U.S. patent application number 16/622055 was filed with the patent office on 2021-05-20 for heteroatom ligand, oligomerization catalyst containing same, and method for preparing oligomer.
The applicant listed for this patent is SK Global Chemical Co., Ltd., SK Innovation Co., Ltd.. Invention is credited to Yong Nam Joe, Myoung Lae Kim, Ho Seong Lee, Jin Haek Yang.
Application Number | 20210146346 16/622055 |
Document ID | / |
Family ID | 1000005401757 |
Filed Date | 2021-05-20 |
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United States Patent
Application |
20210146346 |
Kind Code |
A1 |
Lee; Ho Seong ; et
al. |
May 20, 2021 |
Heteroatom Ligand, Oligomerization Catalyst Containing Same, and
Method for Preparing Oligomer
Abstract
The present invention relates to a heteroatom ligand, an
oligomerization catalyst containing the same, and a method for
preparing an oligomer by using the same. Specifically, the present
invention relates to a heteroatom ligand having a silsesquioxane
derivative, an oligomerization catalyst containing the same, and a
method for preparing an oligomer by using the same.
Inventors: |
Lee; Ho Seong; (Daejeon,
KR) ; Yang; Jin Haek; (Daejeon, KR) ; Kim;
Myoung Lae; (Daejeon, KR) ; Joe; Yong Nam;
(Daejeon, KR) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
SK Innovation Co., Ltd.
SK Global Chemical Co., Ltd. |
Seoul
Seoul |
|
KR
KR |
|
|
Family ID: |
1000005401757 |
Appl. No.: |
16/622055 |
Filed: |
May 15, 2018 |
PCT Filed: |
May 15, 2018 |
PCT NO: |
PCT/KR2018/005523 |
371 Date: |
December 12, 2019 |
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
B01J 31/143 20130101;
C07C 11/04 20130101; C07C 11/107 20130101; C07C 2/30 20130101 |
International
Class: |
B01J 31/14 20060101
B01J031/14; C07C 11/04 20060101 C07C011/04; C07C 11/107 20060101
C07C011/107; C07C 2/30 20060101 C07C002/30 |
Foreign Application Data
Date |
Code |
Application Number |
Jun 16, 2017 |
KR |
10-2017-0076510 |
Claims
1. A heteroatom ligand represented by the following Chemical
Formula 1: ##STR00017## wherein A and E are independently of each
other selected from the group consisting of phosphorus, arsenic,
antimony, oxygen, bismuth, sulfur, selenium, and nitrogen, D is a
linking group between A and E, Z is a silsesquioxane derivative, R
is hydrocarbylene, R.sub.1 and R.sub.2 are independently of each
other substituted or unsubstituted hydrocarbyl or substituted or
unsubstituted heterohydrocarbyl, p is an integer of 1 to 18, and n
and m are independently of each other determined by each valency or
oxidation state of A or E.
2. The heteroatom ligand of claim 1, wherein the silsesquioxane
derivative is represented by the following Chemical Formula 2:
*--(SiO.sub.3/2).sub.q(R.sup.7).sub.q-1 [Chemical Formula 2]
wherein R.sup.7 is hydrogen, hydroxy, a halogen, hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl, or substituted
heterohydrocarbyl, and q is 2, 4, 6, 8, 10, 12, 14, 16, or 18.
3. The heteroatom ligand of claim 2, wherein R.sup.7 is
C1-C10alkyl.
4. The heteroatom ligand of claim 2, wherein in Chemical Formula 2,
q is 8.
5. The heteroatom ligand of claim 1, wherein D is any one selected
from the group consisting of organic linking groups including
substituted or unsubstituted hydrocarbylene or substituted or
unsubstituted heterohydrocarbylene; and inorganic linking groups
including a single atomic link.
6. The heteroatom ligand of claim 1, wherein the heteroatom ligand
is selected from the following Chemical Formulae 3 to 5:
##STR00018## wherein Z is a silsesquioxane derivative, R.sup.11 to
R.sup.14 are independently of one another hydrocarbyl, substituted
hydrocarbyl, heterohydrocarbyl, or substituted heterohydrocarbyl, R
and R.sup.21 are independently of each other substituted or
unsubstituted C6-C20arylene, substituted or unsubstituted
C6-C20aryleneC1-C10alkylene, substituted or unsubstituted
C6-C20aryleneC2-C10alkenylene, substituted or unsubstituted
C6-C20aryleneC2-C10alkynylene, substituted or unsubstituted
C1-C10alkylene, substituted or unsubstituted C2-C10alkenylene,
substituted or unsubstituted C2-C10alkynylene, or substituted or
unsubstituted C3-C20heteroarylene, and R.sup.22 is substituted or
unsubstituted C6-C20aryl, substituted or unsubstituted
C6-C20arylC1-C10alkyl, substituted or unsubstituted
C6-C20arylC2-C10alkenyl, substituted or unsubstituted
C6-C20arylC2-C10alkynyl, C1-C10alkyl, C2-C10alkenyl, substituted or
unsubstituted C2-C10alkynyl, substituted or unsubstituted
C3-C20heteroaryl, or ##STR00019##
7. The heteroatom ligand of claim 6, wherein in Chemical Formulae 3
to 5, R.sup.11 to R.sup.14 are independently of one another
substituted or unsubstituted C6-C20aryl, substituted or
unsubstituted C6-C20arylC1-C10alkyl, substituted or unsubstituted
C6-C20arylC2-C10alkenyl, or substituted or unsubstituted
C6-C20arylC2-C10alkynyl, R and R.sup.21 are independently of each
other C1-C10alkylene, and R.sup.22 is C1-C10alkyl or
##STR00020##
8. The heteroatom ligand of claim 6, wherein the silsesquioxane
derivative is *--(SiO.sub.3/2).sub.q(R.sup.7).sub.q-1, wherein
R.sup.7 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl,
or substituted heterohydrocarbyl, and q is 2, 4, 6, 8, 10, 12, 14,
16, or 18.
9. The heteroatom ligand of claim 7, wherein R.sup.11 to R.sup.14
are independently of one another C6-C20aryl substituted by any one
or more selected from the group consisting of halogens,
C1-C10alkyl, haloC1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, and haloC1-C10alkoxy.
10. An oligomerization catalyst comprising: the heteroatom ligand
of claim 1 and a transition metal.
11. A method for preparing an oligomer, the method comprising:
introducing the oligomerization catalyst of claim 10 to a reactor;
introducing an olefin to the reactor; and reacting the olefin with
the oligomerization catalyst to be oligomerized.
12. The method for preparing an oligomer of claim 11, wherein the
olefin is ethylene, and the oligomer is 1-hexene or 1-octene.
13. The method for preparing an oligomer of claim 11, further
comprising: introducing a cocatalyst containing a metal in an
amount of 100 to 5,000 times the moles of the transition metal to
the reactor.
14. The method for preparing an oligomer of claim 13, wherein the
cocatalyst is an organic aluminum compound, organic aluminoxane, an
organic boron compound, an organic salt, or a mixture thereof.
15. The method for preparing an oligomer of claim 14, wherein the
cocatalyst is one or a mixture or two or more selected from the
group consisting of methylaluminoxane (MAO), modified
methylaluminoxane (MMAO), ethylaluminoxane (EAO),
tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO),
trimethylaluminum (TMA), triethylaluminum (TEA),
triisobutylaluminum (TIBA), tri-n-octylaluminum,
methylaluminumdichloride, ethylaluminum dichloride,
dimethylaluminum chloride, diethylaluminum chloride,
aluminumisopropoxide, ethylaluminum sesquichloride, and
methylaluminum sesquichloride.
Description
TECHNICAL FIELD
[0001] The present invention relates to a heteroatom ligand, an
oligomerization catalyst including the same, and a method for
preparing an oligomer using the oligomerization catalyst.
BACKGROUND ART
[0002] An oligomer, specifically 1-hexene or 1-octene is an
important commercial raw material which is widely used in a
polymerization process as a monomer or comonomer for preparing a
linear low-density polyethylene, and is obtained by purifying a
product produced by an oligomerization reaction of ethylene.
However, a conventional ethylene oligomerization reaction had an
inefficient aspect of producing significant amounts of butene,
higher oligomers, and polyethylene together with 1-hexene and
1-octene. Since the conventional ethylene oligomerization technique
as such generally produces various .alpha.-olefins depending on a
Schulze-Flory or Poisson product distribution, a product yield to
be desired is limited.
[0003] Recently, a study on selectively trimerizing ethylene to
produce 1-hexene or selectively tetramerizing ethylene to produce
1-octeneis by transition metal catalysis has been conducted, and
most of the known transition metal catalysts are chromium-based
catalysts.
