DESCRIPTION
CATALYST FOR OLEFIN MULTIMERIZATION AND METHOD FOR PRODUCING
OLEFIN MULTIMER IN PRESENCE OF CATALYST FOR OLEFIN MULTIMERIZATION
TECHNICAL FIELD
[0001]
The present invention relates to an olefin oligomerization
catalyst and a method for producing an olefin oligomer performed
in the presence of the catalyst.
BACKGROUND ART
[0002]
a-olefins, which serve, for example, as raw material for
polyolefin, are important compounds widely used in industrial
fields. Among them, 1-hexene is highly demanded, particularly
as raw material for polyolefin, and a method for producing 1-hexene
with high industrial efficiency in production cost, productivity,
and the like has been desired. However, most of methods for
producing an industrial polyolefin exhibit insufficient
catalytic reactivity (for example, see Patent Literature 1 to 3
and Non-Patent Literature 1 and 2).
[0003]
Under such circumstances, the present applicant has already
reported a novel catalyst that shows high efficiency in
a-polyolefin production (see Patent Literature 4).
SF-2755 2
In addition, in order to simplify a reaction process in
production of a-olefin, there have been used catalysts prepared
by supporting a transition metal compound on a solid carrier (for
example, see Patent Literature 5 to 7).
CITATION LIST
PATENT LITERATURE
[0004]
[Patent Literature 1] U.S. Pat. No. 5,856,257
[Patent Literature 2] JP-T-2004-524959
[Patent Literature 3] WO 01/68572
[Patent Literature 4] WO 2009/5003
[Patent Literature 5] JP-A-2006-117642
[Patent Literature 6] JP-T-2004-502527
[Patent Literature 7] JP-T-2006-517528
NON-PATENT LITERATURE
[ 0005]
[Non-Patent Literature 1] Journal of American Chemical Society,
2001, vol. 123, pp. 7423-7424.
[Non-Patent Literature 2] Journal of Organometallic Chemistry,
2004, vol. 689, pp. 3641-3668.
SUMMARY OF INVENTION
Technical Problem
[0006]
The present inventors produced a catalyst formed by
SF-2755 3
supporting a transition metal compound on a solid carrier, as
disclosed in Patent Literature 5 to 7 mentioned above, in order
to simplify a reaction process in production of o;-olefin regarding
an olefin oligomerization catalyst disclosed in Patent Literature
4 developed by the inventors themselves, and performed ethylene
trimerization reaction as an example.
[0007]
Hmqever, it has been found that production of 1-hexene by
the ethylene trimerization reaction using such a catalyst causes
by-production of hollow polyethylene particles. In the
production process of o;-olefin, it is difficult to separate and
dry the polyethylene particles using any existing device. Thus,
there has been a problem in that the production process is
complicated.
[0008]
Objectives to be achieved by the present invention in view
of the problem described above is to provide an olefin
oligomerization catalyst that allows properties of particles of
a polymer component by-produced in a production process for
o;-olefin to be obtained in such a shape that does not negatively
affect separation and drying processes for the particles, and to
provide a method for producing an olefin oligomer performed in
the presence of the olefin oligomerization catalyst.
Solution to Problem
l SF-2755 4
[0009]
The present inventors conducted intensive and extensive
studies to solve the above problem, and as a result of which, found
that an olefin oligomerization catalyst obtained by contacting
a transition metal compound with a preliminary contact solid
catalyst component prepared by a specific preparation process
allows particle properties of a polymer component by-produced in
an a-olefin production process to be obtained in such a shape that
does not negatively affect separation and drying processes for
the particles, and thereby completed the present invention.
[0010]
Specifically, the present invention relates to the
following [1] to [7]:
[1] An olefin oligomerization catalyst obtained by
contacting (D) a transition metal compound having a transition
metal atom selected from Group III to Group X of the periodic table
with a preliminary contact solid catalyst component (II) obtained
by contacting a solid catalyst component (I) formed by supporting
(B) an organoaluminum oxy-compound (b-2) on (A) a solid carrier
with (C) at least one compound selected from the group consisting
of an organometallic compound ( c-1) , an organoaluminum
oxy-compound(c-2), and a compound (c-3) that reacts with the
transition metal compound (D) to form a pair of ions.
[2] The olefin oligomerization catalyst (III) according to
SF-2755 5
[1], in which as the component (B), an organoaluminum compound
(b-1) is further used.
[3] The olefin oligomerization catalyst (III) according to
[1] or [2], in which the component (C) is the organoaluminum
oxy-compound (c-2) .
[4] The olefin oligomerization catalyst according to any
one of [1] to [3], in which the transition metal compound (D) is
a transition metal compound having a transition metal atom
selected from Group III to Group VI of the periodic table.
[5] The olefin oligomerization catalyst according to any
one of [1] to [3], in which the transition metal compound (D) is
represented by general formula (1) below:
[0011]
[0012]
R1
I
:y
Z/I .....
R6...". 'c'/N --•• ···\M x / (n-1)
0
• • • ( 1 )
SF-2755 6
(in the general formula ( 1) , R1 to R6 may be the same as or
different from each other and each represent a hydrogen atom, a
halogen atom, a hydrocarbon group, a heterocyclic compound residue,
an oxygen-containing group, a nitrogen-containing group, a
boron-containing group, an aluminum-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
tin-containing group, in which two or more thereof may be linked
to each other, and R1 may be linked to Z;
[0013]
M represents a transition metal atom selected from Group
III to Group X of the periodic table;
n represents a valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group, or a
tin-containing group, in which atoms or groups represented by X
may be the same as or different from each other, and the groups
represented by X may be liked to each other to form a ring;
[0014]
Y represents an oxygen atom, a nitrogen atom, a phosphorus
SF-2755 7
atom, or a sulfur atom;
Z represents a hydrocarbon group or a heterocyclic compound
residue that may have a substituent, and the minimum number of
bonds linking Y and N is 4 to 6;
[0015]
in the formula, a bond linking Y and Z may be a double bond
or a triple bond, and a bond linking Y and R1 may be a double bond
or a triple bond; and
additionally, in the formula, each dotted line represents
a coordination bond) .
