EP0641298A1 - Method of oligomerization of 1-butene - Google Patents
Method of oligomerization of 1-buteneInfo
- Publication number
- EP0641298A1 EP0641298A1 EP92912983A EP92912983A EP0641298A1 EP 0641298 A1 EP0641298 A1 EP 0641298A1 EP 92912983 A EP92912983 A EP 92912983A EP 92912983 A EP92912983 A EP 92912983A EP 0641298 A1 EP0641298 A1 EP 0641298A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- butene
- oligomerization
- reaction
- acid
- mol
- 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.)
- Withdrawn
Links
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 238000006384 oligomerization reaction Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000314 lubricant Substances 0.000 claims abstract description 10
- 239000000654 additive Substances 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 6
- 230000035484 reaction time Effects 0.000 claims description 20
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 150000002763 monocarboxylic acids Chemical class 0.000 claims description 5
- 239000012442 inert solvent Substances 0.000 claims description 4
- GWYFCOCPABKNJV-UHFFFAOYSA-N isovaleric acid Chemical compound CC(C)CC(O)=O GWYFCOCPABKNJV-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 3
- 230000014759 maintenance of location Effects 0.000 abstract 1
- 150000002762 monocarboxylic acid derivatives Chemical class 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- 239000000047 product Substances 0.000 description 24
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 15
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000012071 phase Substances 0.000 description 8
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 7
- -1 polybutylenes Polymers 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000005292 vacuum distillation Methods 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 4
- 238000007334 copolymerization reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 3
- 150000001298 alcohols Chemical class 0.000 description 3
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 3
- 125000002091 cationic group Chemical group 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- 229910015900 BF3 Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- 150000004996 alkyl benzenes Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 238000012718 coordination polymerization Methods 0.000 description 2
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 229920001748 polybutylene Polymers 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical group ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 206010053317 Hydrophobia Diseases 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- 206010037742 Rabies Diseases 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000005234 alkyl aluminium group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 125000001743 benzylic group Chemical group 0.000 description 1
- 235000013844 butane Nutrition 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Chemical group 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical class CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical class CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229960002317 succinimide Drugs 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 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
-
- 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
- C07C2531/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
Definitions
- This invention is concerned with a method of oligomerization of 1-butene.
- the butene used for preparation of oligomers of butene has conventionally been iso- or tert-butene, that has been oligomerized to an oligomer of a suitable molar mass.
- These oligo- and polymers that are formed in the oligomerization of isobutene are called with a common name, poly-i-butenes or polybutylenes depending on the composition of the starting material.
- the source of i-butene has mainly been the so called raffinate I flow. In this raffinate I flow there are 1- and 2-butenes as well as butanes in addition to the isobutene. Alternatively the starting material used has been purified isobutene.
- cationic mechanism One of the most important mechanisms of polymerization of olefines are the cationic mechanism and the coordination polymerization. Of these mechanisms, coordination polymerization is primarily used for preparation of poly-1-butene plastics if the structure of the product to be formed is wished to define very exactly in forehand.
- the cationic mechanism produces only oligomers or viscotic fluids, so called liquid polymers, in the polymerization of 1-butene.
- the catalysts used in the cationic mechanism have been Lewis acids such as BF 3 , AlClo, AlBr «, TiCL, SnCL etc. It is known that Lewis acid catalysts cannot alone initiate a polymerization reaction but need a proton donor or a cocatalyst. Such cocatalysts are for example water, alcohols, carboxylic acids, inorganic acids, given alkyl halides or halogenes.
- the oligomerization can be carried out in bulk, in other words without any auxiliary solvent or in the presence of an inert solvent.
- Such inert solvents are for example alkanes such as hexane and heptane and cycloalkanes such as cyclohexane and cycloheptane.
- Oligomers suitable for different applications have thus conventionally been prepared by oligomerization of isobutene or of the raffinate I flow.
- the catalyst used has been for example BFg and AlClg.
- water, short-chained alcohols and organic acids have been mentioned as cocatalysts.