[0004] International Patent Publication No. WO 02/04119 discloses a
chromium-based catalyst using a ligand represented by a general
formula of (R.sup.1)(R.sup.2)X--Y--X(R.sup.3)(R.sup.4) as an
ethylene trimerization catalyst, wherein X is phosphorus, arsenic,
or antimony, Y is a linking group such as --N(R.sup.5)--, and at
least one of R.sup.1, R.sup.2, R.sup.3, and R.sup.4 has a polar or
electron donating substituent.
[0005] Another known document discloses a use of
(o-ethylphenyl).sub.2PN(Me)P(o-ethylphenyl).sub.2 which is a
compound having no polar substituent on at least one of R.sup.1,
R.sup.2, R.sup.3, and R.sup.4 as a ligand representing a catalyst
activity on 1-hexene under a catalyst condition (Antea Carter et
al., Chem. Commun., 2002, p. 858-859).
[0006] Meanwhile, it is known from International Patent Publication
No. WO 04/056479 that ethylene is tetramerized by a chromium-based
catalyst including a PNP ligand from which a substituent is omitted
on a phenyl ring attached to phosphorus, thereby improving
selectivity in producing 1-octene, and the document discloses
(phenyl).sub.2PN(isopropyl)P(phenyl).sub.2 and the like as an
example of a heteroatom ligand used for a tetramerization catalyst
for tetramerization of these ethylenes.
[0007] The related art document discloses that the chromium-based
catalyst including a heteroatom ligand having nitrogen and
phosphorus as a heteroatom tetramerizes ethylene without a polar
substituent for a hydrocarbyl or heterohydrocarbyl group bonded to
a phosphorus atom, thereby producing 1-octene in a selectivity of
more than 70% by mass.
[0008] However, the related art documents do not suggest a clear
example as to specifically what form may tetramerize ethylene
highly selectively to produce 1-octene or trimerize ethylene to
produce 1-hexene, regarding a structure of a ligand containing a
heteroatom, suggests only a structure of a PNP type skeleton such
as (R.sup.1)(R.sup.2)P-- (R.sup.5)N--P(R.sup.3)(R.sup.4) as a
ligand having a 1-octene selectivity of about 70% by mass, and only
limitedly suggests a substitutable substituent form from among the
heteroatom ligands.
[0009] Meanwhile, in a catalyst system for tetramerization of
ethylene, a catalyst activity at a high reaction temperature is
decreased, a considerable polymer byproduct is formed to lower the
selectivity, and serious problems are caused in a polymerization
process.
[0010] Specifically, a tetramerization has decreased catalyst
activity at a high temperature to decrease the productivity and
selectivity of olefins, in particular 1-octene, and increase
production of byproducts. This causes tube blockage and fouling,
leading to shut down inevitably, thereby causing serious problems
in an olefin polymerization process.
[0011] Accordingly, it is required to develop an olefin
oligomerization catalyst having a structure in which olefin
oligomerization catalyst activity is not decreased even at a high
temperature while it is easy to adjust a catalyst amount, and
olefin is oligomerized with high activity and high selectivity to
produce 1-hexene or 1-octene.
DISCLOSURE
Technical Problem
[0012] An object of the present invention is to provide a
heteroatom ligand having excellent catalyst activity at the time of
olefin oligomerization simultaneously with high solubility in a
solvent to easily adjust a catalyst amount and maintain activity
even at a high temperature, thereby being capable of producing an
oligomer with high activity and high selectivity.
[0013] Another object of the present invention is to provide an
oligomerization catalyst including a transition metal coordinated
with a heteroatom ligand and an organic ligand and a cocatalyst and
a method for preparing an oligomer using the same.
Technical Solution
[0014] In one general aspect, a heteroatom ligand oligomerizes an
olefin with high activity and high selectivity even at a high
temperature for use in oligomerization of an olefin, specifically
trimerization or tetramerization of ethylene, and is represented by
the following Chemical Formula 1:
##STR00001##
[0015] wherein
[0016] A and E are independently of each other selected from the
group consisting of phosphorus, arsenic, antimony, oxygen, bismuth,
sulfur, selenium, and nitrogen,
[0017] D is a linking group between A and E,
[0018] Z is a silsesquioxane derivative,
[0019] R is hydrocarbylene,
[0020] R.sub.1 and R.sub.2 are independently of each other
substituted or unsubstituted hydrocarbyl or substituted or
unsubstituted heterohydrocarbyl,
[0021] p is an integer of 1 to 18, and varies with the number of Si
contained in the silsesquioxane derivative, and
[0022] n and m are independently of each other determined by each
valency or oxidation state of A or E.
[0023] In Chemical Formula 1 according to an exemplary embodiment
of the present invention, the silsesquioxane derivative may be
represented by the following Chemical Formula 2:
*--(SiO.sub.3/2).sub.q(R.sup.7).sub.q-1 [Chemical Formula 2]
[0024] wherein R.sup.7 is hydrogen, hydroxy, halogen, hydrocarbyl,
substituted hydrocarbyl, heterohydrocarbyl, or substituted
heterohydrocarbyl, and
[0025] q is 2, 4, 6, 8, 10, 12, 14, 16, or 18.
[0026] In addition, R.sup.7 is C6-C20aryl, C1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, C6-C20arylC1-C10alkyl,
C1-C10alkylC6-C20aryl, C3-C10cycloalkyl, C3-C10heterocycloalkyl, or
C3-C20heteroaryl, wherein R.sup.7 may be substituted by any one or
more selected from the group consisting of halogens, nitro, amino,
cyano, C6-C20aryl, C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl,
C6-C20arylC2-C10alkynyl, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, C6-C20aryloxy, C1-C10alkoxycarbonyl,
C1-C10alkylcarbonyloxy, C2-C10alkenylcarbonyloxy,
C2-C10alkynylcarbonyloxy, aminocarbonyl, C1-C10alkylcarbonylamino,
C2-C10alkenylcarbonylamino, C2-C10alkynylcarbonylamino,
C3-C10cycloalkyl, thioC1-C10alkyl, thioC2-C10alkenyl,
thioC2-C10alkynyl, C1-C10alkylsilyl, C2-C10alkenylsilyl,
C2-C10alkynylsilyl, C6-C20arylsilyl, C3-C20heteroaryl, and
C2-C10heterocycloalkyl. In addition, q may be an integer of 8.
[0027] Specifically, R.sup.7 may be C1-C10alkyl.
[0028] In Chemical Formula 1, D may be any one selected from the
group consisting of organic linking groups including substituted or
unsubstituted hydrocarbylene or substituted or unsubstituted
heterohydrocarbylene; and inorganic linking groups including a
single atomic link.
[0029] In terms of having excellent catalyst activity and
solubility even at a high temperature, preferably, Chemical Formula
1 may be selected from the following Chemical Formulae 3 to 5:
##STR00002##
[0030] wherein
[0031] Z is a silsesquioxane derivative,
[0032] R.sup.11 to R.sup.14 are independently of one another
hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl, or
substituted hydrocarbyl, specifically independently of one another
C6-C20aryl, C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl,
C6-C20arylC2-C10alkynyl, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, C6-C20aryloxy, C1-C10alkoxycarbonyl,
C1-C10alkylcarbonyloxy, C2-C10alkenylcarbonyloxy,
C2-C10alkynylcarbonyloxy, aminocarbonyl, C1-C10alkylcarbonylamino,
C2-C10alkenylcarbonylamino, C2-C10alkynylcarbonylamino,
C3-C10cycloalkyl, thioC1-C10alkyl, thioC2-C10alkenyl,
thioC2-C10alkynyl, C1-C10alkylsilyl, C2-C10alkenylsilyl,
C2-C10alkynylsilyl, C6-C20arylsilyl, C3-C20heteroaryl, 5- to
7-membered heterocycloalkyl or --NR.sup.31R.sup.32, wherein
R.sup.31 and R.sup.32 are independently of each other C1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C6-C20aryl, diC1-C10alkylamino,
diC2-C10alkenylamino, or diC2-C10alkynylamino,
[0033] R and R.sup.21 are independently of each other
C6-C20arylene, C6-C20aryleneC1-C10alkylene,
C6-C20aryleneC2-C10alkenylene, C6-C20aryleneC2-C10alkynylene,
C1-C10alkylene, C2-C10alkenylene, C2-C10alkynylene, or
C3-C20heteroarylene,
[0034] R.sup.22 is C6-C20arylene, C6-C20aryleneC1-C10alkylene,
C6-C20aryleneC2-C10alkenylene, C6-C20aryleneC2-C10alkynylene,
C1-C10alkylene, C2-C10alkenylene, C2-C10alkynylene,
C3-C20heteroarylene, or
##STR00003##
and
[0035] arylene, arylenealkylene, arylenealkenylene,
arylenealkynylene, alkylene, alkenylene, alkynylene, and
heteroarylene of R, R.sup.21, and R.sup.22 and aryl, arylalkyl,
alkyl, arylalkenyl, alkenyl, arylalkynyl, alkynyl, alkoxy, aryloxy,
cycloalkyl, heteroaryl, and heterocycloalkyl of R.sup.11 to
R.sup.14 may be further substituted by one or more selected from
the group consisting of halogens, C1-C10alkyl, haloC1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, haloC1-C10alkoxy,
C6-C20aryl, and C6-C20aryloxy.