[6] A method for producing an olefin oligomer, in which
an oligomerization reaction of an olefin is performed in the
presence of the olefin oligomerization catalyst according to any
one of [1] to [5].
[7] The method for producing an olefin oligomer according
to [6], in \vhich the olefin is ethylene, and the olefin oligomer
is 1-hexene.
ADVANTAGEOUS EFFECTS OF INVENTION
[0016]
Use of the olefin oligomerization catalyst according to the
present invention allows particles of a polymer compound
by-produced in an olefin oligomerization reaction not to be hollow,
thus allowing the simplification of the production process.
BRIEF DESCRIPTION OF DRAWINGS
SF-2755 8
[0017]
Fig. 1 is an electromicroscopic photograph (200 times) of
a solid catalyst component (I-1) prepared in Example 1;
Fig. 2 is an electromicroscopic photograph (200 times) of
by-produced polyethylene obtained by reaction in Example 1;
Fig. 3 is an electromicroscopic photograph (200 times) of
by-produced polyethylene obtained by reaction in Comparative
Example 1;
Fig. 4 is an electromicroscopic photograph (200 times) of
a solid catalyst component (I-2) used in Example 15;
Fig. 5 is an electromicroscopic photograph (200 times) of
by-produced polyethylene obtained by reaction in Example 15; and
Fig. 6 is an electromicroscopic photograph (200 times) of
by-produced polyethylene obtained by reaction in Comparative
Example 3.
DESCRIPTION OF EMBODIMENTS
[0018]
An olefin oligomerization catalyst used in the present
invention can be produced in a method as described below.
In the present invention, oligomerization of olefin means
dimerization to decamerization of olefin, preferably
dimerization to hexamerization of olefin, and more preferably
dimerization to tetramerization of olefin.
[0019]
SF-2755 9
An olefin oligomerization catalyst (III) according to the
present invention is obtained by contacting (D) a transition metal
compound with a preliminary contact solid catalyst component (II)
obtained by contacting a solid catalyst component (I) described
later formed by supporting (B) an organoaluminum
oxy-compound(b-2) on (A) a solid carrier with (C) at least one
compound selected from the group consisting of an organometallic
compound (c-1), an organoaluminum oxy-compound (c-2), and a
compound (c-3) that reacts with the transition metal compound (D)
to form a pair of ions.
[0020]
Hereinafter, each constituent component will be described.
[Solid Catalyst Component (I)]
In the present invention, the solid catalyst component (I)
is obtained by supporting the organoaluminum oxy-compound (b-2)
as the component (B) on the solid carrier(A). More preferably,
the solid catalyst component (I) is obtained by furhter supporting
an organoaluminum compound (b-1) in addition to the organoaluminum
oxy-compound (b-2) as the component (B) on the solid carrier (A) .
[0021]
Hereinafter, a detailed description will be given of the
solid carrier (A), and (B) the organoaluminum oxy-compound (b-2)
and the organoaluminum compound (b-1).
<(A) Solid Carrier>
SF-2755 10
1
The solid carrier (A) used in the present invention is a
granular or fine particle solid formed from an inorganic compound
or an organic compound.
[0022]
Examples of the inorganic compound include inorganic oxides,
inorganic halides, clays, a clay minerals, and ion-exchangeable
layered compounds.
Examples of the inorganic oxides (excluding alkali metal
and Th02 • In addition, there are also mentioned, as the inorganic
oxides, for example, composite oxides including the
aforementioned inorganic oxides, such as natural zeolite,
inorganic oxides may be mixtures of these inorganic oxides.
[0023]
Among them, preferred are inorganic oxides containing, as
a main ingredient, at least one selected from Si02 and Al20 3, and
more preferably Si02 • The main ingredient means an ingredient
having a highest weight ratio in cases where a plurality of
inorganic oxides are contained.
[0024]
The inorganic oxides may contain a small amount of a
secondary ingredient, for example, a carbonate such as Na2C03 , K2C03,
SF-2755 11
CaC03, or MgC03; a sulphate such as Na2S04, Al2(S04)3, or BaS04; a
nitrate such as KN03, Mg (N03) 2, orAl (N03) 3; or an alkali metal oxide
such as Na20, K20, or Li20.
[0025]
Properties of the solid carrier formed from any of the
inorganic oxides vary depending on the kind of the inorganic oxide,
the production method therefor, and the like. The solid carrier
has a particle size ranging usually from 0.5 to 300 ~m, and a
specific surface area ranging usually from 50 to 1000 m2/g. In
addition, the carrier formed from any of the inorganic oxides is
typically porous, and has a pore volume ranging preferably from
0. 3 to 3. 0 cm3 /g. The carrier having such properties is optionally
fired at 100 to 1000°C and used.
[0026]
Examples of the inorganic halides include MgC12, MgBr2, MnC12,
and MnBr2. Any of the inorganic halides that has a granular or
fine particle shape can be directly used as the solid carrier,
but may be optionally pulverized by a ball mill, a vibration mill,
or the like before being used as the solid carrier. Alternatively,
there may be used fine particles obtained by dissolving any of
the inorganic halides in a solvent such as alcohol and
precipitating with a precipitation agent.
[0027]
The clays are those usually made of a clay mineral as a main
SF-27 55 12
ingredient. In addition, the ion-exchangeable layered compounds
are those having a crystal structure in which planes formed by
an ionic bonding or the like are laminated in parallel to each
other with a weak bonding force, and in which the contained ions
are exchangeable. Most clay minerals are ion-exchangeable
layered compounds. Additionally, the clays, the clay minerals,
and the ion-exchangeable layer compounds that can be used are not
limited to natural ones but can also be synthetic ones.