- 1-Butanol has generally been used together with BF « as cocatalyst when the intention has been to produce fractions suitable as lubricants and additives of those. These fractions have generally been produced by copolymerization.
- Larkin et al. (US 4 417 082, 4395 578 and 4434309) used 1-butene as short chained define and Cg...C j g alkene as long chained define in the copolymerization.
- the catalyst system was consisted of BFg and -1-butanol and possibly a transition metal cation.
- Nipe et al. (US 4 225 739) also used BFg as 1-butanol catalyst for the copolymerization but the short chained olefine was propene instead of 1- butene.
- Torck et al. for example used a BF -HF complex in tetra methylene sulphone solution as di- and trimerization catalyst.
- Chen et al. US 4 849 572 used water and/or methanol as cocatalyst and thus the M of the product was 520....1500 g/mol. Halaska et al.
- Carboxylic acid cocatalysts are very httle known for oligomerization of short- chained olefines. Sheng et al. (US 4 263 465) used a carboxylic acid with not more than five carbon atoms as cocatalyst. Their process was carried out in two steps. The first step comprised 1-butene as a fraction for oligomerization, the numerical average length of the carbon chain of which was 8...18, preferably 10...16 carbon atoms. In the second step the product fraction of the first step is cooligomerized together with Cg...C «g alfaolefines.
- Carboxylic acids containing for example five carbon atoms have been used for oligomerization of long- chained olefines.
- patent publication GB 1 378 449 there has for example been used n- and i-valerianic acid, methyl butanoic acid and mixtures of those to catalyst the oligomerization of Cg...C.p olefines together with BFg.
- Poly-i butene and polybutylene have been produced already in many years even in an industrial scale, but the produc- tion of poly-n-butene by oligomerization of 1-butene is not known.
- the oligomerization of 1-butene is carried out in a one step process by using a boron trifluoride cocatalyst complex as catalyst, wherein the cocatalyst is water, C 2 -CJ Q monoalcohol or C p -Cg monocarboxylic acid, prefer- ably valerianic acid.
- a boron trifluoride cocatalyst complex as catalyst, wherein the cocatalyst is water, C 2 -CJ Q monoalcohol or C p -Cg monocarboxylic acid, prefer- ably valerianic acid.
- the light fractions of poly-i-butene and poly ⁇ butylene can be substituted the numerical average molar mass being 110...ca 650 or even 850 g/mol.
- the object of this invention is an oligomerization method of 1-butene by which poly-n-butenes can be produced, the numerical average molar mass being in the aforesaid range.
- Oligomers of short-chained olefines are technically important intermediates which can be used for preparation of very different end products.
- the most important of the short-chained olefines are propene and different isomers of butene and pentene.
- the oligomers of butene, M of which is 110...2500 g/mol, is used for example as solvents, fuels, in preparation of chemicals and in prep- * aration of lubricants and additives for those.
- properties of the oligomers there can be mentioned for example resistance against oxidation caused by heat, a low freezing point, low volatility, and a good temperature- viscosity relation. The aforesaid properties are important, especially when the oligomers are used for producing lubricants and additives for those. Because of the reactive double bond, the oligomers can be used as intermediates in the production of different chemical compounds.
- oligomers of 1-butene are used for preparation of for example alkyl benzenes, alkyl phenols and alkyl succinic acid anhydride.
- Surfactants are prepared from alkyl benzenes and phenols by sulphonation.
- the oligomers of 1-butene can be used for example for preparing sulphonates, phenates, thiophosponates and ashless dispersants, alkenyl succinic imides.
- the molar mass of the hydrocar ⁇ bon part in these compounds is ca 350...1200 g/mol, even 2500 g/mol in alkenyl succinic imide.
- a steel reactor with the volume of 300 ml was internally cooled by a cooling coil and, when necessary, externally heated by a outer electric bath.
- the reactor was equipped with a mixer.
- 1-Butene and the catalyst were fed into the reactor via a valve to the liquid phase.
- the temperature of the reaction mixture was studied by a thermocouple.