[0036] Preferably, they may be further substituted by one or more
selected from the group consisting of halogens, C1-C10alkyl,
haloC1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, and
haloC1-C10alkoxy.
[0037] More preferably, in Chemical Formulae 3 to 5, R.sup.11 to
R.sup.14 are independently of one another C6-C20aryl,
C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl, or
C6-C20arylC2-C10alkynyl; R and R.sup.21 are independently of each
other C1-C10alkylene, R.sup.22 is C1-C10alkylene or
##STR00004##
aryl, arylalkyl, arylalkenyl, and arylalkynyl of R.sup.11 to
R.sup.14 and alkylene of Rn and R.sup.22 may be further substituted
by one or more selected from the group consisting of halogens,
C1-C10alkyl, haloC1-C10alkyl, C1-C10alkoxy, haloC1-C10alkoxy,
C6-C20aryl, and C6-C20aryloxy.
[0038] Preferably, the silsesquioxane derivative in Chemical
Formulae 3 to 5 may be *--(SiO.sub.3/2).sub.q(R.sup.7).sub.q-1
(wherein R.sup.7 and q are as defined in Chemical Formula 2).
[0039] In another general aspect, an oligomerization catalyst
includes the heteroatom ligand of the present invention and a
transition metal.
[0040] In still another general aspect, a method for preparing an
oligomer includes introducing an oligomerization catalyst to a
reactor, introducing an olefin to the reactor, and reacting the
olefin with the oligomerization catalyst to perform
oligomerization.
[0041] A cocatalyst according to an exemplary embodiment of the
present invention may be an organic aluminum compound, organic
aluminoxane, an organic boron compound, an organic salt, or a
mixture thereof, and specifically, one or a mixture or two or more
selected from the group consisting of methylaluminoxane (MAO),
modified methylaluminoxane (MAO), ethylaluminoxane (EAO),
tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO),
trimethylaluminum (TMA), triethylaluminum (TEA),
triisobutylaluminum (TIBA), tri-n-octylaluminum,
methylaluminumdichloride, ethylaluminum dichloride,
dimethylaluminum chloride, diethylaluminum chloride,
aluminumisopropoxide, ethylaluminum sesquichloride, and
methylaluminum sesquichloride.
[0042] The method for preparing an oligomer according to an
exemplary embodiment of the present invention may further include
introducing a cocatalyst containing a metal in an amount of 100 to
5,000 times the moles of the transition metal to the reactor.
[0043] In the method for preparing an oligomer according to an
exemplary embodiment of the present invention, the olefin may be
ethylene, and the oligomer may be 1-hexene, 1-octene, or a mixture
thereof.
Advantageous Effects
[0044] The heteroatom ligand having a silsesquioxane derivative of
the present invention is coordinated with a transition metal,
whereby catalyst activity and selectivity are excellent even at a
high temperature, and furthermore, solubility in a solvent is high,
so that an aliphatic hydrocarbon compound may be used as a reaction
solvent instead of a conventionally used aromatic hydrocarbon
compound, an oligomer may be prepared with high activity even with
a small amount of catalyst, and an introduction amount of a
catalyst may be easily adjusted.
[0045] In addition, the oligomerization catalyst of the present
invention has excellent catalyst activity even at a high
temperature, has a high solubility in a solvent to maintain
catalyst activity, allows mass production with a use of a small
amount of the cocatalyst, and does not cause fouling and tube
blockage which occurs in a high temperature process so that shut
down is not required, and thus, is very economical.
[0046] In addition, the method for preparing an oligomer of the
present invention may produce an oligomer with high activity and
high selectivity even at a high temperature, and does not cause
fouling and tube blockage, and thus, allows preparation of an
olefin with a very efficient process.
BEST MODE
[0047] "Hydrocarbyl" or "heterohydrocarbyl" described herein refers
to a radical having one binding site derived from hydrocarbon or
heterohydrocarbon, "hydrocarbylene" refers to a radical having two
binding sites derived from hydrocarbon, and "hetero" refers to a
carbon being substituted by one or more atoms selected from the
group consisting of O, S and N atoms.
[0048] "Substituted" described herein refers to a group or a site
having one or more substituents attached to a structural skeleton
of a group or part. It means that the mentioned group or structural
skeleton is substituted by any one or more selected from the group
consisting of deuterium, hydroxy, halogen, carboxyl, cyano, nitro,
oxo (.dbd.O), thio (.dbd.S), alkyl, haloalkoxy, alkenyl, alkynyl,
aryl, aryloxy, alkoxycarbonyl, alkylcarbonyloxy,
alkenylcarbonyloxy, alkynylcarbonyloxy, aminocarbonyl,
alkylcarbonylamino, alkenylcarbonylamino, alkylcarbonylamino,
alkenylcarbonylamino, alkynylcarbonylamino, thioalkyl, thioalkenyl,
thioalkynyl, alkylsilyl, alkenylsilyl, alkynylsilyl, arylsilyl,
arylalkyl, arylalkenyl, arylalkynyl, cycloalkyl, cycloalkylalkyl,
cycloalkenyl, amino, alkylamino, dialkylamino, heteroaryl, a
heterocyclylalkyl ring, heteroarylalkyl, and heterocycloalkyl.
[0049] Specifically, it means that the mentioned group or
structural skeleton is substituted by any one or more selected from
the group consisting of deuterium, hydroxy, halogen, carboxyl,
cyano, nitro, oxo(.dbd.O), thio(.dbd.S), C1-C10alkyl, haloC1-C10
alkoxy, C2-C10alkenyl, C2-C10alkynyl, C6-C20aryl, C6-C20aryloxy,
C1-C10alkoxycarbonyl, C1-C10alkylcarbonyloxy,
C2-C10alkenylcarbonyloxy, C2-C10alkynylcarbonyloxy, aminocarbonyl,
C1-C10alkylcarbonylamino, C2-C10alkenylcarbonylamino,
C2-C10alkylcarbonylamino, C2-C10alkenylcarbonylamino,
C2-C10alkynylcarbonylamino, thioC1-C10alkyl, thioC2-C10alkenyl,
thioC2-C10alkynyl, C1-C10alkylsilyl, C2-C10alkenylsilyl,
C2-C10alkynylsilyl, C6-C20arylsilyl, C6-C20arylC1-C10alkyl,
C6-C20arylC2-C10alkenyl, C6-C20arylC2-C10alkynyl, C3-C10cycloalkyl,
C3-C10cycloalkylC1-C10alkyl, C2-C10cycloalkenyl, amino,
C1-C10alkylamino, diC1-C10alkylamino, C6-C20heteroaryl,
C3-C20heterocycloalkyl ring, C3-C10heteroarylC1-C10alkyl, and
C3-C10heterocycloalkyl.
[0050] "Alkene" described herein refers to a straight chain,
branched chain, or cyclic hydrocarbon containing one or more
carbon-to-carbon double bonds.
[0051] "Alkyne" described herein refers to a straight chain,
branched chain, or cyclic hydrocarbon containing one or more
carbon-to-carbon triple bonds, and the alkene and alkyne described
in the present invention may have, as an example, 2 to 10 carbon
atoms, preferably 2 to 7 carbon atoms.
[0052] "Alkyl", "alkoxy", and other substituents containing an
"alkyl" moiety described herein include both straight chain or
branched chain forms, and have, as an example, 1 to 10 carbon
atoms, preferably 1 to 7 carbon atoms, more preferably 1 to 5
carbon atoms.
[0053] In addition, "aryl" described herein refers to an organic
radical derived from an aromatic hydrocarbon by removal of one
hydrogen, including a single- or fused ring system containing, as
an example, 4 to 7, preferably 5 or 6 ring atoms in each ring, and
even a form in which a plurality of aryls are linked by a single
bond. Specific examples thereof include phenyl, naphthyl, biphenyl,
anthryl, indenyl, fluorenyl, and the like, but are not limited
thereto.