[0028]
Examples of the crystal structure of the ion-exchangeable
layered compounds include layered crystal structures such as a
hexagonal close-packed structure, an antimony structure, a CdCl2
structure, and a Cdi2 structure.
Examples of the clays and the clay minerals include kaolin,
bentonite, kibushi clay, gairome clay, allophane, hisingerite,
pyrophyllite, mica, montmorillonite, vermiculite, chlorite,
palygorskite, kaolinite, nacrite, dickite, and halloysite.
[0029]
Examples of the ion-exchangeable layered compounds include
crystalline acid salts of multivalent metals, such as
a-Zr (HAs04) 2·H20, a-Zr (KP04) 2·3H20, a-Ti (HP04) 2 1 a-Ti (HAs04) 2·H20,
a-Sn (HP04) 2·H20, y-Zr (HP04) 2 1 y-Ti (HP04) 2 1 and y-Ti (NH 4P04) 2·H20.
[ 0030 l
Such clays, clay minerals, and ion-exchangeable layered
SF-2755 13
compounds have a pore volume of preferably not less than 0.1 cc/g,
and particularly preferably 0. 3 to 5 cc/g as measured by mercury
intrusion porosimetry in pores with a pore radius of not less than
20 angstroms. Herein, the pore volume is measured in a pore radius
range of 20 to 3 x 104 angstroms by the mercury intrusion
porosimetry that uses a mercury porosimeter. When a material
whose volume of pores with a radius of not less than 20 angstroms
is less than 0.1 cc/g is used as the carrier, it tends to be
difficult to obtain high oligomerization activity.
[0031]
It is also preferable to perform a chemical treatment on
the clays and the clay minerals. The chemical treatment is not
particularly limited, and examples thereof include a surface
treatment for removing impurities attached to a surface of a clay
or clay mineral that is to be used and a treatment for giving an
influence on the crystal structure of the clay or the clay mineral.
Examples of the chemical treatment include acid treatment,
alkaline treatment, salt treatment, and organic substance
treatment. Performing acid treatment, for example, removes
impurities on the surface of the clay or the clay mineral, as well
as allows elution of cations such as Al, Fe, and Mg in the crystal
structure included in the clay or the clay mineral, thereby
increasing a surface area of the clay or the clay mineral.
Performing alkaline treatment, for example, breaks the crystal
SF-2755 14
structure included in the clay or the clay mineral, changing the
crystal structure. Alternatively, performing salt treatment or
organic substance treatment, for example, forms an ion complex,
a molecular complex, an organic derivative, or the like, allowing
a change of the surface area of the clay or the clay mineral. In
addition, when an ion-exchangeable layered compound is included
in the clay or the clay mineral, an interlayer distance
therebetween can be changed.
[0032]
The ion-exchangeable layered compound used in the present
invention may be a layered compound whose inter layer distance has
been enlarged by exchanging an interlayer exchangeable ion with
another bulky (large) ion through the use of ion exchangeable
properties thereof. Such a bulky ion plays a supportive role in
supporting the layered structure, and is usually called as pillar.
In addition, the introduction of another substance (for example,
a guest compound or a guest ion) betlveen the layers of a layered
compound as mentioned above is referred to as intercalation.
Examples of a guest compound and a guest ion to be intercalated
include cationic inorganic compounds such as TiC14 and ZrC14; metal
alkoxides such as Ti(OR) 4, Zr(OR) 4, PO(OR) 3 , and B(OR) 3 (R
represents a hydrocarbon group or the like); and metal hydroxide
ions such as [Al1304(0H)24l 7+, [Zr4(0H) 14 ] 2+, and [Fe30(0COCH3 ) 6 ]+.
These guest compounds and guest ions are used alone or in a
~
~/ SF-2755 15
combination of two or more thereof.
[0033]
In addition, in the intercalation of these guest compounds
and guest ions, a dimer obtained by hydrolyzing a metal alkoxide
such as Si (OR) 4 , Al (OR) 3 , or Ge (OR) 4 (R represents a hydrocarbon
group or the like) or the like, a colloidal inorganic compound
such as Si02 , or like may be allowed to coexist. Additionally,
examples of the pillar include oxides generated by intercalating
the aforementioned metal hydroxide ions between the layers and
then thermally dehydrating.
[0034]
The clay, theclaymineral, andtheion-exchangeablelayered
compound used in the present invention can be directly used as
the solid carrier as long as they have a granular or fine particle
shape. Alternatively, before using as the solid carrier, the clay,
the clay mineral, and the ion-exchangeable layered compound may
be optionally additionally pulverized using a ball mill or the
like, sifting, or the like. Additionally, alternatively, the
clay, the clay mineral, and the ion-exchangeable layered compound
may be used by nev1ly adding water to allow them to adsorb the water
or thermally dehydrating. These operations may be performed
alone or in a combination of two or more thereof.
[0035]
Among the clays, clay minerals, and ion-exchangeable
·-4/
~/ SF-2755 16
layered compounds, preferred are clays and clay minerals, and
particularly preferred are montmorillonite, vermiculite,
hectorite, taeniolite, and synthetic mica.
[0036]
Solid carriers formed from the inorganic compounds
described above are used alone or in a combination of two or more
thereof.
Examples of the organic compounds include (co)polymers
generated by containing, as a main ingredient, a-olefin having
2 to 14 carbon atoms, such as ethylene, propylene, 1-butene, or
4-methyl-1-pentene, (co) polymers generated by containing, as a
main ingredient, vinylcyclohexane or styrene, and modified
products thereof. Examples of the solid carrier formed from an
organic compound include granular or fine particle solids formed
from the above compounds. These granular or fine particle solids
have a particle size ranging from 10 to 300 ~m.
[0037]
<(b-2) Organoaluminum Oxy-Compound>
In the present invention, the organoaluminum oxy-compound
(b-2) included in the component (B) supported on the solid carrier
(A) may be a conventionally known organoaluminum oxy-compound
(aluminoxane), and for example, may be a benzene-insoluble
organoaluminum oxy-compound as exemplified in JP-A-H2-78687.
