEODENE® 10 and 12 are commercially available olefins from the Shell Chemical Company. Wash the residual olefin and catalyst in the container into the autoclave with 200 mL of n-hexane and seal the autoclave.
• reflux ratio is defined as the mass flow of distillate sent back to col ⁇ umn divided by mass flow of distillate removed from the column.
• the reflux ratio may be varied from 1.0 to 4.0. Recover a number of distillate fractions with various levels of unreacted olefin and unreacted amine. Cease column boilup and stop the dis ⁇ tillation and cool. Recover about 2.13 (4.7 pounds) of still bottoms.
• the final product should result in about 0.09 wt% residual peroxide, 2.1 wt% petroleum ether extract, no detectible free amine, and 28 wt% active amine ox ⁇ ide. Color measured using a spectrophotometer with a 1 mm cell referenced to water results in a % transmittance of 96.4% at 470 nm.
• 6-Dodecene was prepared via metathesis of 1-heptene using Grubbs Catalyst [1 st gen- eration, benzylidene-bis(tricyclohexylphosphine)dichlororuthenium]. The 6-dodecene was purified from the reaction mixture using fractional vacuum distillation.
• the 6-dodecene produced in Step 1 was aminomethylated using the following experi- mental procedure:
• Rh 2 O 3 , TPP and the olefin were heated under nitrogen ( ⁇ 1 bar) to 150 0 C.
• Me 2 NH was injected using syngas (H 2 :CO 2:1) 76bar and syngas was fed at this pressure for 2Oh.
• GC and GCMS analysis showed the following product distribution: olefm conversion 90% aldehydes 17.2% enamines 11.4% alcohols 8.3% amines 63%
• the amine product distribution was as follows: a 2-Pentyloctyldimethylamine 32.7% b 2-Butylnonyldimethylamine 27.3% c 2-Propyldecyldimethylamine 12.2% d 2-Ethylundecyldimethylamine 9.5% e 2-Methyldodecyldimethylamine 13.6% f Linear-tridecyldimethylamine 4.8
• Example 4 Dehydrogenation of long chain paraffin hydrocarbons, followed by ami- nomethylation.
• Rh 2 O 3 , TPP and the olefin were heated under nitrogen ( ⁇ 1 bar) to 15O 0 C.
• Me 2 NH was injected using syngas (H 2 : CO 2:1) 76bar and syngas was fed at this pressure for 2Oh.
• GC analysis showed: (small amounts of products from ClO & C13 olefins as well as aromatics in the feed were ignored at this stage).
• 1-Hexene was dimerized using zirconocene dichloride (Cp 2 ZrCl 2 ) and methylalumox- ane (Al:Zr:olef ⁇ n 50:1 :1000) and purified via fractional vacuum distillation.
• the major product was 2-butyl-l-octene (C12-vinylidene).
• Me 2 NH 3.38g Rh 2 O 3 , TPP and the olefin were heated under nitrogen ( ⁇ 1 bar) to 15O 0 C.
• Me 2 NH was injected using syngas (H 2 )CO 2:1) 76bar and syngas was fed at this pressure for 2Oh.
• the amine distribution was >97% to the required 3-butylnonyldimethylamine isomer.

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