[0054] "Heteroaryl" described herein refers to an aryl group
containing one or more atoms selected from the group consisting of
B, N, O, S, P(.dbd.O), Si, and P as an aromatic ring skeleton atom
and carbon as a remaining aromatic ring skeleton atom. As an
example, "heteroaryl" is a 5- to 6-membered monocyclic heteroaryl,
or a polycyclic heteroaryl condensed with one or more benzene
rings, and may be partially saturated. In addition, the heteroaryl
in the present invention also includes a form in which one or more
heteroaryls are linked by a single bond.
[0055] The term "alkenyl" described herein alone or as a part of
another group refers to a straight chain, branched chain, or cyclic
hydrocarbon radical containing one or more carbon-to-carbon double
bonds. As an example, the alkenyl radical is a lower alkenyl
radical having 2 to 10, preferably 2 to about 7 carbon atoms. The
most preferred lower alkenyl radical is a radical having 2 to about
5 carbon atoms. In addition, the alkenyl group may be substituted
at any usable attachment point. An example of the alkenyl radical
includes ethenyl, propenyl, allyl, butenyl and 4-methylbutenyl. The
terms alkenyl and lower alkenyl include radicals being cis- and
trans-oriented, or alternatively, having E and Z orientations
[0056] The term "alkynyl" described herein alone or as a part of
another group refers to a straight chain, branched chain, or cyclic
hydrocarbon radical containing one or more carbon-to-carbon triple
bonds. The alkenyl radical is a lower alkynyl radical having, as an
example, 2 to 10, preferably 2 to about 7 carbon atoms. The most
preferred is a lower alkenyl radical having 2 to about 5 carbon
atoms. Examples of the radical include propargyl, butynyl, and the
like. In addition, the alkynyl group may be substituted at any
usable attachment point.
[0057] "Cycloalkyl" described herein refers to a non-aromatic
monocyclic or polycyclic system, having preferably 3 to 10 carbon
atoms. The monocyclic ring includes cyclopropyl, cyclobutyl,
cyclopentyl, and cyclohexyl, without limitation. An example of the
polycyclic cycloalkyl group includes perhydronaphthyl,
perhydroindenyl, and the like; and a bridged polycyclic cycloalkyl
group includes adamantyl, norbornyl, and the like.
[0058] "Heterocycloalkyl" described herein refers to a substituted
or unsubstituted non-aromatic 3- to 15-membered ring radical
consisting of carbon atoms and 1 to 5 heteroatoms selected from the
group consisting of nitrogen, phosphorus, oxygen, and sulfur; a
heterocycloalkyl radical may be a monocyclic, bicyclic, or
tricyclic ring system which may be fused or bridged or include a
spirocyclic system; and if necessary, a nitrogen, phosphorus,
carbon, oxygen, or sulfur atom in the heterocyclic ring radical may
be oxidized to various oxidation states in some cases. In addition,
if necessary, a nitrogen atom may be quaternarized.
[0059] "An alicyclic ring" described herein refers to a
non-aromatic monocyclic or polycyclic ring system, and the carbon
in the ring may have a carbon-carbon double bond or a carbon-carbon
triple bond. The alicyclic ring may have preferably 3 to 10 carbon
atoms.
[0060] "An oligomerization catalyst" herein is defined as including
both a transition metal complex form prepared with a ligand and a
transition metal and a composition form of a ligand and a
transition metal.
[0061] "An oligomerization catalyst composition" herein is defined
as further including a cocatalyst or an additive in the
"oligomerization catalyst" described above.
[0062] The present invention provides an oligomerization catalyst
having a surprisingly improved solubility in a solvent while
maintaining high activity at a high temperature, unlike a
conventional catalyst, and the oligomerization catalyst according
to an exemplary embodiment of the present invention includes a
heteroatom ligand represented by the following Chemical Formula
1:
##STR00005##
[0063] A and E are independently of each other selected from the
group consisting of phosphorus, arsenic, antimony, oxygen, bismuth,
sulfur, selenium, and nitrogen,
[0064] D is a linking group between A and E,
[0065] Z a silsesquioxane derivative,
[0066] R is hydrocarbylene,
[0067] R.sub.1 and R.sub.2 are independently of each other
substituted or unsubstituted hydrocarbyl or substituted or
unsubstituted heterohydrocarbyl,
[0068] p is an integer of 1 to 18, and
[0069] n and m are independently of each other determined by each
valency or oxidation state of A or E.
[0070] In Chemical Formula p varies with the silsesquioxane
derivative, specifically the number of Si possessed by the
silsesquioxane derivative, and as an example, in Chemical Formula
1, when silsesquioxane is POSS, p may be an integer of 1 to 8.
[0071] In terms of having high activity and high selectivity, in
Chemical Formula 1, the silsesquioxane derivative may be
represented by the following Chemical Formula 2:
*--(SiO.sub.3/2).sub.q(R.sup.7).sub.q-1 [Chemical Formula 2]
[0072] wherein R.sup.7 is hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl, or substituted heterohydrocarbyl, and
[0073] q is an integer of 2, 4, 6, 8, 10, 12, 14, 16, or 18.
[0074] Preferably, in Chemical. Formula 2 according to an exemplary
embodiment of the present invention, R.sup.7 is hydrogen, hydroxy,
a halogen, C6-C20aryl, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, C6-C20arylC1-C10alkyl, C1-C10alkylC6-C20aryl,
C3-C10cycloalkyl, C3-C10heterocycloalkyl, or C3-C20heteroaryl, and
the aryl, alkyl, alkenyl, alkynyl, alkoxy, arylalkyl, alkylaryl,
cycloalkyl, heterocycloalkyl, and heteroaryl may be further
substituted by any one or more selected from the group consisting
of halogens, nitro, amino, cyano, C6-C20aryl,
C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl,
C6-C20arylC2-C10alkynyl, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, C6-C20aryloxy, C1-C10alkoxycarbonyl,
C1-C10alkylcarbonyloxy, C2-C10alkenylcarbonyloxy,
C2-C10alkynylcarbonyloxy, aminocarbonyl, C1-C10alkylcarbonylamino,
C2-C10alkenylcarbonylamino, C2-C10alkynylcarbonylamino,
C3-C10cycloalkyl, thioC1-C10alkyl, thioC2-C10alkenyl,
thioC2-C10alkynyl, C1-C10alkylsilyl, C2-C10alkenylsilyl,
C2-C10alkynylsilyl, C6-C20arylsilyl, C3-C20heteroaryl, and
C2-C10heterocycloalkyl; and preferably, R.sup.7 is hydrogen,
C6-C20aryl, C1-C10alkyl, C1-C10alkoxy, C3-C10cycloalkyl,
C3-C10heterocycloalkyl, or C3-C20heteroaryl, and the aryl, alkyl,
alkoxy, cycloalkyl, heterocycloalkyl, and heteroaryl may be further
substituted by any one or more selected from the group consisting
of halogen, nitro, amino, cyano, C6-C20aryl, C6-C20arylC1-C10alkyl,
C6-C20arylC2-C10alkenyl, C6-C20arylC2-C10alkynyl, C1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, C6-C20aryloxy,
C1-C10alkoxycarbonyl, C1-C10alkylcarbonyloxy,
C2-C10alkenylcarbonyloxy, C2-C10alkynylcarbonyloxy, aminocarbonyl,
C1-C10alkylcarbonylamino, C2-C10alkenylcarbonylamino,
C2-C10alkynylcarbonylamino, C3-C10cycloalkyl, thioC1-C10alkyl,
thioC2-C10alkenyl, thioC2-C10alkynyl, C1-C10alkylsilyl,
C2-C10alkenylsilyl, C2-C10alkynylsilyl, C6-C20arylsilyl,
C3-C20heteroaryl, and C2-C10heterocycloalkyl.
[0075] In Chemical Formula 2, q may be preferably an integer of 4,
6, 8, or 10, and more preferably an integer of 8.
[0076] More preferably, in Chemical Formula 2, R.sup.7 may be
hydrogen, C6-C20aryl, C1-C10alkyl, or C3-C10cycloalkyl, more
preferably C1-C10alkyl, and q may be an integer of 8.
[0077] In Chemical Formula 1, D may be any one selected from the
group consisting of organic linking groups including substituted or
unsubstituted hydrocarbylene or substituted or unsubstituted
heterohydrocarbylene; and inorganic linking groups including a
single atom link, and in Chemical Formula 1 according to an
exemplary embodiment of the present invention, R may be
C6-C20arylene or C1-C10alkylene, preferably C1-C10alkylene.