[0038]
·.· .. ········? / '----'-:-.- ./ SF-2755 17
The above organoaluminum oxy-compound can be produced, for
example, by methods as below, and is usually obtained as a solution
included in a hydrocarbon solvent.
(1) A method in which an organoaluminum compound such as
trialkylaluminum is added to a hydrocarbon medium suspension of
a compound containing adsorbed water or a salt containing water
of crystallization, such as magnesium chloride hydrate, copper
sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate,
or cercus chloride hydrate to react the organoaluminum compound
with the adsorbed water or the water of crystallization.
(2) A method in which water, ice, or water vapor is allowed
to directly act on an organoaluminum compound such as
trialkylaluminum in a medium such as benzene, toluene, ethyl ether
or tetrahydrofuran.
(3) A method in which an organoaluminum compound such as
trialkylaluminum is allowed to react with an organotin oxide such
as dimethyl tin oxide or dibutyltin oxide in a medium such as decane,
benzene, or toluene.
[0039]
The organoaluminum oxy-compound may contain a small amount
of another organic metal component. In addition, a solvent or
unreacted organoaluminum compound may be distilled away from the
above organoaluminum oxy-compound solution produced, and then the
organoaluminum oxy-compound may be redissolved in a solvent or
SF-2755 18
suspended in a poor solvent for the organoaluminum oxy-compound.
[0040]
Examples of the organoaluminum compound used to prepare the
organoaluminum oxy-compound include the same organoaluminum
compounds as those exemplified as organoaluminum compounds
belonging to the compound (b-1) that will be described later.
[0041]
Among them, preferred are trialkylaluminum and
tricycloalkylaluminum, and particularly preferred is
trimethylaluminum.
The above organoaluminum compounds are used alone or in a
combination of two or more thereof.
[0042]
Examples of the solvent used to prepare the organoaluminum
oxy-compound include aromatic hydrocarbons such as benzene,
toluene, xylene, cumene, and cymene; aliphatic hydrocarbons such
as pentane, hexane, heptane, octane, decane, dodecane, hexadecane,
and octadecane; alicyclic hydrocarbons such as cyclopentane,
cyclohexane, cyclooctane, and methylcyclopentane; petroleum
fractions such as gasoline, kerosene, and gas oil; and halides
of hydrocarbons such as the aromatic hydrocarbons, the aliphatic
hydrocarbons, or the alicyclic hydrocarbons mentioned above,
particularly hydrocarbons such as chlorides and bromides and
halogenated hydrocarbons. In addition, examples of the solvent
SF-2755 19
l
also include ethers such as ethyl ether and tetrahydrofuran.
Among these solvents, particularly preferred are the aromatic
hydrocarbons and the aliphatic hydrocarbons.
[0043]
The aforementioned benzene-insoluble organoaluminum
oxy-compound is a compound that is insoluble or slightly soluble
in benzene and in which anAl component that dissolves in benzene
at 60°C is contained in an amount of usually 10% or less, preferably
5% or less, and particularly preferably 2% or less in terms of
Al atom.
[0044]
In addition, examples of the organoaluminum oxy-compounds
include boron-containing organoaluminum oxy-compounds
represented by general formula (ii) below:
[0045]
• • • ( i )
[0046]
(in the formula (ii), R15 represents a hydrocarbon group
having 1 to 10 carbon atoms; R16
, which may be the same as or
different from each other, each represent a hydrogen atom, a
halogen atom, or a hydrocarbon group having 1 to 10 carbon atoms).
SF-2755 20
The boron-containing organoaluminum oxy-compounds
represented by the general formula (ii) can be produced by reacting
an alkylboronic acid represented by general formula (iii) below
with an organoaluminum oxy-compound in an inert solvent under an
inert gas atmosphere at a temperature of -80°C to room temperature
for 1 minute to 24 hours.
[0047)
... (iii)
(in the formula (iii), R15 represents the same group as that in
the above formula (ii)).
Examples of the alkylboronic acids represented by the
general formula (iii) include methylboronic acid, ethylboronic
acid, isopropylboronic acid, n-propylboronic acid,
n-butylboronic acid, isobutylboronic acid, n-hexylboronic acid,
cyclohexylboronic acid, phenylboronic acid,
3,5-difluorophenylboronic acid, pentafluorophenylboronic acid,
and 3,5-bis(trifluoromethyl)phenylboronic acid. Among them,
preferred are methylboronic acid, n-butylboronic acid,
isobutylboronic acid, 3,5-difluorophenylboronic acid, and
pentafluorophenylboronic acid. These compounds are used alone
or in a combination of two or more thereof.
[0048]
Examples of the organoaluminum compounds to be reacted with
the alkylboronic acids include the same organoaluminum compounds
SF-2755 21
as those exemplified as organoaluminum compounds belonging to the
compound (b-1) that will be described later. Among them,
preferred are trialkylaluminum and tricycloalkylaluminum, and
more preferably, trimethylaluminum, triethylaluminum, and
triisobutylaluminum. These compounds are used alone or in a
combination of two or more thereof.
[0049]
These organoaluminum oxy-compounds (b-2) are used alone or
in a combination of two or more thereof.
<(b-1) Organoaluminum Compound>
Examples of the organoaluminum compound (b-1) that is
optionally used as the compound (B) in the present invention
include compounds represented by general formula (i) below:
[0050]
RamAl (ORb) nHpXq ... ( i)
(in the formula (i), R" and Rb, which may be the same as or
different from each other, each represent a hydrocarbon group
having 1 to 15, and preferably 1 to 4 carbon atoms; X represents
a halogen atom; 0 < m ~ 3, 0 ~ n <3, 0 ~ p < 3, 0 ~ q < 3, and m
+ n + p + q = 3).
