Note: Descriptions are shown in the official language in which they were submitted.
2152fi63
Wo 94/15895 PCT/F193/00~40
Method for oligomerization of olefins and olefin mixtures
The present invention relates to a method for the oligomPri7~tion of olefins and olefin
5 Illix.Lul~S by using a boron trifluoride cocatalyst complex.
The oligomerization and polymeri7~tion of various olefins constitute commonly known
technology. These reactions may occur thermally without a catalyst; as radical reactions
over, for example, peroxide catalysts or coordination polymPri7~tion catalysts; by an
10 anionic mechanism over basic catalysts; by a cationic mech~nicm over Friedel-Crafts
catalysts; and by polymerization by using molecular sieves, for example zeolites.
An anionic mech~ni~m is used mainly for olefin r~impri7~til~n reactions, for example, for
the ~im~ri7~tion of propylene to 4-methyl-1-pentene. Coordination polymerization is used
15 mainly for the preparation of various pl~ctics~ such as polyethylene, polypropylene, and
poly-l-butene, in which it is desirable to determine in advance precisely the structure of
the formed product. A c~tionic me~h~nicm and polymeri7~tion by using molecular sieves
produce in the polymçri7~tion of olefins only light oligomers or viscous liquids, so-called
liquid polymers.
The catalysts used in the c~tionic m~h~nicm have been Lewis acids such as BF3, AlCl3,
AlBr3, TiC14, SnC14, etc. It is known that Lewis-acid catalysts cannot alone initiate a
polymerization reaction; they require a proton donor, i.e. a cocatalyst. Examples of such
cocatalysts are water, alcohols, carboxylic acids, inorganic acids, certain alkyl halides,
25 and halogens. The oligomerization can be carried out in bulk, i.e. without an auxiliary
solvent, or in the presence of an inert solvent. FY~mples of such inert solvents are alkanes
such as hexane and heptane, and cyclo~lk~nes such as cycloheY~ne and cycloheptane.
BF-catalyzed oligomt-ri7~tion has been known at least since 1873, when Butlerov and
30 Gorianov reported that isobutene and propylene became oligom~ri7ed by a BF3 treatment
at room temperature (Kennedy, J., Cationic polym~ri7~tion of olefins, J. Wiley & Sons,
New York, 1975, p. 8).
Oligom~ri7~ion occurs in the presence of an active catalyst complex. Such a catalyst
Wo 94/15895 PCT/FI93/00540
2152fi6~ 2
complex can be prepared through a reaction between BF3 and a cocatalyst, separate from
the oligomerization reactor or in situ in the reactor. Water, short-chain alcohols, and or-
ganic acids are commonly mentioned as the cocatalysts used. A 1-butanol cocatalyst has
commonly been used together with BF3 when the object has been to produce fractions
5 suitable for use as lubricants or their additives. For the above uses, the monomer has
commonly been some long-chain alpha-olefin or internal olefin, or their mixture. In
particular, 1-decene has been used as the monomér.
The combination of BF3, 1-butanol and 1-decene has been used by, for example, Cupples
10 et al. (US 4 282 392), Shubkin (US 4 910 355), Dileo (EP 352 723), and Akatsu (EP
364 889). Other cocatalysts used with BF3 and decene include water (Bronstert, EP
271 034), alcohol alcoxylate (Theriot, EP 467 345), alcohol mixtures (Pratt, US 4 587 3-
68), an alcohol ester mixture (Brennan, US 3 997 621), and a mixture of butanol and
ethyl glycol or of butanol, ethyl glycol and methylethyl ketone (Morgansson and Vayda,
15 US 4 409 415, US 4 436 947, EP 77 113).
Watts et al. (US 4 413 156), Darden et al. (US 4 420 646), Hammond et al. (US
4 420 647, EP 136 377), and Larkin et al. (US 4 434 308) used as the initial m~tçn~lc C8-
Cl8 internal olefins or mixtures of C8-C,8 internal olefins and alpha-olefins. The oligomeri-
20 zation of this fraction with a BF3-1-butanol catalyst yielded as products fractions suitable
for use for the preparation of additives for lubricants.
Nipe et al. (US 4 225 739) also used a BF3-1-butanol catalyst for copolymerization in
which the short-chain olefin was propylene and the long-chain olefin was a mixture of C~s~
25 C,8 olefins.
Larkin et al. (US 4 395 578, US 4 417 082, and US 4 434 309) used for copolymerization
1-butene or propylene as the short-chain olefin and from one to three C6-Cl8 alkenes of
different lengths as the long-chain olefin. The catalyst system consisted of BF3 and 1-
30 butanol and possibly a transition-metal cation.