[0078] Preferably, the heteroatom ligand according to an exemplary
embodiment of the present invention may be selected from the
following Chemical Formula 3 to 5:
##STR00006##
[0079] wherein
[0080] Z is a silsesquioxane derivative,
[0081] R.sup.11 to R.sup.14 are independently of one another
C6-C20aryl, C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl,
C6-C20arylC2-C10alkynyl, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, C6-C20aryloxy, C1-C10alkoxycarbonyl,
C1-C10alkylcarbonyloxy, C2-C10alkenylcarbonyloxy,
C2-C10alkynylcarbonyloxy, aminocarbonyl, C1-C10alkylcarbonylamino,
C2-C10alkenylcarbonylamino, C2-C10alkynylcarbonylamino,
C3-C10cycloalkyl, thioC1-C10alkyl, thioC2-C10alkenyl,
thioC2-C10alkynyl, C1-C10alkylsilyl, C2-C10alkenylsilyl,
C2-C10alkynylsilyl, C6-C20arylsilyl, C3-C20heteroaryl, 5- to
7-membered heterocycloalkyl or --NR.sup.31R.sup.32, wherein
R.sup.31 and R.sup.32 are independently of each other C1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C6-C20aryl, diC1-C10alkylamino,
diC2-C10alkenylamino, or diC2-C10alkynylamino,
[0082] R and R.sup.21 are independently of each other
C6-C20arylene, C6-C20aryleneC1-C10alkylene,
C6-C20aryleneC2-C10alkenylene, C6-C20aryleneC2-C10alkynylene,
C1-C10alkylene, C2-C10alkenylene, C2-C10alkynylene, or
C3-C20heteroarylene,
[0083] R.sup.22 is C6-C20arylene, C6-C20aryleneC1-C10alkylene,
C6-C20aryleneC2-C10alkenylene, C6-C20aryleneC2-C10alkynylene,
C1-C10alkylene, C2-C10alkenylene, C2-C10alkynylene,
C3-C20heteroarylene, or
##STR00007##
and
[0084] arylene, arylenealkylene, arylenealkenylene,
arylenealkynylene, alkylene, alkenylene, alkynylene, and
heteroarylene of R, R.sup.21, and R.sup.22 and aryl, arylalkyl,
alkyl, arylalkenyl, alkenyl, arylalkynyl, alkynyl, alkoxy, aryloxy,
cycloalkyl, heteroaryl, and heterocycloalkyl of R.sup.11 to
R.sup.14 may be further substituted by one or more selected from
the group consisting of halogen, C1-C10alkyl, haloC1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, haloC1-C10alkoxy,
C6-C20aryl, and C6-C20aryloxy.
[0085] Preferably, in Chemical Formulae 3 to 5, R.sup.11 to
R.sup.14 are independently of one another C6-C20aryl,
C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl, or
C6-C20arylC2-C10alkynyl,
[0086] R and R.sup.21 are independently of each other
C1-C10alkylene,
[0087] R.sup.22 is C1-C10alkylene or
##STR00008##
and
[0088] the aryl, arylalkyl, arylalkenyl, and arylalkynyl of
R.sup.11 to R.sup.14 and the alkylene of Rn and R.sup.22 may be
further substituted by one or more selected from the group
consisting of halogen, C1-C10alkyl, haloC1-C10alkyl, C1-C10alkoxy,
haloC1-C10alkoxy, C6-C20aryl, and C6-C20aryloxy.
[0089] Preferably, the silsesquioxane derivative in Chemical
Formulae 3 to 5 is *--(SiO.sub.3/2).sub.q(R.sup.7).sub.q-1, wherein
R.sup.7 is hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl,
or substituted heterohydrocarbyl, preferably C1-C10alkyl, and q may
be an integer of 2, 4, 6, 8, 10, 12, 14, 16, or 18, and preferably
an integer of 8.
[0090] Specifically, the oligomerization catalyst according to an
exemplary embodiment of the present invention includes a heteroatom
ligand and a transition metal, and the oligomerization catalyst
composition according to an exemplary embodiment of the present
invention may include the oligomerization catalyst and a
cocatalyst.
[0091] The oligomerization catalyst according to an exemplary
embodiment of the present invention may be prepared by including
the heteroatom ligand, and may be prepared by further including an
organic ligand and a transition metal compound.
[0092] The oligomerization catalyst prepared with a transition
metal compound including the heteroatom ligand according to an
exemplary embodiment of the present invention and an organic ligand
may be represented by the following Chemical Formula 6:
##STR00009##
[0093] wherein
[0094] Z is a silsesquioxane derivative,
[0095] D is selected from the group consisting of organic linking
groups including substituted or unsubstituted hydrocarbylene or
substituted or unsubstituted heterohydrocarbylene; and inorganic
linking groups including a single atom link,
[0096] R is hydrocarbylene,
[0097] R.sup.11 to R.sup.14 are independently of one another
hydrocarbyl,
[0098] L is an organic ligand,
[0099] X is a halogen,
[0100] a is 0 or an integer of 1 to 3, and when a is an integer of
2 or more, L may be identical to or different from each other,
and
[0101] p is an integer of 1 to 8.
[0102] Preferably, in Chemical Formula 6 according to an exemplary
embodiment of the present invention, p may be an integer of 1 to 4,
more preferably 1.
[0103] Preferably, the oligomerization catalyst including the
heteroatom ligand including the silsesquioxane represented by
Chemical Formula 6 may be represented by the following Chemical
Formulae 7 to 9:
##STR00010##
[0104] wherein
[0105] Z is a silsesquioxane derivative,
[0106] R and R.sup.21 are independently of each other
C6-C20arylene, C6-C20aryleneC1-C10alkylene,
C6-C20aryleneC2-C10alkenylene, C6-C20aryleneC2-C10alkynylene,
C1-C10alkylene, C2-C10alkenylene, C2-C10alkynylene, or
C3-C20heteroarylene,
[0107] R.sup.22 is C1-C10alkylene or
##STR00011##
and
[0108] R.sup.11 to R.sup.14 are independently of one another
C6-C20aryl, C6-C20arylC1-C10alkyl, C6-C20arylC2-C10alkenyl,
C6-C20arylC2-C10alkynyl, C1-C10alkyl, C2-C10alkenyl, C2-C10alkynyl,
C1-C10alkoxy, C6-C20aryloxy, C1-C10alkoxycarbonyl,
C1-C10alkylcarbonyloxy, C2-C10alkenylcarbonyloxy,
C2-C10alkynylcarbonyloxy, aminocarbonyl, C1-C10alkylcarbonylamino,
C2-C10alkenylcarbonylamino, C2-C10alkynylcarbonylamino,
C3-C7cycloalkyl, thioC1-C10alkyl, thioC2-C10alkenyl,
thioC2-C10alkynyl, C1-C10alkylsilyl, C2-C10alkenylsilyl,
C2-C10alkynylsilyl, C6-C20arylsilyl, C3-C20heteroaryl, 5- to
7-membered heterocycloalkyl or --NR.sup.31R.sup.32, wherein
R.sup.31 and R.sup.32 are independently of each other C1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C6-C20aryl, diC1-C10alkylamino,
diC2-C10alkenylamino, or diC2-C10alkynylamino,
[0109] aryl, arylalkyl, arylalkenyl, and arylalkynyl of R.sup.11 to
R.sup.14 and the alkylene of R.sup.21 and R.sup.22 may be further
substituted by one or more selected from the group consisting of
halogen, C1-C10alkyl, haloC1-C10alkyl, C1-C10alkoxy,
haloC1-C10alkoxy, C6-C20aryl, and C6-C20aryloxy,
[0110] L is an organic ligand,
[0111] X is a halogen,
[0112] a is 0 or an integer of 1 to 3, and when a is an integer of
2 or more, L may be identical to or different from each other,
and
[0113] p is an integer of 1 to 8, and
[0114] arylene, arylenealkylene, arylenealkenylene,
arylenealkynylene, alkylene, alkenylene, alkynylene, and
heteroarylene of R, R.sup.21, and R.sup.22 and aryl, arylalkyl,
alkyl, arylalkenyl, alkenyl, arylalkynyl, alkynyl, alkoxy, aryloxy,
cycloalkyl, heteroaryl, and heterocycloalkyl of R.sup.11 to
R.sup.14 may be further substituted by one or more selected from
the group consisting of C1-C10alkyl, haloC1-C10alkyl,
C2-C10alkenyl, C2-C10alkynyl, C1-C10alkoxy, haloC1-C10alkoxy,
C6-C20aryl, C6-C20aryloxy, and halogen.
[0115] The transition metal compound according to an exemplary
embodiment of the present invention may further include an organic
ligand.