Examples of the above organoaluminum compounds (b-1)
include compounds as below:
[0051]
Organoaluminum compounds represented by general formula:
SF-2755 22
RamAl(ORb)3-m ... (i-1)
(in the formula (i-1), Ra and Rb, which may be the same as
or different from each other, each represent a hydrocarbon group
having 1 to 15, and preferably 1 to 4 carbon atoms; 0 < m ~ 3,
and preferably 1.5 ~ m ~ 3);
organoaluminum compounds represented by general formula:
RamAlX3-m ... (i-2)
(in the formula (i-2), Ra represents a hydrocarbon group
having 1 to 15, and preferably 1 to 4 carbon atoms; X represents
a halogen atom; 0 < m ~ 3, and preferably 0 < m < 3);
organoaluminum compounds represented by general formula:
Raml\1H3-m ... { i -3)
(in the formula (i-3), Ra represents a hydrocarbon group
having 1 to 15, and preferably 1 to 4 carbon atoms; 0 < m ~ 3,
and preferably 2 ~ m < 3); and
organoaluminum compounds represented by general formula:
RamAl (ORb) nXq... ( i-4)
(in the formula (i-4), Ra and Rb, which may be the same as
or different from each other, each represent a hydrocarbon group
having 1 to 15, and preferably 1 to 4 carbon atoms; X represents
a halogen atom; 0 < m ~ 3, 0 ~ n <3, 0 ~ q < 3, and m + n + q =
3) .
[0052]
More specific examples of the organoaluminum compounds
SF-2755 23
(b-1) include tri(n-alkyl)aluminums such as trimethylaluminum,
triethylaluminum, tri(n-butyl)aluminum, tripropylaluminum,
tripentylaluminum, trihexylaluminum, trioctylaluminum, and
tridecylaluminum; tri-(branched-chain alkyl)aluminums such as
triisopropylaluminum, triisobutylaluminum,
tri(sec-butyl)aluminum, tri(tert-butyl)aluminum,
tri(2-methylbutyl)aluminum, tri(3-methylbutyl)aluminum,
tri(2-methylpentyl)aluminum, tri(3-methylpentyl)aluminum,
tri(4-methylpentyl)aluminum, tri(2-methylhexyl)aluminum,
tri(3-methylhexyl)aluminum, and tri(2-ethylhexyl)aluminum;
tricycloalkylaluminums such as tricyclohexylaluminum and
tricyclooctylaluminum; triarylaluminums such as
triphenylaluminum and tritolylaluminum; dialkylaluminum
hydrides such as diethylaluminum hydride and diisobutylaluminum
hydride; alkenylaluminums such as isoprenylaluminums represented
by a formula such as ( iC4H9) xAly (CsH1ol z (in the formula, x, y, and
z each represent a positive value; z ~ 2x; and iC4H9 represents
an isobutyl group); alkylaluminum alkoxides such as
isobutylaluminum methoxide, isobutylaluminum ethoxide, and
isobutylaluminum isopropoxide; dialkylaluminum alkoxides such as
dimethylaluminum methoxide, diethylaluminum ethoxide, and
dibutylaluminum butoxide; alkylaluminum sesquialkoxides such as
ethyaluminum sesquiethoxide and butylaluminum sesquibutoxide;
partially alkoxylated alkylaluminums having an average
SF-2755 24
composition represented by a formula such as Ra2.5Al (ORb) o.s (in the
formula, Ra and Rb, which may be the same as or different from each
other, each represent a hydrocarbon group having 1 to 15, and
preferably 1 to 4 carbon atoms); dialkylaluminum aryloxides such
as diethy1aluminum phenoxide, diethylaluminum
(2,6-di-tert-butyl-4-methylphenoxide), ethylaluminum
bis(2,6-di-tert-butyl-4-methylphenoxide),
diisobutylaluminum(2,6-di-tert-butyl-4-methylphenoxide), and
isobutylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide);
dialkylaluminum halides such as dimethylaluminum chloride,
diethylaluminum chloride, dibutylaluminum chloride,
diethylaluminum bromide, and diisobutylaluminum chloride;
alkylaluminum sesquihalides such as ethylaluminum sesquichloride,
butylaluminum sesquichloride, and ethylaluminum sesquibromide;
partially halogenated alkylaluminums such as alkylaluminum
dihalides including ethylaluminum dichloride, propylaluminum
dichloride, and butylaluminum dibromide; dialkylaluminum
hydrides such as diethylaluminum hydride and dibutylaluminum
hydride; partially hydrogenated alkylaluminums such as
alkylaluminum dihydrides including ethylaluminum dihydride and
propylaluminum dihydride; and partially alkoxylated and
halogenated alkylaluminums such as ethylaluminum ethoxychloride,
butylaluminum butoxychloride, and ethylaluminum ethoxybromide.
[0053]
~I SF-2755 25
Among them, from the viewpoint of activity, selectivity,
and availability of the catalyst, preferred are trialkylaluminums
and tricycloalkylaluminums, and particularly preferred are
trimethylaluminum, triethylaluminum, and triisobutylaluminum.
[0054] These organoaluminum compounds (b-1) are used alone
or in a combination of two or more thereof.

The solid catalyst component (I) according to the present
invention can be prepared by contacting the solid carrier (A) with
the organoaluminum oxy-compound (b-2) as the component (B). The
component (B) is preferably a combination of the organoaluminum
oxy-compound (b-2) and the organoaluminum compound (b-1).
[0055]
The preparation method allows the organoaluminum
oxy-compound (b-2) to be supported on a surface of the solid
carrier (A). In this case, when the organoaluminum compound (b-1)
is used in combination as the component (B), a group (for example,
an SiOH group in a case in which the solid carrier (A) is Si02 )
that exists on the surface of the solid carrier (A) and is highly
reactive with the organoaluminum oxy-compound (b-2) is processed
by the organoaluminum compound (b-1), so that uneven distribution
of the organoaluminum oxy-compound (b-2) can be suppressed to
allow the compound to be more evenly supported.
