Title: Multinuclear half metallocene catalyst and preparation of styrene polymer using the same
Abstract: The present invention relates to a catalyst for preparing vinyl aromatic polymer and styrene polymerization using the same, and particularly to a transition metal half metallocene catalyst with a novel structure for preparing syndiotactic styrene polymer having high activity, superior stereoregularity, high melting point and various molecular weight distributions and a process for preparing styrene polymer using the same. The present invention provides a multinuclear half metallocene compound in which two or more of transition metals of groups 3 to 10 on periodic table are connected through bridge ligand simultaneously containing π-ligand cycloalkandienyl group and σ-ligand functional group and its preparation, and a process for preparing styrene polymer using the compound as a catalyst. Polymers with various molecular weight distributions as well as vinyl aromatic polymer having predominant syndiotactic structure can be prepared with high activity using the multinuclear half metallocene catalyst.
Patent Number: 6,894,129 Issued on 05/17/2005 to Lee, et al.
| Inventors:
|
Lee; Min-Hyung (Daejeon, KR);
Jeong; You-Mi (Daejeon, KR);
Ryu; Jin-Young (Daejeon, KR)
|
| Assignee:
|
LG Chem, Ltd. (KR)
|
| Appl. No.:
|
380022 |
| Filed:
|
July 11, 2002 |
| PCT Filed:
|
July 11, 2002
|
| PCT NO:
|
PCTKR02/01317
|
| 371 Date:
|
March 6, 2003
|
| 102(e) Date:
|
March 6, 2003
|
| PCT PUB.NO.:
|
WO0300647 |
| PCT PUB. Date:
|
January 23, 2003 |
Foreign Application Priority Data
| Jul 11, 2001[KR] | 2001-41580 |
| Current U.S. Class: |
526/114; 502/103; 502/117; 502/152; 502/155; 526/160; 526/161; 526/172; 526/346; 526/347; 526/347.1; 556/1; 556/52; 556/55 |
| Intern'l Class: |
C08F 004/60; C08F004/64; C08F004/64.2; C08F112/08 |
| Field of Search: |
526/114,160,161,172,346,347,347.1
502/152,155
556/52,55
|
References Cited [Referenced By]
U.S. Patent Documents
| 6010972 | Jan., 2000 | Zacharias et al.
| |
| 6010974 | Jan., 2000 | Kim et al.
| |
| 6235917 | May., 2001 | Graf et al.
| |
| Foreign Patent Documents |
| 2026552 | Mar., 1991 | CA.
| |
| 0 210 615 | Nov., 1990 | EP.
| |
| 0 964 004 | Dec., 1999 | EP.
| |
| 0 985 676 | Mar., 2000 | EP.
| |
| 4314790 | Nov., 1992 | JP.
| |
| WO 0052063 | Sep., 2000 | WO.
| |
| WO 0078827 | Dec., 2000 | WO.
| |
Other References
Y. Kim, et al., "New half-sandwich metallocene catalyst for polyethylene and
polystyrene", Journal of Organometallic Chemistry 634, 2001, pp. 19-24.
Y. Tianger, et al., "Recent Advances in Synthesis of Novel Half-Sandwich Group
4 Metallocene Complexes", Chemical Journal on Internet, retrieved on Aug. 29, 2002.
Y. Kim, et al., New Half-Metallocene Catalysts Generating Polyethylene with Bimodal
Molecular Weight Distribution and Syndiotactic Polystyrene, Macromol Rapid Commun.,
22, 2001, pp. 573-578.
International Search Report; PCT/KR02/01317; Oct., 9, 2002.