- the temperature of the reaction mixture was tried to keep at the wished value with the precision of ⁇ 1°C from the desired value.
- 100 ml n-heptane was added as solvent to the reactor in nitrogen atmosphere and also cocatalyst the amount of which is mentioned in the example.
- the solvent had been dried with molecular sieves. Thereafter 60...70 g of liquid 1-butene was added to the reactor.
- the reactor was pressurized with BFg gas and the catalyst complex was formed in situ and the reaction started immediately.
- the pressure of the reactor was kept constant by means of BFg gas.
- the reaction parameters were the following: the pressure 2.5...10 bar expressed as over pressure, the reaction temperature 10...70°C and the reaction time 1...121 minutes or 1...6 hours.
- the reaction was finished by adding an excess of either NaOH solution or water to the reactor.
- the product fraction was washed with NaOH solution and thereafter with water until the pH of the fraction was neutral.
- the product distribution was analyzed by the GC method. Examples 1 and 2
- the cocatalyst used was 14.2 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 4.0 bar and the temperature 20°C.
- the reaction time in Example 1 was 9 minutes and in Example 2 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the numerical average molar mass of the product distributions of the Examples were 237 g/mol and 310 g/mol.
- the cocatalyst used was 5.1 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 4.0 bar and the temperature 20°C.
- the reaction time in Example 3 was 9 minutes and in Example 4 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the numerical average molar mass of the product distributions of the Examples were 268 g/mol and 383 g/mol.
- the viscosity index 81 was defined for this unhydrated product, measured in 100°C, the kinematic viscosity being 4.3 cSt.
- the cocatalyst used was 37.8 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 4.0 bar and the temperature 20°C.
- the reaction time in Example 5 was 9 minutes and in Example 6 49 minutes. After the reaction times mentioned the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the numerical average molar mass of the product distributions of the Examples were 220 g/mol and 302 g/mol.
- the cocatalyst used was 13.4 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 2.5 bar and the temperature 20°C.
- the reaction time was in Example 7 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the cocatalyst used was 13.0 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 4.0 bar and the temperature 20°C.
- the reaction time was 6 hours. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the numerical average molar mass of the product distributions of the Example were 386 g/mol.
- the cocatalyst used was 4.8 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 10 bar and the temperature 10°C.
- the reaction time in Example 9 was 9 minutes and in Example 10 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the cocatalyst used was 4.9 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 10 bar and the temperature 40°C.
- the reaction time in Example 11 was 4 minutes and in Example 12 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the numerical average molar mass of the product distributions of the Examples were 275 g/mol and 371 g/mol.
- the lower fractions (C.g_) were separated by vacuum distillation from the product of Example 6, whereby M - 429 g/mol.
- the viscosity index 82 was defined for this unhydrated product measured in 100°C, the kinematic viscosity being 7.0 cSt.
- the cocatalyst used was 5.0 mmol n-valerianic acid per one mole of 1-butene.
- the pressure of the reactor was 10 bar and the temperature 70°C.
- the reaction time in Example 13 was 9 minutes and in Example 14 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution.
- the hydrogen carbon phases were analyzed and the results were the following:
- the numerical average molar mass of the product distributions of the Examples were 219 g/mol.
- 1-butene can be oligomerized also with other organic acid cocatalysts than n- valerianic acid, both with alcohols and water as Examples 15...21 show.
- the pres ⁇ sure of the reactor was 4.0 bar and the temperature 20°C, the reaction time 5 being 36 minutes.
- the cocatalysts were acetic acid (Ex. 15), n-octanoic acid (Ex. 16), ethanol (17), 1-pentanol (18), 1-octanol (19) and water (20).
- the comparison examples is a reaction carried out in the same conditions with n-valerianic acid.
- the cocatalyst used was 14.5...15.9 mmol cocatalyst per one mole as 1-butene.