[0056]
;---=---...• ...-~ ~:~:I /
./
;/
SF-27 55 26
The preparation of the solid catalyst component (I) may use
a solvent. The solvent to be used is preferably an organic
compound inactive to the solid carrier (A) and the component (B).
Examples of such an organic compound include aliphatic
hydrocarbons such as propane, butane, hexane, heptane, octane,
decane, dodecane, and kerosene; alicyclic hydrocarbons such as
cyclopentane, cyclohexane, and methylcyclopentane; aromatic
hydrocarbons such as benzene, toluene, and xylene; halogenated
hydrocarbons such as ethylene chloride, chlorobenzene, and
dichloromethane; and mixtures thereof.
[0057]
In the preparation of the solid catalyst component (I), (B)
the organoaluminum oxy-compound (b-2) is used in an amount of
usually 10-5 to 10-1 mol, and preferably 2 x 10-5 to 5 x 10-2 mol
per gram of the solid carrier (A) in terms of aluminum atom.
Additionally, when the organoaluminum compound (b-1) is further
used in combination as the component (B), the organoaluminum
compound (b-1) is used, as an upper limit, in an amount of usually
5 x 10-1 mol, and preferably 2 x 10-2 mol per gram of the solid
carrier (A) in terms of aluminum atom.
[0058]
When the amount of the organoaluminum oxy-compound (b-2)
used is less than 10-5 mol per gram of the solid carrier(A), it
is not preferable since catalytic activity becomes insufficient,
SF-2755 27
which is economically disadvantageous. In addition, 1vhen the
amount of the organoaluminum oxy-compound (b-2) used is more than
10-1 mol per gram of the solid carrier (A) , there is generated an
excessive amount of the organoaluminum oxy-compound (b-2) that
cannot be supported on the component (A) , which is not preferable
since it is not only economically disadvantageous but also can
result in by-production of an amorphous polymer component in an
a-olefin production process, whereby continuous operability can
be negatively affected.
[0059]
When the amount of the organoaluminum compound (b-1) used
is more than 5 ·x 10-2 mol per gram of the solid carrier (A) , there
is generated an excessive amount of the organoaluminum compound
(b-1) that cannot be supported on the component (A), which is not
preferable since it is not only economically disadvantageous but
also can result in by-production of an amorphous polymer component
in an a-olefin production process, whereby continuous operability
can be negatively affected.
[0060]
A temperature of contact of the above-described respective
components with each other is usually -50 to 150°C, and preferably
-20 to 120°C, and a time length of the contact is 1 to 1000 minutes,
and preferably 5 to 600 minutes.
In the solid catalyst component (I) thus obtained,
SF-2755 28
preferably, (B) the organoaluminum oxy-compound (b-2) and the
optionally used organoaluminum compound (b-1) are supported in
an amount of 10-5 to 10-1 mol, and preferably 2 x 10-5 to 5 x 10-2
mol per gram of the solid carrier (A) in terms of aluminum atom.
[0061]
[Preliminary Contact Solid Catalyst Component (II)]
In the present invention, the preliminary contact solid
catalyst component (II) is obtained by contacting the solid
catalyst component (I) thus obtained with (C) at least one
component selected from the group consisting of the organometallic
compound (c-1), the organoaluminum oxy-compound (c-2), and a
compound (c-3) that reacts with (D) the transition metal compound
that will be described later to form a pair of ions.
[ 00 62]
In each of the olefin oligomerization catalysts as disclosed
in Patent Literature 4 to 7 mentioned above, a transition metal
compound is supported on a solid carrier corresponding to the solid
catalyst component (I) described above. However, in an olefin
oligomerization reaction performed using such a catalyst, there
has been observed a phenomenon in which a hollow olefin polymer
component is by-produced. An analysis of the catalyst was made
to find the reason of the phenomenon, and it was found that a
transition metal as a reaction center was significantly unevenly
distributed on an outermost surface of the solid carrier. This
SF-2755 29
seems to indicate that a factor for which the by-produced olefin
polymer component becomes hollow is that the olefin polymer is
by-produced due to the transition metal unevenly distributed on
the uppermost surface of the solid carrier in the olefin
oligomerization reaction. Then, although a detailed reason for
by-production of a hollow olefin polymer is unknown, the reason
is assumed to be that since the organoaluminum oxy-compound
supported on the uppermost surface of the solid carrier has a high
degree of association, a layer derived from such an organoaluminum
oxy-compound includes a complex entanglement of molecular chains
and therefore there is almost no remaining space that allows the
transition metal compound to enter an internal surface of the
carrier.
[0063]
On the other hand, in the preliminary contact solid catalyst
component (II) according to the present invention, it is assumed
that contacting the solid catalyst component (I) with the
component (C) causes recombination of an Al-0-Al bond derived from
the organoaluminum oxy-compound supported on the surface of the
solid catalyst component (I), and the degree of association of
the organoaluminum oxy-compound (b-2) is reduced, 1vhereby the
entanglement of molecular chains is reduced to form a space. As
a result, in preparation of the olefin oligomerization catalyst
(III), it seems that the transition metal compound (D) described
~ / ~//
i
SF-2755 30
later is allowed to be relatively evenly distributed onto the
internal surface of the preliminary contact solid catalyst
component (II) without staying only on the uppermost surface
thereof, so that olefin polymer is generated even from the internal
surface thereof in an oligomerization reaction of an olefin. This
seems to be able to suppress the by-production of a hollow olefin
polymer component.
[ 0 0 64]
Hereinafter, a detailed description will be given of each
of the organometallic compound (c-1), the organoaluminum
oxy-compound (c-2), and a compound (c-3) that reacts with the
following transition metal compound (D) to form a pair of ions.
[0065]
<(c-1) Organometallic Compound>
The organometallic compound (c-1) is an organometallic
compound other than the organoaluminum oxy-compound (c-2)
described later, and typical examples thereof include
organometallic compounds containing a metal selected from Group
I of the periodic table (Li, Na, K, Rb, Cs, Fr), Group II thereof
(Be, Mg, Ca, Sr, Ba, Ra), Group XII thereof (Zn, Cd, Hg), and Group
XIII thereof (Al, Ga, In, Tl). Examples of these organometallic
compounds (C-1) include organoaluminum compounds(c-1a), (c-1b),
and (c-1c) described below.