[0116] The transition metal compound including an organic ligand
may be represented by the following Chemical Formula 10, but is not
limited thereto:
M(L.sup.1).sub.s(L.sup.2).sub.t [Chemical Formula 10]
[0117] wherein M is a transition metal, L.sup.1 and L.sup.2 are an
organic ligand, and s and t are independently of each other an
integer of 0 or more and have an oxidation number of s+t=M.
[0118] In Chemical Formula 10, the transition metal is not
particularly limited, but may be Group 4, Group 5, or Group 6
transition metals, preferably, may be selected from the group
consisting of chromium, molybdenum, tungsten, titanium, tantalum,
vanadium, or zirconium, and more preferably, may be chrome.
[0119] In Chemical Formula 10, any organic ligand is possible as
long as it may be bonded to a transition metal, and as an example,
the organic ligand may be selected from the group consisting of
halogen, alkyl, alkene, alkenyl, cycloalkyl, heterocycloalkyl,
aryl, and heteroaryl.
[0120] Specifically, L in Chemical Formulae 6 to 9 and L.sup.1 and
L.sup.2 in Chemical Formula 10, which are the organic ligand
according to an exemplary embodiment of the present invention, may
be independently of each other selected from the group consisting
of halogen, C1-C10alkyl, C3-C10cycloalkyl, C3-C10heterocycloalkyl,
or the following structural formula, but is not limited
thereto.
##STR00012## ##STR00013##
[0121] In the above structural formula, R.sup.41 and R.sup.42 are
independently of each other hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl, or substituted hydrocarbyl, R.sup.43 is
hydrogen, halogen, hydrocarbyl, substituted hydrocarbyl,
heterohydrocarbyl, or substituted heterohydrocarbyl;
[0122] R.sup.44 and R.sup.45 are independently of each other
hydrogen, hydrocarbyl, substituted hydrocarbyl, heterohydrocarbyl,
or substituted heterohydrocarbyl.
[0123] L in Chemical Formulae 6 to 9 and L.sup.1 and L.sup.2 in
Chemical Formula 10 may be preferably C3-C10heterocycloalkyl. The
oligomerization catalyst according to an exemplary embodiment of
the present invention includes a heteroatom ligand, whereby
solubility is excellent to have excellent catalyst activity without
using a large amount of a cocatalyst, an introduction amount of the
catalyst at the time of oligomerization of an olefin may be
adjusted, and furthermore, excellent activity is maintained even at
a high temperature, so that tube blockage and fouling do not occur
in an olefin preparation process, and thus, the oligomerization
catalyst is very economical and efficient.
[0124] Specifically, the oligomerization catalyst according to an
exemplary embodiment of the present invention has a heteroatom
ligand having a silsesquioxane derivative, whereby selectivity at
the time of olefin polymerization using the catalyst is very high,
activity at a high temperature is excellent, solubility of the
oligomerization catalyst is excellent, so that various solvents may
be used, and thus, the oligomerization catalyst is applicable to
various process conditions and allows mass production.
[0125] The cocatalyst may be an organic aluminum compound, an
organic aluminoxane, an organic boron compound, an organic salt, or
a mixture thereof.
[0126] The organic aluminum compound may include a compound of
Al(R.sup.a).sub.3 (wherein R.sup.a is independently of each other
C1-C12alkyl, C2-C10alkenyl, C2-C10alkynyl, C1-C12alkoxy, or a
halogen) or LiAlH.sub.4 and the like.
[0127] The organic aluminum compound may include one or a mixture
or two or more selected from the group consisting of
trimethylaluminum (TMA), triethylaluminum (TEA),
triisobutylaluminum (TIBA), tri-n-octylaluminum, methylaluminum
dichloride, ethylaluminum dichloride, dimethylaluminum chloride,
diethylaluminum chloride, aluminum isopropoxide, ethylaluminum
sesquichloride, and methylaluminum sesquichloride.
[0128] The organic aluminoxane may be an oligomer compound which
may be prepared by adding water and an alkylaluminum compound, for
example, by adding water to trimethylaluminum. The produced
aluminoxane oligomer compound may be linear, cyclic, cage, or a
mixture thereof.
[0129] The organic aluminoxane may be selected from the group
consisting of alkylaluminoxane, for example, methylaluminoxane
(MAO), ethylaluminoxane (EAO), tetraisobutylaluminoxane (TIBAO),
and isobutylaluminoxane(IBAO), and also modified alkylaluminoxane,
for example, modified methylaluminoxane (MAO). The modified
methylaluminoxane (manufactured by Akzo Nobel N.V.) includes a
hybrid alkyl group such as isobutyl or n-octyl groups in addition
to a methyl group.
[0130] As a specific example, the organic aluminoxane may be one or
a mixture two or more selected from the group consisting of
methylaluminoxane(MAO), modified methylaluminoxane (MAO),
ethylaluminoxane(EAO), tetraisobutylaluminoxane(TIBAO), and
isobutylaluminoxane(IBAO).
[0131] The organic boron compound as the cocatalyst may be
boroxine, NaBH.sub.4, triethylborane, triphenylborane,
triphenylborane ammonia complex, tributylborate,
triisopropylborate, tris(pentafluorophenyl)borane,
triethyl(tetrapentafluorophenyl)borate,
dimethylphenylammonium(tetrapentafluorophenyl)borate,
diethylphenylammonium(tetrapentafluorophenyl)borate,
methyldiphenylammonium(tetrapentafluorophenyl)borate, or
ethyldiphenylammonium(tetrapentafluorophenyl)borate, and the
organic boron compound thereof may be mixed with the organic
aluminum compound.
[0132] Preferably, the cocatalyst may be one or a mixture of two or
more selected from the group consisting of methylaluminoxane (MAO),
modified methylaluminoxane (MMAO), ethylaluminoxane (EAO),
tetraisobutylaluminoxane (TIBAO), isobutylaluminoxane (IBAO),
trimethylaluminum (TMA), triethylaluminum (TEA),
triisobutylaluminum (TIBA), tri-n-octylaluminum,
methylaluminumdichloride, ethylaluminum dichloride,
dimethylaluminum chloride, diethylaluminum chloride,
aluminumisopropoxide, ethylaluminum sesquichloride, and
methylaluminum sesquichloride, preferably methylaluminoxane (MAO)
or modified methylaluminoxane (MMAO), and a ratio of the
oligomerization catalyst and the cocatalyst may be 1:1 to 10,000:1,
preferably 1:1 to 2,000:1, as a mole ratio of the metal of the
cocatalyst:transition metal of the oligomerization catalyst.
[0133] The oligomerization catalyst composition according to the
present invention may further include other possible components in
addition to the oligomerization catalyst and the cocatalyst, as
long as the component does not impair the nature of the present
invention.
[0134] In addition, the method for preparing an oligomer according
to an exemplary embodiment of the present invention includes
introducing an oligomerization catalyst to a reactor, introducing
an olefin to the reactor, and reacting the olefin with the
oligomerization catalyst to perform oligomerization.
[0135] The method for preparing an oligomer according to an
exemplary embodiment of the present invention may further include
introducing a cocatalyst containing a metal in an amount of 100 to
5000 times the moles of the transition metal to the reactor,
wherein the cocatalyst is as described above.
[0136] The oligomerization catalyst and the additive which are
separate components of the olefin oligomerization catalyst
composition disclosed in the present invention are blended at the
same time or sequentially in an optional order in the presence of a
solvent to provide an olefin oligomerization catalyst composition.
Mixing of each component of the catalyst component may be performed
at a temperature of -20 to 250.degree. C. and while the catalyst
components are mixed, the presence of the olefin may generally
represent a protection effect to provide improved catalyst
performance. A more preferred temperature range is 45 to
100.degree. C.
[0137] An oligomer prepared from the olefin which is a reaction
product disclosed in the present invention, in particular, 1-hexene
or 1-octene, may be prepared by a heterogeneous liquid phase
reaction, a two-phase liquid/liquid reaction, or a bulk phase
reaction or a gas phase reaction in which a product olefin acts as
a main medium, in the presence of an inert solvent, using the
oligomerization catalyst of an olefin, particularly ethylene
according to the present invention, a common apparatus, and a
contact technique.