Abstract
The invention is concerned with a method of oligomerization of 1-butene to a hydrogen carbon comprising in average 12-48 carbon atoms and an unsaturated double bond, wherein the reaction temperature is ca -30...90 DEG C, the total pressure ca 1-15 bar and the retention time in the reaction ca 5 minutes...10 hours by using a complex of BF3 and water, C2-C10 monoalcohol or C2-C8 monocarboxylic acid as catalyst. The product obtained can be used as solvent or lubricant and as intermediate when preparing different chemicals for example lubricants or additives of those.
Description
Method of oligomerization of 1-butene
This invention is concerned with a method of oligomerization of 1-butene.
KNOWN TECHNIQUE
The butene used for preparation of oligomers of butene has conventionally been iso- or tert-butene, that has been oligomerized to an oligomer of a suitable molar mass. These oligo- and polymers that are formed in the oligomerization of isobutene are called with a common name, poly-i-butenes or polybutylenes depending on the composition of the starting material. The source of i-butene has mainly been the so called raffinate I flow. In this raffinate I flow there are 1- and 2-butenes as well as butanes in addition to the isobutene. Alternatively the starting material used has been purified isobutene.
One of the most important mechanisms of polymerization of olefines are the cationic mechanism and the coordination polymerization. Of these mechanisms, coordination polymerization is primarily used for preparation of poly-1-butene plastics if the structure of the product to be formed is wished to define very exactly in forehand. The cationic mechanism produces only oligomers or viscotic fluids, so called liquid polymers, in the polymerization of 1-butene.
The catalysts used in the cationic mechanism have been Lewis acids such as BF3, AlClo, AlBr«, TiCL, SnCL etc. It is known that Lewis acid catalysts cannot alone initiate a polymerization reaction but need a proton donor or a cocatalyst. Such cocatalysts are for example water, alcohols, carboxylic acids, inorganic acids, given alkyl halides or halogenes. The oligomerization can be carried out in bulk, in other words without any auxiliary solvent or in the presence of an inert solvent. Such inert solvents are for example alkanes such as hexane and heptane and cycloalkanes such as cyclohexane and cycloheptane.
Oligomers suitable for different applications have thus conventionally been prepared by oligomerization of isobutene or of the raffinate I flow. The catalyst used has been for example BFg and AlClg. Generally, water, short-chained alcohols and organic acids have been mentioned as cocatalysts. 1-Butanol has generally been used together with BF« as cocatalyst when the intention has been to produce fractions suitable as lubricants and additives of those. These fractions have generally been produced by copolymerization. Larkin et al. (US 4 417 082, 4395 578 and 4434309) used 1-butene as short chained define and Cg...Cjg alkene as long chained define in the copolymerization. The catalyst system was consisted of BFg and -1-butanol and possibly a transition metal cation. Nipe et al. (US 4 225 739) also used BFg as 1-butanol catalyst for the copolymerization but the short chained olefine was propene instead of 1- butene. Watts et al. (US 4 413 156) used a mixture of Cg-C, olefine as starting material from which C^.-C ^ inner olefines were prepared by means of a disproportion reaction. By further oligomerization of this fraction with BFg as 1- butanol, catalyst fractions of a product that were suitable for preparation of additives for lubricants were obtained. The processes described in the above mentioned patents are either two step polymerizations or copolymerizations.
The catalysts used in the oligomerization of the raffinate I flow partly depends on the wished product distribution. Torck et al. (GB 1312950) for example used a BF -HF complex in tetra methylene sulphone solution as di- and trimerization catalyst. Chen et al. (US 4 849 572) used water and/or methanol as cocatalyst and thus the M of the product was 520....1500 g/mol. Halaska et al. (EP 337 737) was using BFg or alkyl aluminium chlorides for the oligomerization of a raffinate II flow that contains 1- and 2-butenes as main components which chlorides have the common formula of R AlCl or RA1C , wherein R is CI_Q alkyl. They used HF, HC1 or compounds containing a reactive chlorine or fluorine atom bond to a tertiaric, benzylic or allylic carbon atom as cocatalyst. These catalyst systems are the same as the catalysts used by Loveless et al. (US 4041098) for oligomerization of C^...C14 olefines, preferably Cg...C^g olefines.