|
Primary Examiner: Rabago; Roberto
Attorney, Agent or Firm: Cantor Colburn LLP
Claims
1. A multinuclear half metallocene compound for preparing styrene polymer, represented
by one of the following formulas:
##STR5##
wherein,
M
1, M
2, M
3 and M
4 are, independently
or simultaneously in the same formula, transition atoms of groups 3 to 10 on the
periodic table;
Cp
1, Cp
2, Cp
3 and Cp
4 are, independently
or simultaneously in the same formula, a cycloalkandienyl ligand represented by
one of the following formulas:
##STR6##
wherein, r
1, r
2, r
3, r
4, r
5,
r
6, r
7, r
8, r
9, r
10, r
11,
r
12 and r
13 are, independently or simultaneously in the same
formula, hydrogen atom, halogen, C1-20 alkyl, cycloalkyl, alkenyl, alkylsilyl,
haloalkyl, alkoxy, alkylsiloxy, amino, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl,
aminoalkyl, alkylphosphinoalkyl, C6-40 aryl, arylalkyl, alkylaryl, arylsilyl, arylalkylsilyl,
haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy,
arylsiloxalkyl, arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or arylphosphinoalkyl
group; and
each of m and n is an integer of 1 or more;
X
a, X
b, X
c, X
d, X
e, X
f,
X
g, X
h and X
i, which are σ-ligand functional
groups, are independently or simultaneously in the same formula, hydrogen atom,
halogen, hydroxy, C1-20 alkyl, cycloalkyl, alkylsilyl, alkenyl, alkoxy, alkenyloxy
thioalkoxy, alkylsiloxy, amide, alkoxyalcohol, alcoholamine, carboxyl, sulfonyl,
C6-40 aryl, alkylaryl, arylalkyl, arylsilyl, haloaryl, aryloxy, arylalkoxy, thioaryloxy,
arylsiloxy, arylalkylsiloxy, arylamide, arylalkylamide, aryloxoalcohol, alcohoarylamine,
or arylaminoaryloxy group;
R
1, R
2, R
3 and R
4, which are bridging
groups connecting the transition metal M
1, M
2, M
3 or
M
4 with the cycloalkandienyl ligand Cp
1, Cp
2,
Cp
3 or Cp
4, are independently or simultaneously in the same
formula, C1-20 alkyl, cycloalkyl, alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy,
amino, dialkylether, dialkylthioether, alkylsiloxyalkyl, alkylaminoalkyl, alkylphosphinoalkyl,
C6-40 aryl, arylalkyl, alkylaryl, arylsilyl, arylalkylsilyl, haloaryl, aryloxy,
aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxoalkyl,
arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or arylphosphinoalkyl
group;
Z is a carbon, silicon or germanium;
Q is a nitrogen, phosphorous, C-r
14, Si-r
15 or Ge-r
16;
Y
1, Y
2 and Y
3, which are σ-ligand functional
groups, are independently or simultaneously in the same formula, oxygen, sulfur,
carboxylic group, sulfonyl group, N-r
17 or P-r
18; wherein,
in the C-r
14, Si-r
15, Ge-r
16, N-r
17 and
P-r
18, each of r
14, r
15, r
16, r
17
and r
18 is selected from a group consisting of hydrogen, halogen,
C1-20 alkyl, cycloalkyl,1 alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy,
amino, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl, aminoalkyl, alkylphosphinoalkyl,
aryl, arylalkyl, alkylaryl, arylsilyl, arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl,
thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxoalkyl, arylsiloxoaryl
arylamino, arylaminoalkyl, arylaminoaryl and arylphosphinoalkyl group; and
p is an integer of 1 to 3, q is an integer of 0 to 2, and p+q=3.
2. A process for preparing styrene polymer comprising polymerizing styrene monomers
in the presence of a catalyst system, wherein the catalyst system comprises:
a cocatalyst selected from a group consisting of
alkylaluminoxane;
a mixture of alkylaluminoxane and alkylaluminum; and
a mixture of weak coordinate Lewis acid and alkylaluminum; and
a multinuclear half metallocene compound catalyst represented by one of the following
formulas:
##STR7##
wherein,
M
1, M
2, M
3 and M
4 are, independently
or simultaneously in the same formula, transition atoms of groups 3 to 10 on the
periodic table;
Cp
1, Cp
2, Cp
3 and Cp
4 are, independently
or simultaneously in the same formula, cycloalkandienyl ligand represented by one
of the following formulas:
##STR8##
wherein, r
1, r
2, r
3, r
4, r
5,
r
6, r
7, r
8r
9, r
10, r
11,
r
12 and r
13 are, independently or simultaneously in the same
formula, hydrogen atom, halogen, C1-20 alkyl, cycloalkyl, alkenyl, alkylsilyl,
haloalkyl, alkoxy, alkylsiloxy, amino, alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl,
aminoalkyl, alkylphosphinoalkyl, C6-40 aryl, arylalkyl, alkylaryl, arylsilyl, arylalkylsilyl,
haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy,
arylsiloxalkyl, arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or arylphosphinoalkyl
group; and
each of m and n is an integer of 1 or more;
X
a, X
b, X
c, X
d, X
e, X
f,
X
g, X
h and X