Pasky (US 4 451 684) used for co-oligom~n7~tion propylene oligomers having an average
carbon chain length of 12-i8 and C5-C6 olefins, the catalyst complex comprising BF3 and
_ Wo 94/15895 215 2 6 6 9 PCT/Fl93/00540
butanol.
Nelson and Zuech (US 4 484 014) used a two-step method in which the first step was a
coordination catalyzed reaction for the oligomerization of ethylene with TEA (triethyl
5 aluminum) into C6-C,6 olefins. The reaction occurs at a higher temperature than does
normal oligomPri7~tion of ethylene. For this reason the C6-CI6 fraction contained branched
olefins 10 - 55 %, whereas under normal conditions nearly 100 % straight-chain alpha-
olefins would have been produced with TEA. In the second step, the produced mixture of
ethylene oligomers was further oligomerized in a batch reaction into a lubricant fraction
10 by using a BF3-propanol catalyst. In this, the catalyst complex formed in situ through a
reaction between BF3 and propanol.
Schick and Gemmil (US 4 182 922) used propylene or a mixture of ethylene and propyle-
ne as the monomer feed in the first step. This mixture was oligomerized with a catalyst
15 of VOC13 and ethyl aluminum chloride. The produced oligomer mixture was further co-
oligomerized with a longer-chain olefin or a mixture of propylene and a longer-chain
olefin by using a BF3-propanol complex formed in situ. The longer-chain olefin used was
butene, hexene or decene. The longer-chain olefin or the mixture of propylene and a
longer-chain olefin was fed into the second step in a 'h-batch manner. The viscosity index
20 of the reaction products was dependent on the longer-chain olefin used. When butene was
used, the viscosity index of the end product was 113 and, when decene was used, it was
133.
Hsia Chen and Tabak (US 4 568 786) used as the feed in the first step a mixture of
25 propylene and butene, which was oligomerized with an HZSM-5-zeolite catalyst. From
the formed product there was separated a C9-Cl8 fraction, which was oligomerized in the
second step with a zeolite or BF3 catalyst. In a BF3-catalyzed batch reaction, butanol was
used as a cocatalyst, and the complex was formed separate from the oligomerization
reactor.
30
Herkelcberg et al. (US 4 319 064, US 4 386 229) used as the 1st step a disproportionation
reaction of l-octene and/or l-decene to produce a mixture of C8-Cl8 internal olefins. This
mixture or a part of it was oligomerized in the 2nd step with a BF3-propanol or BF3-
WO 94115895 215 2, 6 6 9 4 PCTtFI93/00540
phosphoric acid catalyst complex formed in situ.
The catalysts used for the oligomerization of the Raffinate I stream flow, which contains
n-butenes and inert butanes in addition to the principal component i-butene, depend in part
5 on the desired product distribution. Torck et al. (GB 1 312 950) used as a di- and
trim~ri7~tion catalyst, for example, a BF3-HF complex in a tetramethylene sulfonic
solution. Chen et al. (US 4 849 572) used water and/or methanol as a cocatalyst, in which
case the product, poly-i-butene, had M" = 520-1500 g/mol. Samson (EP 145 235) used
a BF3-ethanol complex for the oligomeri7~tion of R~ffin~te I.
For the oligomerization of the ~ffin~te II stream, which contains 1- and 2-butenes and
inert butanes as the principal components, Halaska et al. (EP 337 737) used BF3 or alkyl
aluminum chlorides having a general formula of R2AlCl or RAlCl2, where R is a Cl-C8
alkyl. As cocatalysts they used HF, HCl, or compounds which contained a reactive15 chlorine or fluorine atom bound to a tertiary, benzylic or allylic carbon atom. These
catalyst systems are the same as the catalysts used in the patent of Loveless et al. (US
4 041 098) for the oligom~ri7~tion of C3-CI4 olefins, preferably C8-C10 olefins.
Pure 1-butene was oligomerized by Audisio and Priola (Makromolekulare Chemie, vol.
20 191, 1990, pp. 725-730) by using a separately prepared catalyst complex which was made
up of BF3 and water or phosphoric acid.
Carboxylic acid cocatalysts are little known in the oligomerization of short-chain olefins.