[0066]
! SF-2755 31
(c-1a) : Organoaluminum compounds represented by general
formula (c-1a) below:
RamAl (ORb) nHpXq ... (c-1a)
(in the formula (c-1a) 1 Ra and Rb 1 which may be the same as
or different from each other 1 each represent a hydrocarbon group
having 1 to 15 1 and preferably 1 to 4 carbon atoms; X represents
a halogen atom; 0 < m ~ 3 1 0 ~ n < 3 1 0 ~ p < 3 1 0 ~ q < 3 1 and
m + n + p + q = 3).
(c-1b) : Complex alkylated products of a metal of Group I
of the periodic table and aluminum represented by general formula
(c-1b) below:
M2A1Ra 4 ... ( c-1b)
(in the formula (c-1b) 1 M2 represents Li 1 Na 1 or K; and Ra
represents a hydrocarbon group having 1 to 15 1 and preferably 1
to 4 carbon atoms).
(c-1c) : Dialkyl compounds of a metal of Group II or XII of
the periodic table represented by general formula (c-1c) below:
RaRbM3 ... ( c-1c)
(in the formula (c-1c) 1 Ra and Rb 1 which may be the same as
or different from each other 1 each represent a hydrocarbon group
having 1 to 15 1 and preferably 1 to 4 carbon atoms; and M3 represents
Mg 1 Zn 1 or Cd).
Examples of organoaluminum compounds belonging to the
compounds (c-1a) can be the same ones as the above organoaluminum
SF-2755
compounds (b-1) .
[ 0067]
32
Examples of the compounds belonging to the compounds (c-lb)
include LiAl (C2H5 ) 4 and LiAl (C7H1s) 4 •
Examples of the compounds belonging to the (c-lc) include
dimethylmagnesium, diethylmagnesium, dibutylmagnesium,
butylethylmagnesium, dimethylzinc, and diethylzinc.
[0068]
Examples of the organometallic compounds (c-1) other than
the compounds (c-la) to ( c-lc) include methyllithium,
ethyllithium, propyllithium, butyllithium, methylmagnesium
bromide, methylmagnesium chloride, ethylmagnesium bromide,
ethylmagnesium
propylmagnesium
chloride,
chloride,
butylmagnesium chloride.
[0069]
propylmagnesium bromide,
butylmagnesium bromide, and
In addition, the organometallic compounds (c-1) may be
combinations of such compounds that allow formation of the above
organoaluminum compounds in the above oligomerization reaction
system, such as a combination of an aluminum halide and
alkylli thium and a combination of an aluminum halide and
alkylmagnesium.
[0070]
Among the organometallic compounds (c-1), preferred are the
SF-2755 33
i I
organoaluminum compounds (c1-a).
The organometallic compounds (c-1) are used alone or in a
combination of two or more thereof.
[0071]
<(c-2) Organoaluminum Oxy-Compound>
Examples of organoaluminum oxy-compounds belonging to the
compound (c-2) can be the same ones as the above organoaluminum
oxy-compounds (b-2).
[0072]
Among these compounds, from the viewpoint of activity,
selectivity, and availability of the catalyst, methylaluminoxane
is particularly preferable.
<(c-3) Compound that Reacts with Transition Metal Compound (D)
to Form Pair of Ions>
The compound (c-3) that reacts with the transition metal
compound (D) to form a pair of ions is a compound that reacts with
the transition metal compound (D) described later to form a pair
of ions. Accordingly, at least compounds that are contacted with
the transition metal compound (D) to form a pair of ions are
included in the compound. The compounds (c-3) that reacts with
the transition metal compound (D) to form a pair of ions are
hereinafter referred to also as "ionized ionic compounds".
[0073]
Examples of the ionized ionic compounds belonging to the
SF-2755 34
compounds (C-3) include Lewis acids, ionic compounds, borane
compounds, and carborane compounds, as described in
JP-A-Hl-501950, JP-A-Hl-502036, JP-A-H3-179005, JP-A-H3-179006,
JP-A-H3-207703, JP-A-H3-207704, U.S. Pat. No. 5321106, and the
like. Furthermore, examples of the ionized ionic compounds
belonging to the above compounds (c-3) also include isopoly acid
compounds and heteropoly acid compounds.
[0074]
Examples of the Le1vis acids include compounds represented
by BR3 (R represents a phenyl group or fluorine that may have a
substituent such as fluorine, a methyl group, or a trifluoromethyl
group) . Examples of the compounds represented by BR3 include
trifluoroboron, triphenylboron, tris(4-fluorophenyl)boron,
tris(3,5-difluorophenyl)boron, tris(4-fluoromethylphenyl)boron,
tris(pentafluorophenyl)boron, tris{p-tolyl)boron,
tris(o-tolyl)boron, and tris(3,5-dimethylphenyl)boron.
[0075]
Examples of the ionic compounds include compounds
represented by general formula (iv) below:
[0076]
SF-2755 35
• • • ( v)
[0077)
In the above formula (iv), R1
7+ represents H+, a carbonium
cation, an oxonium cation, an ammonium cation, a phosphonium
cation, a cycloheptyltrienyl cation, or a ferrocenium cation
containing a transition metal.
[0078)
Examples of the carbonium cation include tri-substituted
carbonium cations such as triphenylcarbonium cation,
tri(methylphenyl)carbonium cation, and
tri(dimethylphenyl)carbonium cation.
[0079)
Examples of the ammonium cation include trialkylammonium
cations such as trimethylammonium cation, triethylammonium
cation, tri(n-propyl)ammonium cation, and tri(n-butyl)ammonium
cation; N,N-dialkylanilinium cations such as
N,N-dimethylanilinium cation, N,N-diethylanilinium cation, and
N,N,2,4,6-pentamethylanilinium cation; and dialkylammonium
cations such as di(isopropyl)ammonium cation and
dicyclohexylammonium cation.