Carboxylic acid cocatalysts are very httle known for oligomerization of short- chained olefines. Sheng et al. (US 4 263 465) used a carboxylic acid with not more than five carbon atoms as cocatalyst. Their process was carried out in two steps. The first step comprised 1-butene as a fraction for oligomerization, the numerical average length of the carbon chain of which was 8...18, preferably 10...16 carbon atoms. In the second step the product fraction of the first step is cooligomerized together with Cg...C«g alfaolefines. Carboxylic acids containing for example five carbon atoms, have been used for oligomerization of long- chained olefines. According to patent publication GB 1 378 449 there has for example been used n- and i-valerianic acid, methyl butanoic acid and mixtures of those to catalyst the oligomerization of Cg...C.p olefines together with BFg.
During the last ten years the production of MTBE or methyl-tert-butylether, that has strongly increased and is further increased, restricts the availability of isobutene (by increasing the production costs at the same time). The object of this invention is to show that it is possible to produce fractions that substitute low oligomers of isobutene by oligomerization of 1-butene to poly-n-butene (M = 110...ca 650 g/mol or even 850 g/mol). Poly-i butene and polybutylene have been produced already in many years even in an industrial scale, but the produc- tion of poly-n-butene by oligomerization of 1-butene is not known.
In this invention the oligomerization of 1-butene is carried out in a one step process by using a boron trifluoride cocatalyst complex as catalyst, wherein the cocatalyst is water, C2-CJQ monoalcohol or Cp-Cg monocarboxylic acid, prefer- ably valerianic acid.
By the method of this invention the light fractions of poly-i-butene and poly¬ butylene can be substituted the numerical average molar mass being 110...ca 650 or even 850 g/mol.
The object of this invention is an oligomerization method of 1-butene by which poly-n-butenes can be produced, the numerical average molar mass being in the
aforesaid range.
USE
Oligomers of short-chained olefines are technically important intermediates which can be used for preparation of very different end products. The most important of the short-chained olefines are propene and different isomers of butene and pentene. The oligomers of butene, M of which is 110...2500 g/mol, is used for example as solvents, fuels, in preparation of chemicals and in prep- * aration of lubricants and additives for those.
The oligomers of 1-butene prepared according to this invention and which also are known as poly-n-butenes, contain an olefinic double bond in the polymer chain, the reactivity of which is increased. The polydispersity of their molar masses is M^VM = 1.02...1.5. Of the properties of the oligomers there can be mentioned for example resistance against oxidation caused by heat, a low freezing point, low volatility, and a good temperature- viscosity relation. The aforesaid properties are important, especially when the oligomers are used for producing lubricants and additives for those. Because of the reactive double bond, the oligomers can be used as intermediates in the production of different chemical compounds. In the preparation of chemicals, oligomers of 1-butene are used for preparation of for example alkyl benzenes, alkyl phenols and alkyl succinic acid anhydride. Surfactants are prepared from alkyl benzenes and phenols by sulphonation. In the additives of lubricants, the oligomers of 1-butene can be used for example for preparing sulphonates, phenates, thiophosponates and ashless dispersants, alkenyl succinic imides. The molar mass of the hydrocar¬ bon part in these compounds is ca 350...1200 g/mol, even 2500 g/mol in alkenyl succinic imide. Other applications are for example as lubricant in two stroke spark ignition engines, as working oil for metallurgic materials in rolling and drawing, in the leather and rubber industry and to make different surfaces hydrophobia By bydration of the oligomers it is possible to obtain transformator oils, electrically isolating and cable oils of high quality and non-toxic cosmetic
oils and white oils.
EXAMPLES
The following examples have been presented to describe in detail the oligomeriz¬ ation of 1-butene of the invention which, however, are not meant to restrict the scope of invention in any way.