Sheng and Arnold (US 4 263 465) used as a cocatalyst a carboxylic acid having at25 maximum five carbon atoms. Their process was a two-step process. The first step
comprised the oligomerization of l-butene into a fraction having a number-average carbon
chain length of 8-18, preferably 10-16 carbon atoms. In the second step, the product
fraction of the first step is co-oligomerized with C8-CI8 alpha-olefin. In each step there
was used in the batch reaction a catalyst complex which had been prepal~d by a reaction
30 between BF3 and a cocatalyst, separate from the oligomerization reactor.
Carboxylic acids, among them those containing five carbon atoms, have also been used
for the oligomerization of longer-chain olefins. For example, in patent GB 1 378 449, n-
_ Wo 94/15895 2155 2 6 6 9 PCT/F193/00540
and i-valeric acid, methylbutanoic acid, or mixtures of these were used for catalyzing the
oligomeri7~tion of C6-Cl2 olefins, preferably 1-decene, together with BF3. In this patent
the catalyst complex was formed separate from the oligomerization reactor. Furthermore,
two different flows were fed into the reactor, in a 'h-batch manner. These flows consisted
5 of a BF3-cocatalyst complex and a monomer saturated with BF3.
The present invention relates to a method for the oligomeri_ation of olefins and olefin
mixtures in a one-step process by using a boron trifluoride cocatalyst complex. In this
invention, the oligomeri_ation of olefins or olefin mixtures is carried out in a one-step
10 process by using as the catalyst a boron trifluoride cocatalyst complex in which the
cocatalyst is water, a C2-ClO monoalcohol, or a C2-C8 monocarboxylic acid, preferably
pentanol or valeric acid. The invention is characterized by the characteristics presented
below in the patent claims.
lS By the process according to the present invention it is possible to oligomerize olefins and
olefin mixtures. The olefin l~lixlu~e is preferably the so-called R~ffin~te II stream, in
which the principal coll~l)onents are 1- and 2-butenes and butanes, or a mixture of a
longer-chain, C6-C20 olefin and R~ffin~te II. A method for the oligomeri7~tion of such
clures is not previously known in the liteldt~re. In addition, it is also possible by the
20 method to oligomerize long-chain olefins alone, as shown in the examples.
When olefin mixtures are oligom~-ri7pd by the method according to the invention, the
products formed are co-oligomers and not, for example",-ix~u,~s of oligomers of butene
and oligomers of longer-chain olefin (homo-oligomers). In the reaction the olefins may
25 randomly link with a hydrocarbon chain, and this can be demonstrated with the appended
mass spectrometric analyses (the experiments corresponding to the chromatograms
presented are Examples 63-66). The analyses were performed by direct inlet mass
spectrometry by using as the ~ualdt~ls a VG Trio-2-quadrupole mass spectrometer (VG
Masslab, Manchester, U.K.). Analysis conditions: mass range 200-1000 g/mol, scanning
30 time 3 s, electron energy 70 eV, ionization current 200 ~A, ion source temperature
200 C. The temperature program used for the sample evaporation was: S0 C (2 min)
+ S0 C/min 400 C.
WO 94/lS895 215 2 6 6 9 PCT~93/00540
Olefin oligomers are terhnic~lly important intermedi~tes which can be used for the
preparation of highly various end products.
Oligomers plc~aled according to the present invention contain in the polymer chain an
S olefinic double bond having increased reactivity. The p~opelLies of the oligomers include
resistance to oxidation under the effect of heat, a low pour point, low volatility, and a
good ~l~lpeldture-viscosity depçndence. The above pro~el Lies are important, especially if
the oligomers are used for the production of lubricants and their additives. On the other
hand, the method according to the invention can also be used for producing oligomers
10 having a low viscosity index. These oligomers and their derivatives are used in the main
for applications other than lubricants and their additives.
Owing to the reactive double bond the oligomers can be used as intermediates in the
production of various çhemi~l colllpoul-ds. In the pl~aldtion of chemic~lc, oligomers are
lS used for the pr~dtion of, for example, alkyl ben7Pnes, alkyl phenols, and alkyl succinic
acid anhydride. From alkyl be-n7~nes and alkyl phenols, surface active agents are l,lepa~ed
by sulfonation. In additives of lubricants, oligomers can be used, for example, in the
pl~aldtion of sulfonates, phen~t~s, thiophosphonates, and ash-free dispersing agents,
alkenyl succinimides In these colll~ounds the molecular mass of the hydrocarbon fraction
20 is approx. 350-1200 g/mol, in alkenyl succinimide as high as 2500 g/mol. Other uses
include the use as a lubricant in two-stroke spark-ignition engines, as the processing oil
in the rolling and drawing of metallurgic m~t~ri~ls, in the leather and rubber industries,
and in making various surfaces hydrophobic. By the hydrogenation of oligomers it is
possible to obtain high-quality transformer oils, electrical insulation and cable oils, and
25 non-toxic cosmetic oils and white oils.