[0138] The method for preparing an oligomer according to an
exemplary embodiment of the present invention may be performed in
an inert solvent. That is, the oligomerization catalyst, the
cocatalyst, and an optional inert solvent which does not react with
an additive may be used, and the inert solvent may be an aliphatic
hydrocarbon. The aliphatic hydrocarbon is a saturated aliphatic
hydrocarbon, and may include a linear saturated aliphatic
hydrocarbon represented by C.sub.nH.sub.2n+2 (wherein n is an
integer of 1 to 15), an alicyclic saturated aliphatic hydrocarbon
represented by C.sub.mH.sub.2m (wherein m is an integer of 3 to 8),
and a saturated aliphatic hydrocarbon in which one or two or more
lower alkyl groups having 1 to 3 carbon atoms are substituted. A
specific list thereof is as follows: one or more selected from the
group consisting of pentane, hexane, heptane, octane, nonene,
decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane,
2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane,
2,2,4-trimethylpentane, 2,3,4-trimethylpentane, 2-methylhexane,
3-methylhexane, 2,2-dimethylhexane, 2,4-dimethylhexane,
2,5-dimethylhexane, 3,4-dimethyhexane, 2-methylheptane,
4-methylheptane, cyclohexane, methylcyclohexane, ethylcyclohexane,
isopropylcyclohexane, 1,4-dimethylcyclohexane, and
1,2,4-trimethylcyclohexane, but not limited thereto.
[0139] In the method for preparing an oligomer according to an
exemplary embodiment of the present invention, the oligomerization
reaction may be performed at a temperature of 0 to 200.degree. C.,
preferably 15 to 130.degree. C., and more preferably 45 to
100.degree. C., under a reaction pressure of an atmospheric
pressure to 100 bar, preferably an atmospheric pressure to 80 bar,
and more preferably an atmospheric pressure to 60 bar.
[0140] In an exemplary embodiment of the present invention, under
the oligomerization reaction condition, as an example, a yield of
1-hexene from ethylene may be 10% by mass or more, preferably 30%
by mass or more. In this case, the yield refers to grams of
1-hexene formed per 100 g of total C6 products.
[0141] In an exemplary embodiment of the present invention, under
the oligomerization reaction condition, as an example, a yield of
1-octene from ethylene may be 40% by mass or more, preferably 60%
by mass or more. In this case, the yield refers to grams of
1-octene formed per 100 g of total C8 products.
[0142] It is recognized therefrom that the method for preparing an
oligomer of the present invention uses the oligomer catalyst
composition including the heteroatom ligand containing
silsesquioxane of the present invention, whereby activity of the
catalyst is maintained even at a high temperature, and a produced
amount of 1-octene is significantly high, unlike the conventional
method.
[0143] In the method for preparing an oligomer according to an
exemplary embodiment of the present invention, the olefin may be
ethylene, and the oligomer may be 1-hexene, 1-octene, or a mixture
thereof.
[0144] The method for preparing an oligomer according to an
exemplary embodiment of the present invention may be performed in a
plant including an optional type of reactor. Examples of the
reactor include a batch reactor, a semi-bath reactor, and a
continuous reactor, but are not limited thereto. The plant may
include a reactor, an olefin reactor and an inlet of a catalyst
composition in the reactor, a line for flowing out an
oligomerization reaction product from the reactor, and at least one
separator for separating the oligomerization reaction product in
combination, in which the catalyst composition is the
oligomerization catalyst composition disclosed in the present
invention and may include an oligomerization catalyst having a
transition metal coordinated with an organic ligand and a
heteroatom ligand, a cocatalyst, and an additive.
[0145] The method for preparing an oligomer according to an
exemplary embodiment of the present invention improves the problems
raised in the process, thereby easily producing 1-hexene, 1-octene,
or a mixture thereof.
[0146] The following Examples specifically describe the effect of
the present invention. However, the following Examples are only
illustrative of the present invention, and do not limit the scope
of the present invention.
[Ligand Preparation Example 1] Preparation of (phenyl).sub.2PN
(propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2
[0147] Preparation of Aminopropylisobutyl Polyhedral Oligomeric
Silsesquioxane
##STR00014##
[0148] Trisilanol silsesquioxane (4.52 g, 5.7 mmol, Sigma-Aldrich
Corporation) was dissolved in anhydrous THF (40 ml) in a dried 100
ml flask under a nitrogen atmosphere, and
(3-aminopropyl)triethoxysilane (1.6 ml, 7.2 mmol, Sigma-Aldrich
Corporation) was added thereto. The mixture was reacted at room
temperature for 48 hours or more, a volatile material was removed
under a reduced pressure, and the residue was washed with
acetonitrile (2.times.20 ml) to obtain 4.1 g (82%) of an
aminopropylisobutyl polyhedral oligomeric silsesquioxane product as
a white solid.
[0149] .sup.1H NMR (500 MHz, CDCl.sub.3): .delta. 2.69 (t, 2H, J=7
Hz, --CH.sub.2NH.sub.2 tether), 1.85 (m, 7H, CH), 1.54 (m, 2H,
CH.sub.2 tether), 1.36 (s, 2H, NH.sub.2), 0.95 (m, 42H, CH.sub.3),
0.60 (m, 2H, Si--CH.sub.2 tether, 14H, Si--CH.sub.2).
[0150] .sup.13C NMR (600 MHz, CDCl.sub.3): .delta. 44.7, 27.1,
25.7, 23.9, 22.5, 9.2.
[0151] FT-ICR MS: m/z [M+H].sup.+ calcd for
C.sub.31H.sub.71NO.sub.12Si.sub.8: 874.5789; found: 874.3172.
[0152] Preparation of (phenyl).sub.2PN(propylisobutyl polyhedral
oligomeric silsesquioxane)P(phenyl).sub.2
##STR00015##
[0153] Aminopropylisobutyl polyhedral oligomeric silsesquioxane
(0.2 g, 0.23 mmol) was dissolved in dichloromethane (3 ml) in a 20
ml vial under a nitrogen atmosphere, triethylamine (0.13 ml, 0.96
mmol) was mixed therewith, and chlorodiphenylphosphine (0.106 g,
0.48 mmol) was added thereto. The mixture was stirred at room
temperature for one hour, a volatile material was removed under
reduced pressure, the residue was reslurried and washed with
methanol (2.times.2 ml) and then filtered to obtain 0.21 g (77%) of
(phenyl).sub.2PN(propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2 as a white solid product.
[0154] .sup.1H NMR (500 MHz, CDCl.sub.3) .delta.: 7.36 (br, 8H,
aromatics), 7.28 (br, 12H, aromatics), 3.16 (m, 2H, --CH.sub.2--),
1.82 (m, 7H, CH), 1.41 (t, 2H, J=6 Hz, --CH.sub.2N), 0.90 (m, 42H,
CH.sub.3), 0.58 (m, 14H, Si--CH.sub.2), 0.38 (t, 2H, J=8 Hz,
Si--CH.sub.2).
[0155] .sup.13C NMR (600 MHz, CDCl.sub.3) .delta.: 139.9, 132.5,
128.5, 127.9, 45.8, 25.7, 24.2, 23.8, 22.5, 9.2.
[0156] .sup.31P NMR (500 MHz, CDCl.sub.3) .delta.: 62.1.
[0157] FT-ICR MS: m/z [M+H].sup.+ calcd for
C.sub.55H.sub.89NO.sub.12P.sub.2Si.sub.8: 1242.9262; found:
1242.4033.
[Example 1] Ethylene Oligomerization Reaction Using Pentane, and
Cr(III)Cl3(tetrahydrofuran)3, (phenyl)2PN(propylisobutyl polyhedral
oligomeric silsesquioxane)P(phenyl)2, and mMAO-3A at 45.degree.
C.
[0158] A 50 ml autoclave reactor was washed with nitrogen under
vacuum, 20 ml of pentane was added, and 0.5 ml (0.94 mmol) of
mMAO-3A (7 wt %-A1) commercially available from Akzo Nobel N.V. was
added thereto. 7.0 mg (20 umol) of
Cr(III)Cl.sub.3(tetrahydrofuran).sub.3 and 28.8 mg (20 umol) of
(phenyl) 2PN (propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2 of Ligand Preparation Example 1 in 1
ml of dichloromethane were mixed in a glove box and stirred at room
temperature for 5 minutes. A volatile material was removed by
drying under reduced pressure, 10 ml of methylcyclohexane was added
to dissolve the residue completely, and 0.5 ml (1 umol) of an
aliquot was introduced to the reactor. A pressure reactor was
filled with 30 bar of ethylene and stirring was performed at a
stirring speed of 600 rpm. After 15 minutes, supply of ethylene to
the reactor was stopped, stirring was stopped to stop the reaction,
and the reactor was cooled to 10.degree. C. or lower. An excess
amount of ethylene in the reactor was discharged, and 1.5 ml of
2-ethylhexane was injected to the reactor. A small amount of
organic layer sample was passed through a micron syringe filter,
and was analyzed with GC-FID. The remaining organic layer was
filtered and a solid wax/polymer product was separated. These solid
products were dried in an oven at 100.degree. C. overnight, and the
resultant product was recorded. A product distribution in this
example is summarized in the following Table 1.