The oligomerization reactions of 1-butene was carried out as following if not otherwise mentioned:
A steel reactor with the volume of 300 ml was internally cooled by a cooling coil and, when necessary, externally heated by a outer electric bath. The reactor was equipped with a mixer. 1-Butene and the catalyst were fed into the reactor via a valve to the liquid phase. The temperature of the reaction mixture was studied by a thermocouple. The temperature of the reaction mixture was tried to keep at the wished value with the precision of ± 1°C from the desired value. 100 ml n-heptane was added as solvent to the reactor in nitrogen atmosphere and also cocatalyst the amount of which is mentioned in the example. The solvent had been dried with molecular sieves. Thereafter 60...70 g of liquid 1-butene was added to the reactor. After the addition of the monomer, the reactor was pressurized with BFg gas and the catalyst complex was formed in situ and the reaction started immediately. The pressure of the reactor was kept constant by means of BFg gas. The reaction parameters were the following: the pressure 2.5...10 bar expressed as over pressure, the reaction temperature 10...70°C and the reaction time 1...121 minutes or 1...6 hours. The reaction was finished by adding an excess of either NaOH solution or water to the reactor. The product fraction was washed with NaOH solution and thereafter with water until the pH of the fraction was neutral. The product distribution was analyzed by the GC method.
Examples 1 and 2
The cocatalyst used was 14.2 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 4.0 bar and the temperature 20°C. The reaction time in Example 1 was 9 minutes and in Example 2 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
The numerical average molar mass of the product distributions of the Examples were 237 g/mol and 310 g/mol. The lower fractions (C^β_) were separated by vacuum distillation from the product of Example 2, whereby M = 360 g/mol.
Examples 3 and 4
The cocatalyst used was 5.1 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 4.0 bar and the temperature 20°C. The reaction time in Example 3 was 9 minutes and in Example 4 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
^32+
47.0
The numerical average molar mass of the product distributions of the Examples were 268 g/mol and 383 g/mol. The lower fractions (C^g_) were separated by
vacuum distillation from the product of Example 4, whereby M = 407 g/mol. The viscosity index 81 was defined for this unhydrated product, measured in 100°C, the kinematic viscosity being 4.3 cSt.
Examples 5 and 6
The cocatalyst used was 37.8 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 4.0 bar and the temperature 20°C. The reaction time in Example 5 was 9 minutes and in Example 6 49 minutes. After the reaction times mentioned the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
The numerical average molar mass of the product distributions of the Examples were 220 g/mol and 302 g/mol. The lower fractions (C.g_) were separated by vacuum distillation from the product of Example 6, whereby M = 357 g/mol.
Example 7
The cocatalyst used was 13.4 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 2.5 bar and the temperature 20°C. The reaction time was in Example 7 49 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
The selectivities
C C^4--ccoonnvv.. CCgg CCi|2p CC-1ig6 CC20 < C*24 C2g Cg2+ Ex. 7 81.8% 0.6 43.3 40.7 10.5 3.9 1.0
The numerical average molar mass of the product distributions of the Example were 202 g/mol.
Example 8
The cocatalyst used was 13.0 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 4.0 bar and the temperature 20°C. The reaction time was 6 hours. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
Selectivities
C4-conv. Cg C12 CC1166 CC22C0 C24 C28 Cg2+ Ex. 8 ca 99% 0.9 4.2 9.0 8.0 7.5 8.4 58.4
The numerical average molar mass of the product distributions of the Example were 386 g/mol. The lower fractions (C-g_) were separated by vacuum distilla¬ tion from the product of Example 8, whereas M = 467 g/mol.
Examples 9 and 10
The cocatalyst used was 4.8 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 10 bar and the temperature 10°C. The reaction time in Example 9 was 9 minutes and in Example 10 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
°32+
31.3
The numerical average molar mass of the product distributions of the Examples were 247 g/mol and 349 g/mol. The lower fractions (C- ) were separated by vacuum distillation from the product of Example 6, whereby M = 365 g/mol.
Examples 11 and 12
The cocatalyst used was 4.9 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 10 bar and the temperature 40°C. The reaction time in Example 11 was 4 minutes and in Example 12 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
The numerical average molar mass of the product distributions of the Examples were 275 g/mol and 371 g/mol. The lower fractions (C.g_) were separated by vacuum distillation from the product of Example 6, whereby M - 429 g/mol. The viscosity index 82 was defined for this unhydrated product measured in 100°C, the kinematic viscosity being 7.0 cSt.