To illustrate the present invention, the oligomeri_ation of olefins and olefin mixtures by
a one-step method is further described in a number of examples, which do not, however,
limit the scope of the invention in any way.
Unless otherwise mentioned, the oligomeri7~tion reactions of olefins and olefin mixtures
were performed in a steel reactor the volume of which was 300 ml and which was cooled
internally by means of a cooling coil and was heated, when necesc~ry, externally in an
2152669
WO 94/15895 PCT/~93/00540
electric mantle. The reactor was equipped with a stirrer. The lel.lpeldture of the reaction
i~lule was monitored by means of a thermocouple. The telllpelature of the reaction
Illi~lure was m~int~ined at the set value with a precision of + 1 C. The reagents used and
their amounts are m~ntioned in the examples.
The reactor was first charged with a solvent, if necesc~ry~ and with the cocatalyst
mentioned in the examples. Liquid monomer was fed into the reactor in the desired
amount. After the adding of the monomer, the reactor was pres~u~ized by means of BF3
gas, whereupon the catalyst complex formed in situ and the reaction started immediately.
10 The monomer or the monomer mixture and the catalyst were fed into the liquid phase of
the reactor. The reactor pressure was maintained constant by means of BF3 gas. The
pressure was s-lfficient to keep the monomers in the liquid phase. The reaction parameters
used were as follows: pres~ure 0-10 bar, expressed as o~ es~lre; reaction temperature
10-70 C; and reaction time 1-120 minutes or 1-8 hours. The reaction was halted by
15 adding into the reactor an excess of either an NaOH solution or water. The product
fraction was washed with an NaOH solution and was neutralized with water after the
wash. The product distribution was analyzed by the GC method.
The examples illustrate the various possibilities of the process for producing oligomer
20 fractions with different monomers and catalyst systems. The reference examples are
Fx~mplps 1-15. The present invention is illustrated by Examples 16-66. It should be bome
in mind that by the process being disclosed it is possible to produce highly different
product distributions, so the examples only suggest the possibilities offered by the process.
25 Reference examples, in which the monomer is l-butene (Examples 1-15).
Examples 1 and 2.
The cocatalyst used was n-valeric acid at 5.1 mmol per one mole of l-butene. The reactor
30 ~1~;s5ule was 4.0 bar and te-..peldlulc; 20 C. In Example 1 the reaction time was 9 min-
utes and in Example 2 it was 49 ~lh~u~es. After the said reaction times, the reactions were
halted by means of an NaOH solution. The hydrocarbon phases were analyzed, the results
being as follows.
2~5~ G(g9 PCT/F193/00540
Selectivities (%)
Example C4~onversion C" C,z C,6 C20 C24 C2g C3,+
84,6 % - 7,7 23,236,224,0 8,9
2 92,7 % 0,4 1,2 4,112,8 18,9 14,8 47,0
s
The number-average molecular masses of the product distributions according to the
examples were 268 g/mol and 383 g/mol. From the product of Example 2, the C,6
hydrocarbons and fractions lighter than this were separated by vacuum ~ till~tion. The
viscosity index determined on this unhydrogenated product was 81, the kinem~tic viscosity
being KV100 = 4.3 cSt.
Example 3.
The cocatalyst used was n-valeric acid at 13.4 mmol per one mole of 1-butene. The
reactor pl~s~ule was 2.5 bar and le---pelaLure 20 C. In Example 3 the reaction time was
49 minutes. After the said reaction time, the reaction was halted by means of an NaOH
solution. The hydrocarbon phase was analyzed, the result being as follows:
Selectivities (%)
Example C4 conversion C8 C,2 C,6 C20 C24 C28 C32+
3 81.8% 0.6 43.3 40.7 10.5 3.9 1.0
The number-average molecular mass of the product distribution according to the example
was 202 g/mol.
Example 4.
The cocatalyst used was n-valeric acid at 13.0 mmol per one mole of 1-butene. The
reactor pres~u-~; was 4.0 bar and te---~ tu~e 20 C. The reaction time was 6 hours. After
the said reaction time, the reaction was halted by means of an NaOH solution. The
hydrocarbon phase was analyzed, the result being as follows:
2152669
-- WO 94/15895 PCT/~193/00540
Selectivities (%)
E~ample C~ cc.. ~ .o,. C8 C,~ C,h C20 C24 C 8 C32~
4 approx. 99% 0.9 4.2 9.0 8.0 7.5 8.4 58.4
.