[Example 2] Ethylene Oligomerization Reaction Using Hexane, and
Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2, and mMAO-3A at 45.degree. C.
[0159] An oligomerization reaction was performed in the same manner
as in Example 1, except that hexane was used as a reaction solvent.
A product distribution in this example is summarized in the
following Table 1.
[Example 3] Ethylene Oligomerization Reaction Using cyclohexane,
and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3, (phenyl).sub.2PN
(propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2, and mMAO-3A at 45.degree. C.
[0160] An oligomerization reaction was performed in the same manner
as in Example 1, except that cyclohexanone was used as a reaction
solvent. A product distribution in this example is summarized in
the following Table 1.
[Example 4] Ethylene Oligomerization Reaction Using
methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN (propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2, and mMAO-3A at 45.degree. C.
[0161] An oligomerization reaction was performed in the same manner
as in Example 1, except that cyclohexanone was used as a reaction
solvent. A product distribution in this example is summarized in
the following Table 1.
[Example 5] Ethylene Oligomerization Reaction Using
methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN (propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2, and mMAO-3A at 60.degree. C.
[0162] An oligomerization reaction was performed in the same manner
as in Example 1, except that methylcyclohexane was used as a
reaction solvent and a reaction temperature was 60.degree. C. A
product distribution in this example is summarized in the following
Table 1.
[Example 6] Ethylene Oligomerization Reaction Using
methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2, and mMAO-3A at 80.degree. C.
[0163] An oligomerization reaction was performed in the same manner
as in Example 1, except that methylcyclohexane was used as a
reaction solvent and a reaction temperature was 80.degree. C. A
product distribution in this example is summarized in the following
Table 1.
[Example 7] Ethylene Oligomerization Reaction Using
methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN (propylisobutyl polyhedral oligomeric
silsesquioxane)P(phenyl).sub.2, and mMAO-3A at 100.degree. C.
[0164] An oligomerization reaction was performed in the same manner
as in Example 1, except that methylcyclohexane was used as a
reaction solvent and a reaction temperature was 100.degree. C. A
product distribution in this example is summarized in the following
Table 1.
[Comparative Ligand Preparation Example 1] Preparation of
(phenyl).sub.2PN (n-butyl) P (phenyl).sub.2
##STR00016##
[0166] N-butyl amine (0.3 g, 4.1 mmol) was dissolved in
dichloromethane (20 ml) in a 20 ml vial dried under a nitrogen
atmosphere, triethylamine (3.51 ml, 25.2 mmol) was mixed therewith,
and chlorodiphenylphosphine (1.855 g, 8.4 mmol) was added thereto.
The mixture was stirred at room temperature for one hour, a
volatile material was removed under reduced pressure, the residue
was reslurried and washed with methanol (2.times.2 ml) and then
filtered to obtain 1.22 g (67%) of
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2 as a white solid
product.
[0167] .sup.1H NMR (CDCl.sub.3): .delta. 0.60 (t, 3H, J=7 Hz,
CH.sub.3), 0.92 (t, 2H, J=7, CH.sub.2), 1.07 (m, 2H, CH.sub.2),
3.23 (q, 2H, J=9, N--CH.sub.2), 7.31 (s, 12H, aromatics), 7.39 (s,
8H, aromatics)
[Comparative Example 1] Ethylene Oligomerization Reaction Using
Pentane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at 45.degree.
C.
[0168] An oligomerization reaction was performed in the same manner
as in Example 1, except that
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2 was used as a ligand. A
product distribution in this example is summarized in the following
Table 1.
[Comparative Example 2] Ethylene Oligomerization Reaction Using
Hexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at 45.degree.
C.
[0169] An oligomerization reaction was performed in the same manner
as in Comparative Example 1, except that hexane was used as a
reaction solvent. A product distribution in this example is
summarized in the following Table 1.
[Comparative Example 3] Ethylene Oligomerization Reaction Using
Cyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at 45.degree.
C.
[0170] An oligomerization reaction was performed in the same manner
as in Comparative Example 1, except that cyclohexanone was used as
a reaction solvent. A product distribution in this example is
summarized in the following Table 1.
[Comparative Example 4] Ethylene Oligomerization Reaction Using
Methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at 45.degree.
C.
[0171] An oligomerization reaction was performed in the same manner
as in Comparative Example 1, except that methylcyclohexanone was
used as a reaction solvent. A product distribution in this example
is summarized in the following Table 1.
[Comparative Example 5] Ethylene Oligomerization Reaction Using
Methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at 60.degree.
C.
[0172] An oligomerization reaction was performed in the same manner
as in Comparative Example 1, except that methylcyclohexane was used
as a reaction solvent and a reaction temperature was 60.degree. C.
A product distribution in this example is summarized in the
following Table 1.
[Comparative Example 6] Ethylene Oligomerization Reaction Using
Methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at 80.degree.
C.
[0173] An oligomerization reaction was performed in the same manner
as in Comparative Example 1, except that methylcyclohexane was used
as a reaction solvent and a reaction temperature was 80.degree. C.
A product distribution in this example is summarized in the
following Table 1.
[Comparative Example 7] Ethylene Oligomerization Reaction Using
Methylcyclohexane, and Cr(III)Cl.sub.3(tetrahydrofuran).sub.3,
(phenyl).sub.2PN(n-butyl)P(phenyl).sub.2, and mMAO-3A at
100.degree. C.
[0174] An oligomerization reaction was performed in the same manner
as in Comparative Example 1, except that methylcyclohexane was used
as a reaction solvent and a reaction temperature was 100.degree. C.
A product distribution in this example is summarized in the
following Table 1.
TABLE-US-00001 TABLE 1 Reaction Activity temperature 1-Hexene C8
1-Octene C10-C14 Polymer Octene/hexene Catalyst (kg/g Cr/h)
(.degree. C.) C6 (wt %) in C6 (wt %) (wt %) in C8 (wt %) (wt %) (wt
%) (g ratio) Example 1 1150 45 21.1 39.1 63.9 96.9 10.9 4.1 3.0
Comparative 125 45 20.2 45.9 69.8 97.2 8.8 1.2 3.5 Example 1
Example 2 870 45 21.7 34.3 63.3 95.7 10.2 4.8 2.9 Comparative 166
45 19.2 51.3 69.3 96.1 9.9 1.6 3.6 Example 2 Example 3 981 45 22.0
36.4 64.3 95.2 9.8 4.0 2.9 Comparative 214 45 11.5 30.5 71.5 95.8
15.8 1.2 6.2 Example 3 Example 4 1049 45 23.4 41.9 62.7 95.4 10.3
3.6 2.7 Comparative 446 45 13.1 34.2 70.8 96.5 15.9 0.2 5.4 Example
4 Example 5 997 60 24.8 47.4 64.1 95.7 9.0 2.0 2.6 Comparative 575
60 23.0 51.7 68.6 97.0 7.6 0.8 3.0 Example 5 Example 6 873 80 26.4
53.7 63.5 96.6 8.1 2.0 2.4 Comparative 388 80 18.1 67.7 65.8 97.6
16.1 0.1 3.6 Example 6 Example 7 640 100 30.7 63.7 59.9 96.9 7.7
1.7 2.0 Comparative 239 100 29.0 67.6 61.8 97.2 7.7 1.6 2.1 Example
7
[0175] As seen from Table 1, it is recognized that the
oligomerization catalyst composition including the heteroatom
ligand having silsesquioxane of the present invention has excellent
activity as compared with those of the Comparative Examples, and in
particular, maintains activity even at a high polymerization
temperature.
[0176] The heteroatom ligand according to an exemplary embodiment
of the present invention is a heteroatom ligand having a
silsesquioxane derivative and is coordinated with a transition
metal including an organic ligand, whereby soluability is extremely
excellent unlike the conventional art, and allows use of various
polymerization solvents the time oligomerization of olefins,
whereby a range of production process application is very wide and
mass production is possible, solubility is excellent while a
catalyst activity is maintained even at a high temperature, tube
blockage and fouling are absent due to less production of
byproducts, and shut down for removing the byproducts is not
required so as to be very economical.
[0177] Besides, the oligomerization catalyst according to an
exemplary embodiment of the present invention has excellent
catalyst activity even at a high temperature, so that the oligomer
may be prepared in the oligomerization process of olefins even with
a small amount of catalyst and a small amount of cocatalyst
[0178] Furthermore, the oligomerization catalyst according to an
exemplary embodiment of the present invention does not have reduced
activity even at a high temperature and has excellent selectivity,
so that 1-hexene or 1-octene, in particular, 1-octene, may be
prepared with high selectivity from olefin, in particular
ethylene.
* * * * *