Examples 13 and 14
The cocatalyst used was 5.0 mmol n-valerianic acid per one mole of 1-butene. The pressure of the reactor was 10 bar and the temperature 70°C. The reaction time in Example 13 was 9 minutes and in Example 14 121 minutes. After the reaction times mentioned, the reaction was stopped by means of NaOH solution. The hydrogen carbon phases were analyzed and the results were the following:
The numerical average molar mass of the product distributions of the Examples were 219 g/mol. The lower fractions (C.g_) were separated by vacuum distilla¬ tion from the product of Example 14, whereas M = 341 g/mol.
10. Examples 15..21
1-butene can be oligomerized also with other organic acid cocatalysts than n- valerianic acid, both with alcohols and water as Examples 15...21 show. The pres¬ sure of the reactor was 4.0 bar and the temperature 20°C, the reaction time 5 being 36 minutes. The cocatalysts were acetic acid (Ex. 15), n-octanoic acid (Ex. 16), ethanol (17), 1-pentanol (18), 1-octanol (19) and water (20). The comparison examples is a reaction carried out in the same conditions with n-valerianic acid. The cocatalyst used was 14.5...15.9 mmol cocatalyst per one mole as 1-butene.
0
5
Claims
1. Method of oligomerization of 1-butene, characterized in that n-butene is oligomerized in one step by means of a complex consisting of BFg and water, Cp-C-iQ monoalcohol or Cp-C8 monocarboxylic acid to a hydrogen carbon containing 12-48 carbon atoms.
2. Method of claim 1, characterized in that the monocarboxylic acid mentioned is n-valerianic acid, i-valerianic acid, methyl butanoic acid or a mixture of those.
3. Method of claim 1 or 2, characterized in that the temperature in the oligomer¬ ization is -30 - 90°C
4. Method of claim 1,2 or 3, characterized in that the total pressure in the oligomerization reaction is 1-15 bar.
5. Method of any of claims 1-4, characterized in that the reaction time of the oligomerization reaction is 5 min - 10 hours.
6. The use of oligomerization of 1-butene prepared with the method of any of claims 1-5 as solvent or intermediate in preparing lubricants or additives of those.
AMENDED CLAIMS
[received by the International Bureau on 8 December 1992 (08.12.92) ; original claims 1 - 6 replaced by amended claims 1 - 7 (1 page)]
1. Method of oligomerization of 1-butene, characterized in that 1-butene is oligomerized in one step by means of a complex consisting of BF3 and water, C2- C10 monoalcohol or C^-C8 monocarboxylic acid to a hydrogen carbon containing 12-48 carbon atoms, in such a way that the BF3-complex is made m jjitu in a constant BF3-pressure by feeding at first inert solvent, cocatalyst and the 1- butene to the reactor.
2. Method of claim 1, characterized in that the monocarboxylic acid mentioned is n-valerianic acid, i-valerianic acid, methyl butanoic acid or a mixture of those.
3. Method of claim 1 or 2, characterized in that the temperature in the oligomer¬ ization is 0 - 90°C.
4. Method of claim 1,2 or 3, characterized in that the total pressure in the oligomerization reaction is 1-15 bar.
5. Method of any of claims 1-4, characterized in that the reaction time of the oligomerization reaction is 0,5 min - 10 hours.
6. Method of any of claims 1-5, characterized in that the inert solvent is an alkane or a cycloalkane, preferably n-heptane.