S The number-average molecular mass of the product distribution according to Example 4
was 386 g/mol.
Examples 5 and 6.
10 The cocatalyst used was n-valeric acid at 4.9 mmol per one mole of 1-butene. The reactor
pres~ul~ was 10 bar and le,l")eldl~lre 40 C. In Example S the reaction time was 4 min-
utes and in Example 6 it was 121 minutes. After the said reaction times the reactions were
halted by means of an NaOH solution. The hydrocarbon phases were analyzed, the results
being as follows:
Selecti~rities (%)
E~ample C4- ~ tiV.I C8 cl2 cl6 C20 C24 C~8 C32+
60.6 9~ - 6. 1 21 .6 36.2 23.9 12.2
6 appro~c. 99% - 5.7 7.3 9.3 13.3 13.1 51.4
The number-average molecular masses of the product distributions according to the
examples were 275 g/mol and 371 g/mol. The viscosity index determined on this
unhydrogenated product was 82, the kin~m~tic viscosity being KV100 = 7.0 cSt.
25 Fx~mples 7 and 8.
The cocatalyst used was n-valeric acid at 5.0 mmol per one mole of 1-butene. The reactor
plcs~ure was 10 bar and te"")el~ture 70 C. In Example 7 the reaction time was 9 min-
utes and in Example 8 it was 121 minutes. After the said reaction times the reactions were
30 halted by means of an NaOH solution. The hydrocarbon phases were analyzed, the results
being as follows:
WO 94/15895 PCT/F193/00540
215~669 10
Selectivities (%)
E~ample C4 conversion C8 C,2 C~6 C20 C24 C28 C32+
7 63.2% 0.927.1 40.3 24.4 7.3 - -
8 approx. 98% - 8.8 19.7 19.0 29.5 13.4 9.6
s
The number-average molecular masses of the product distributions according to the
eY~mples were 219 g/mol and 286 g/mol. From the product of Example 8, the Cl6
fraction and fractions lighter than this were separated by vacuum dic~ tion. The viscosity
index determined on this unhydrogenated product was 58, the kinem~tic viscosity being
10 KV100 = 2.8 cSt.
Examples 9-15.
l-Butene can also be oligomçri7~d with organic acid catalysts other than n-valeric acid,
15 for example, with alcohols and water, as shown by Fy~mr]es 9-15. The reactor p-ess.-.e
used was 4.0 bar and le,llp~dll~re 20 C, the reaction time being 36 minutes. The
cocatalysts used were acetic acid (Example 9), n-octanoic acid (10), ethanol (11), 1-
pentanol (12), l-octanol (13), and water (14). The reference example (15) is a reaction
ed with n-valeric acid under the same conditions. Cocatalyst was used at a ratio20 of 14.5-15.9 mmol of cocatalyst per one mole of l-butene. The results are shown in the
following table, where nk,~ stands for mmol of cocatalyst per one mole of butene.
E~am- C~ ,l nkk Selectivities (%)
ple
C8-C16C20-C28c32+ C4 conversion
9 C2 acid 15.157.0 43.0 - 77.0%
10C8 acid14.817.459.423.2 83.9%
11ethanol14.5 5.475.419.2 80.4~
12pentanol15.910.069.9 20.1 74.8%
13octanol14.522.761.116.2 79.2%
14 water15.012.7 87.3 - 61.2%
15n-valeric15.018.359.7 22.0 86.7%
acid
2152669
WO 94/15895 PCT/F~93/00540
11
The invention is ill-~trat~d in the following eY~mples 1~62, in which the monomers
shown in the table below were used.
Example Monomer
16-29 Raffinate II, i.e. a mixture of butene and butane
30-50 ~ffin~te II + alpha-olefin
51-62 long-chain alpha-olefin
Example 16.
The cocatalyst used was n-valeric acid at 32 mmol per one mole of the butene mixture.
The reactor pressure was 4.0 bar and temperature 20 C. In Example 16 the reaction time
15 was 75 minutes. After the said reaction time the reaction was halted by means of an
NaOH solution. The hydrocarbon phase was analyzed, the result being as follows:
Example C4 conversion Yields (%)
%
C8-C~6 C20-C28 C32+ Mn (g/mol)
16 100 48,5 48,7 2,8 240
Examples 17 and 18.