~/ SF-2755 36
[0080]
Specific examples of the phosphonium cation include
triarylphosphonium cations such as triphenylphosphonium cation,
tri(methylphenyl)phosphonium
tri(dimethylphenyl)phosphonium cation.
[0081]
cation, and
R17+ preferably represents a carbonium cation, an ammonium
cation, or the like, and particularly preferably represents a
triphenylcarbonium cation, an N,N-dimethylanilinium cation, or
an N,N-diethylanilinium cation.
[0082]
In the above formula (iv), R18 to R21 represent organic groups
that may be the same as or different from each other, and preferably
an aryl group or a substituted aryl group.
Examples of the ionic compounds further include
trialkyl-substi tuted ammonium salts, N, N-dialkylanilinium salts,
dialkylammonium salts, and triarylphosphonium salts.
[0083]
Examples of the trialkyl-substituted ammonium salts include
triethylammonium tetraphenylborate, tri(n-propyl)ammonium
tetraphenylborate,
trimethylammonium
tri(n-butyl)ammonium
tetra(p-tolyl)borate,
tetraphenylborate,
trimethylammonium
tetra(o-tolyl)borate,
tetra(pentafluorophenyl)borate,
tri(n-butyl)ammonium
tri(n-propyl)ammonium
SF-2755 37
tetra(o,p-dimethylphenyl)borate, tri(n-butyl)ammonium
tetra(m,m-dimethylphenyl)borate, tri(n-butyl)ammonium
tetra(p-trifluoromethylphenyl)borate, tri(n-butyl)ammonium
tetra (3,5-ditrifluoromethylphenyl)borate, and
tri(n-butyl)ammonium tetra(o-tolyl)borate.
[0084]
Examples of the N,N-dialkylanilinium salts include
N,N-dimethylanilinium tetraphenylborate, N,N-diethylanilinium
tetraphenylborate, and N,N,2,4,6-pentamethylanilinium
tetraphenylborate.
[0085]
Examples of the dialkylammonium salts include
di(n-propyl)ammonium tetra(pentafluorophenyl)borate and
dicyclohexylammonium tetraphenylborate.
[0086]
Furthermore, examples of the ionic compounds further
include triphenylcarbenium tetrakis(pentafluorophenyl)borate,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate,
ferrocenium tetra(pentafluorophenyl)borate, triphenylcarbenium
pentaphenylcyclopentadienyl complex, N,N-diethylanilinium
pentaphenylcyclopentadienyl complex, and boron compounds
represented by a formula (v) or (vi) below:

CLAIMS
1. An olefin oligomerization catalyst (III) obtained by
contacting (D) a transition metal compound having a transition
metal atom selected from Group III to Group X of the periodic table
with a preliminary contact solid catalyst component (II) obtained
by contacting a solid catalyst component (I) formed by supporting
(B) an organoaluminum oxy-compound (b-2) on (A) a solid carrier
with (C) at least one compound selected from the group consisting
of an organometallic compound ( c-1) , an organoaluminum
oxy-compound(c-2), and a compound (c-3) that reacts with the
transition metal compound (D) to form a pair of ions.
2. The olefin oligomerization catalyst (III) according to
claim 1, further including an organoaluminum compound (b-1) as
the component (B) .
3. The olefin oligomerization catalyst (III) according to
claim 1 or 2, wherein the component (C) is the organoaluminum
oxy-compound (c-2).
4. The olefin oligomerization catalyst (III) according to any
one of claims 1 to 3, wherein the transition metal compound (D)
is a transition metal compound having a transition metal atom
selected from Group III to Group VI of the periodic table.
5. The olefin oligomerization catalyst (III) according to any
one of claims 1 to 3, wherein the transition metal compound (D)
is represented by general formula (1) below:
SF-2755 135
R1
I
z /Y.• ,
I R6..-. -..c-::-N·--... ·\M X
/ (n-1)
0
• • • ( 1 )
(in the general formula ( 1) , R1 to R6 may be the same as or different
from each other and each represent a hydrogen atom, a halogen atom,
a hydrocarbon group, a heterocyclic compound residue, an
oxygen-containing group, a nitrogen-containing group, a
boron-containing group, an aluminum-containing group, a
sulfur-containing group, a phosphorus-containing group, a
silicon-containing group, a germanium-containing group, or a
tin-containing group, in which two or more thereof may be linked
to each other, and R1 may be linked to Z;
M represents a transition metal atom selected from Group
III to Group X of the periodic table;
n represents a valence of M;
X represents a hydrogen atom, a halogen atom, a hydrocarbon
group, an oxygen-containing group, a sulfur-containing group, a
nitrogen-containing group, a boron-containing . group, an
aluminum-containing group, a phosphorus-containing group, a
halogen-containing group, a heterocyclic compound residue, a
silicon-containing group, a germanium-containing group, or a
tin-containing group, in which atoms or groups represented by X
may be the same as or different from each other, and the groups
represented by X may be liked to each other to form a ring;
Y represents an oxygen atom, a nitrogen atom, a phosphorus
atom, or a su+fur atom;
·z represents a hydrocarbon group or a heterocyclic compound
residue that may have a substituent, and the minimum number of
bonds linking Y and N is 4 to 6;
in the formula, a bond linking Y and Z may be a double bond
or a triple bond, and a bon~ linking Y and R1 may be a double bond
l
or a triple bond; and
in the formula, each dotted line represents a coordination
bond) .
6. A method for producing an olefin oligomer, wherein an
oligomerization reaction of an olefin is performed in the presence
of the olefin oligomerization catalyst according to any one of
claims 1 to 5.
7. The method for producing an olefin oligomer according to
claim 6, wherein the olefin is ethylene, and the olefin oligomer
is 1-hexene.