7. The use of oligomerization of 1-butene prepared with the method of any of claims 1-6 as solvent or intermediate in preparing lubricants or additives of those.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FI913690A FI90231C (en) | 1991-08-02 | 1991-08-02 | Method for oligomerization of 1-butene |
FI913690 | 1991-08-02 | ||
PCT/FI1992/000199 WO1993002993A1 (en) | 1991-08-02 | 1992-06-26 | Method of oligomerization of 1-butene |
Publications (1)
Publication Number | Publication Date |
---|---|
EP0641298A1 true EP0641298A1 (en) | 1995-03-08 |
Family
ID=8532953
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP92912983A Withdrawn EP0641298A1 (en) | 1991-08-02 | 1992-06-26 | Method of oligomerization of 1-butene |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP0641298A1 (en) |
FI (1) | FI90231C (en) |
WO (1) | WO1993002993A1 (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FI93828C (en) * | 1992-12-31 | 1995-06-12 | Neste Oy | Method for oligomerization of olefin mixtures, oligomer prepared by the method and its use |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4263465A (en) * | 1979-09-10 | 1981-04-21 | Atlantic Richfield Company | Synthetic lubricant |
-
1991
- 1991-08-02 FI FI913690A patent/FI90231C/en not_active IP Right Cessation
-
1992
- 1992-06-26 WO PCT/FI1992/000199 patent/WO1993002993A1/en not_active Application Discontinuation
- 1992-06-26 EP EP92912983A patent/EP0641298A1/en not_active Withdrawn
Non-Patent Citations (1)
Title |
---|
See references of WO9302993A1 * |
Also Published As
Publication number | Publication date |
---|---|
FI90231B (en) | 1993-09-30 |
FI90231C (en) | 1994-01-10 |
FI913690A0 (en) | 1991-08-02 |
FI913690A (en) | 1993-02-03 |
WO1993002993A1 (en) | 1993-02-18 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
KR0140716B1 (en) | Process for preparing polybutenes having enhanced reactivity using boron trifluoride catalysts | |
US4952739A (en) | Organo-Al-chloride catalyzed poly-n-butenes process | |
US5068490A (en) | BF3-tertiary etherate complexes for isobutylene polymerization | |
AU565575B2 (en) | Cationic polymerisation of 1-olefins | |
US3876720A (en) | Internal olefin | |
EP0646103B1 (en) | Bf3-tertiary etherate complexes for isobutylene polymerization | |
HUT72717A (en) | Amorphous olefin copolymers, lubricating oil compositions containing thereof and processes for preparing the said copolymers and their derivatives | |
US4254294A (en) | Polymerization reactions in the presence of a catalyst containing aluminum oxide, boron oxide and halogen | |
WO2009131765A1 (en) | Hydroxyaromatic functionalized polyalpha-olefins | |
US4417082A (en) | Thermal treatment of olefin oligomers via a boron trifluoride process to increase their molecular weight | |
US4395578A (en) | Oligomerization of olefins over boron trifluoride in the presence of a transition metal cation-containing promoter | |
US4469910A (en) | Method for the oligomerization of alpha-olefins | |
EP0641298A1 (en) | Method of oligomerization of 1-butene | |
US4594469A (en) | Method for the oligomerization of alpha-olefins | |
US2551638A (en) | Production of lubricating oils by condensation of olefinic hydrocarbons | |
EP0367386B1 (en) | Improved A1C13 - catalyzed process for preparing poly-n-butenes from mixed butenes | |
WO1996026913A1 (en) | Process for preparation of poly-n-butenes having high viscosity | |
EP0677033A1 (en) | Method for oligomerization of olefins and olefin mixtures | |
CA2161664A1 (en) | Catalyst composition for alkene oligomerisation and co-oligomerisation | |
US5326921A (en) | AlCl3 -catalyzed process for preparing poly-N-butenes from mixed butenes | |
CS272398B1 (en) | Method of poly-n-butene oils production | |
JP7378344B2 (en) | Method for producing highly reactive polybutene | |
CZ173795A3 (en) | Process for preparing synthetic oils, olefinic copolymer for such oils and process for preparing thereof | |
US11370987B2 (en) | Method of controlling kinematic viscosity of polyalphaolefin | |
EP0883614B1 (en) | Additives usable in preparation of alkenyl succinic anhydride |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 19940117 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE CH DE ES FR GB IT LI NL SE |
|
17Q | First examination report despatched |
Effective date: 19960116 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 19960727 |