The cocat~lyst used was n-valeric acid at 52 mmol per one mole of the butene mixture.
In Example 17 the reactor p~sa~lle was 5.7 bar and te,-~peldtule 30 C. In Example 18
25 the reactor pressure was 4.5 bar and te"~peldture 10 C. The reaction time was 120
minutes in both examples. After the said reaction times the reactions were halted by
means of an NaOH solution. The hydrocarbon phases were analyzed, the results being as
followS:
- 30
WO 94/1~895 2 ~5 2 6 6 9 12 1~Cr/~lg3/00540
Example C4 conversion Yields (%)
C8-C,6 C20-C3 C32+ Mn (g/mol)
17 99,0 33,5 55,6 9,9 258
18 99,5 26,8 55,5 17,2 272
5 From the products of Examples 17 and 18, the-C,6f~c~O,, and fractions lighter than this
were separated by vacuum di~till~tion. Kinem~tic viscosities (KV100, cSt) were measured
and viscosity indices (VI,-)were determined for these unhydrogenated products. For the
product of Example 17, KV100 = 3.3 cSt and VI = 21. For the product of Example 18,
KV100 = 4.0 cSt and VI = 12.
Examples 19 and 20.
The cocatalyst used was n-valeric acid at 10 mmol per one mole of the butene mixture.
In Example 19 the reactor pres:,ulc was 4.7 bar and te"l~,e.dtule 10 C. In Example 20
15 the reactor ple~ re was 5.1 bar and ~Illp~ldluJe 30 C. The reaction time in both
examples was 30 minutes. After the said reaction times the reactions were halted by
means of an NaOH solution. The hydrocall,on phases were analyzed, the results being as
follows:
20 Examples C4 conversion Yields (%)
%
CR_CI6 C~-C3 c32+ Ml, (g/mol)
19 n. 100 58,3 39,2 2,5 232
20 n. 100 79,3 20,0 0,7 199
Examples 21 and 22.
In Example 21, the cocatalyst used was n-valeric acid at 51 mmol per one mole of the
butene mixture. The reactor pressure was 3.1 bar and telllpeld~ul~ 10 C. In Example 22,
the cocatalyst used was n-valeric acid at 53.5 mmol per one mole of the butene mixture.
The reactor pressure was 3.8 bar and lelllpe,dlure 30 C. The reaction time in both ex-
30 amples was 30 minutes. After the said reaction times the reactions were halted by meansof an NaOH solution. The hydrocarbon phases were analyzed, the results being as
2152669
-_ WO 94/15895 PCT/F193/00540
13
follows:
Example C4 conversion Yields (%)
%
C8-CI6 C20-C28 c32+ Mn (~/mol)
21 n. 100 67,7 32,3 0 210
- 5 2I n. 98 93,5 4,5 0 156
Examples 23-29.
The monomer was Raffinate II, i.e. a mixture of butene and butane. Raffinate II can also
be oligomerized with organic acid catalysts other than n-valeric acid, for example, with
10 alcohols and water, as shown by Examples 23-29. The reactor pressure was 6-7 bar and
temperature 20 C, the reaction time being 120 minutes. The cocatalysts used were acetic
acid (Example 23), n-octanoic acid (Example 24), ethanol (Example 25), l-pentanol
(Example 26), 1-octanol (Example 27), and water (Example 28). The reference example
(29) was a reaction pelrolllled under the same conditions by using n-valeric acid.
lS Cocatalyst was used at a ratio of 2.8-3.7 mmol of cocatalyst per one mole of the butane
mixture.
Example Cocatalyst nkk Selectivities (%)
C8-C,6C2o~C28C32+ M" (g/mol)
23 C2 acid 3,71 38,654,4 7,0 238
24 C8 acid 3,02 28,248,9 22,9 278
ethano1 2,72 59,634,5 5,9 185
26 pentanol 2,87 38,539,2 22,3 237
27 octanol 2,82 27,039,7 33,3 282
28 water 3,51 65,425,5 9,1 174
29 n-valericacid 3,2628,8 52,8 18,4 269
Examples 30-35.
30 The table shows the alpha-olefin used as the comonomer, the cocatalyst used, and the
product distributions as yields. Into the reactor there were fed 100 grams of Raffinate II
and 20-21 grams of the alpha-olefin mentioned in the examples. The reaction conditions
used were: temperature 40 C; pressure 7-8 bar; and reaction time 120 minutes. The
WO 94/1589~ 6 6 9 PCTIF193/00540
- 14
cocatalyst used was n-valeric acid (C5 acid) or l-pentanol (C5 alcohol); the amounts are
mentioned in the examples (kk, g). The product properties were determined on products
from which the Cl6 fraction and fractions lighter than this had been removed by vacuum
~isti]l~tion. Kinem~tic viscosity (KV100, cSt), viscosity index (VI,-) and pour point (PP,
5 C) were determined on these unhydrogenated products.
Example Alpha- Cocatalyst kk Selectivities (%)
olefin (~)
Cg-C,6 C O- C32+ KVI0 Vl PP
C~8
C8 C5 acid 2,930,8 55,7 13,5 3,2 47 -60
31 Cl. -"- 2,927,8 61,9 10,3 3,1 70 ~0
32 C,6 ~ 2,930,1 43,9 26,0 3,4 80 -30
33 CB C5_ 2,128,7 48,1 23,2 3,6 54 -54
alcohol
34 C,2 ~"~ 2,226,1 54,0 19,9 3,9 76
C,6 -~- 2,224,6 39,4 36,0 4,3 91
Example 36.
60 g of dodecene and 66 g of Raffinate II were fed into the reactor. The cocatalyst used
20 was 2.2 grams of l-pentanol. The reaction conditions were: reaction time 120 minutes;
temperature 30 C; and pressure 6 bar. After the said reaction time, the reaction was
halted by means of an NaOH solution. The hydrocarbon phase was analyzed, the result
being as follows:
25 C8-Cl6 13-4 %; C20-C2R 43.6 %; C32+ 5.3 %; KV100 119; VI 119; and PP -51 C.
Kinematic viscosity (KV100, cSt), viscosity index (VI,-) and pour point (PP, C) were
determined on the unhydrogenated product from which the Cl6 fraction and fractions
lighter than this had been removed by vacuum ~1istill~tion.
Examples 37-50.
Wo 94tl5895 215 2 6 6 9 PCT/~3100540
The examples show the monomer feed col-lposi~ions, the reaction times, and the product
distributions. ~ffin~te II and alpha-olefin were fed into the reactor in the amounts
mentioned in the examples. The reaction conditions were: ~e1"~ldture 30 C and pressure
4-8 bar, i.e. sufficient to m~int~in ~ffin~te II in liquid state in each experiment. The
S cocatalyst used was n-valeric acid in an amount of 2.85 grams. After the said reaction
times, the reactions were halted by means of an NaOH solution. The hydrocarbon phases
were analyzed, the results are shown in the tables.
The product properties mentioned in the examples, i.e. kinematic viscosity (KVl00, cSt),
10 viscosity index (VI,-) and pour point (PP, C), were determined on an unhydrogenated
product from which the Cl6 fraction and fractions lighter than this had been removed by
vacuum dictill~tion. In Examples 37-41 the alpha-olefin was l~ctene (S9 g) and the feed
was Raffinate II (68 g).
Example Alpha-Cocatalyst Reaction Selectivities (%)
olefin time
(min)
C8- C20-C32+ KV10 Vl PP
C,6 C28
37 l .octene n-valeric 10 2,1
acid 54,7 43,2
38 -"- -~- 30 11,4
33,4 55,2
39 -~ - 60 20,2
24,4 55,5
-"- -"- 120 30,9
17,5 51,5
41 -~- -"- 240 40,4 3,9 83 -57
15,4 44,2
Examples 42-46.
25 In the examples the feed materials were l-dodecene (60 g) and ~ffin~te II (42 g).
S 1 6 PCT/F193/00540
Example Alpha- Cocatalyst Reacti- Selectivities (%)
olefin on time
(min)
C8- C20- C32+ KVlO Vl PP
C,6 C28
42 l-dode-n-valeric 10 56,9 13,0
ceneacid 29,9
43 -~- -"- 30 59,1 25,9
14,8
44 -~- -"- 60 55,1 35,3
9,6
-"- -~- 120 47,1 44,8
8,0
46 -"- -~- 240 38,3 53,9 5,0 119-54
7,8
Examples 47-50.
The alpha-olefin was l-hPl~dectone (71 g) and the feed was ~ffin~te II (38 g).
Example Alpha-Cocatalyst Reaction Selectivities (%)
olefin time
(min)
C8- C20- C32+ KV10 Vl PP
C,6 C28
15 47 l-hexa-n-valeric lO 35,5 25,5
deceneacid 38,9
48 -~ - 70 29,8 55,6
14,6
49 - - -- - 120 25,7 65,4
8,8
-~ - 240 20,6 72,6 5,9 138-15
6,7
20 Examples 5 1 -62.
Into the reactor was fed 100 g of alpha-olefin. The reaction conditions used were a
temperature of 30 C and a pressure of 3.0-3.2 bar, and the cocatalyst was n-valeric acid
in an amount of 2.9-3.0 g. After the said reaction times the reactions were halted by
21S2669
WO 94/1~895 PCT/~193/00540
17
means of an NaOH solution. The hydrocarbon phases were analyzed, the results being as
follows (fractions: mono = monomer; di-tetra = di-, tri-, and tetramers; penta+ =
pentamers and fractions higher than this). In Examples 51-54 the alpha-olefin is 1-octene,
in Examples SS-58 it is i-dodecene, and in Examples 59-62 it is 1-hex~ece-~e.
s
The results are shown in the following table.
Example reaction timeYields (%)
(min)
mono di-tetra penta +
51 10 9,8 86,2 3,9
52 60 2,1 87,0 10,9
53 120 1,2 81,2 17,6
54 240 1,3 63,2 35,6
æ,s 72,9 4,6
56 60 8,6 80,1 11,4
57 120 4,5 77,6 17,8
58 240 2,6 64,4 33,1
59 10 25,1 71,3 3,4
6,0 81,7 12,4
61 120 4,2 76,0 19,9
62 240 4,2 65,9 29,9
Examples 63-66.
In Example 63 the reaction conditions were: reaction temperature 30 C; pressure 3 bar
25 expressed as BF3 overpressure; and reaction time 4 hours. ~ffin~te II was fed in as the
monomer in an amount of 100 g and n-valeric acid as the cocatalyst in an amount of 2.86
g. The obtained product was analyzed mass spectrometrically.
The product in Example 64 was a product prepared according to Example 58, which was
30 analyzed mass spectrometrically.
The product in Example 65 was a product prepared according to Example 46, which was
Wo 94/15895 215 2 6 6 9 PCT/FI93/00540
18
analyzed mass spectrometrically.
The product in Example 66 had been plepa,ed by mixing in mass proportions 50:50 the
products of Example 63 and Example 58. This mixture was analyzed mass spectrometri-
5 cally.
;
The appended mass spectrometric analysës depict the analyses of four different experi-
ments graphically, showing the absolute intensities of corresponding peaks of whole
molecules (the molecular mass of which corresponds to the molecular mass of the alkene
10 having a certain carbon number) with different molecular mass values. The peaks
co.le~l.ollding to fragmented products have been omitted from these alkene graphs; the be-
havior of these peaks with different values of molecular mass, however, corresponds to
the peaks of whole molecules. The following observations can be made from the graphs:
15 - In the alkene graph of butene oligomers (Fig. 1: R~ffin~te II oligomers), the
domin~ting alkene peaks are observable at carbon numbers 16, 20, 24, 28, 32, etc.,
i.e. at carbon numbers col,c~onding multiples, oligomers, of the carbon number
of butene. The absolute inten.~itie~ of the alkene peaks corresponding to buteneoligomers decrease as the carbon number increases steadily.
- Respectively, the alkene peaks dominating in the alkene graph of dodecene oligo-
mers (Fig. 2: Dodecene oligomers) are at carbon numbers 24, 36, 48, etc., i.e. at
carbon numbers corresponding to multiples, oligomers, of the carbon number of
dodecene. The absolute intensities of the alkene peaks colle~onding to dodecene
oligomers decrease as the carbon number increases steadily.
- The alkene peaks dominating in the alkene graph of products produced in the co-
oligomerization between butenes and dodecene (Fig. 3: C12-Raff Il co-oligomers)
are at carbon numbers 16, 20, 24, 28, 36, etc. The absolute intencities of the alkene
peaks decrease as the carbon number increases steadily.
- The alkene peaks dominating in the alkene graph of a blend of butene oligomersand dodecene oligomers (Fig. 4: C12-Raff I oligomer blend) are at carbon numbers
WO 94/15895 2 ~L S ~ 6 6 9 PCT/FI93/00540
19
16, 24, 36 and 48. The peak at carbon number 16 is due to butene oligomers, but
at carbon numbers 24, 36 and 48 the peaks are mainly due to dodecene oligomers.
These graphs show clearly that olefin mixtures oligomerized by the method accor-ding to the invention do not produce mixtures of homo-oligomers but produce co-
oligomers during the reaction when olefins rnay link randomly to the carbon chain.