i, which are σ-ligand functional
groups, are independently or simultaneously in the same formula, hydrogen atom,
halogen, hydroxy, C1-20 alkyl, cycloalkyl, alkylsilyl, alkenyl, alkoxy, alkenyloxy,
thioalkoxy, alkylsiloxy, amide, alkoxyalcohol, alcoholamine, carboxyl, sulfonyl,
C6-40 aryl, alkylaryl, arylalkyl, arylsilyl, haloaryl, aryloxy, arylalkoxy, thioaryloxy,
arylsiloxy, arylalkylsiloxy, arylamide, arylalkylamide, aryloxoalcohol, alcohoarylamine,
or arylaminoaryloxy group;
R
1, R
2, R
3 and R
4, which are bridging
groups connecting the transition metal M
1, M
2, M
3 or
M
4 with the cycloalkandienyl ligand Cp
1, Cp
2,
Cp
3 or Cp
4, are independently or simultaneously in the same
formula, C1-20 alkyl, cycloalkyl, alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy,
amino, dialkylether, dialkylthioether, alkylsiloxyalkyl, alkylaminoalkyl, alkylphosphinoalkyl
C6-40 aryl, arylalkyl, alkylaryl, arylsilyl, arylalkylsilyl, haloaryl, aryloxy,
aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxoalkyl,
arylsiloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or arylphosphinoalkyl
group;
Z is carbon, silicon or germanium;
Q is nitrogen, phosphorous, C-r
14, Si-r
15 or Ge-r
16;
Y
1, Y
2 and Y
3, which are σ-ligand functional
groups, are independently or simultaneously in the same formula, oxygen, sulfur,
carboxylic group, sulfonyl group, N-r
17, or P-r
18; wherein,
in the C-r
14, Si-r
15, Ge-r
16, N-r
17
and P-r
18, each of r
14, r
15, r
16, r
17
and r
18 is selected from a group consisting of hydrogen, halogen,
C1-20 alkyl, cycloalkyl, alkenyl, alkylsilyl, haloalkyl, alkoxy, alkylsiloxy, amino,
alkoxyalkyl, thioalkoxyalkyl, alkylsiloxyalkyl, aminoalkyl, alkylphosphinoalkyl,
aryl, arylalkyl, alkylaryl, arylsilyl, arylalkylsilyl, haloaryl, aryloxy, aryloxoalkyl,
thioaryloxoalkyl, aryloxoaryl, arylsiloxy, arylalkylsiloxy, arylsiloxoalkyl, arylsiloxoaryl,
arylamino, arylaminoalkyl, arylaminoaryl and arylphosphinoalkyl group; and
p is an integer of 1 to 3, q is an integer of 0 to 2, and p+q=3.
3. The process for preparing styrene polymer according to claim 2, wherein the
styrene monomers are styrene, styrene derivatives, a mixture of styrene and its
derivatives, a mixture of styrene and olefin, or a mixture of styrene derivatives
and olefin.
4. The process for preparing styrene polymer according to claim 2, wherein the
polymerization product is styrene homopolymer, styrene derivative homopolymer,
copolymer of styrene and its derivative, copolymer of styrene and olefin, or copolymer
of styrene derivative and olefin.
Description
BACKGROUND OF THE INVENTION
(a) Field of the Invention
The present invention relates to a catalyst for preparing vinyl aromatic polymer
and polymerization process of styrene using the same, and particularly to a transition
metal half metallocene catalyst with a novel structure for preparing syndiotactic
styrene polymer having high activity, superior stereoregularity, high melting point
and various molecular weight distributions and a process for preparing polymer
using the same.
(b) Description of the Related Art
Styrene polymer is largely classified into three kinds of polymers of atactic,
isotactic and syndiotactic polystyrene according to arrangement of benzene ring
attached to a polymer main chain.
Amorphous atactic polystyrene is a thermoplastic polymer obtained by general
radical or ion polymerization. It is prepared by various processing methods such
as injection molding, extrusion molding or vacuum forming, etc. and is used for
packaging material, housing material for daily commodities, toy, electrical and
electronic products, etc. Isotactic polystyrene having stereoregularity is mainly
obtained using heterogeneous Ziegler-Natta catalyst but it is not widely used due
to low productivity and low crystallization speed.
Meanwhile, syndiotactic polystyrene is used for engineering plastics more
than general-purpose resin because it has properties of crystalline polymer due
to high stereoregularity, i.e., heat resistance and chemical resistance, and good
mechanical properties such as high crystallization speed while maintaining processing
forming property and electrical property of general amorphous polystyrene. Therefore,
syndiotactic polystyrene is suitable for material for electronic parts or automobile
engine parts, and is used for parts of cellular phone or microwave oven using high
frequency property.
Such syndiotactic polystyrene can be generally prepared using a 4 group transition
metal compound metallocene catalyst with π-ligand and σ-ligand. As
the π-ligand, cyclopentadienyl, indenyl, fluorenyl group or derivatives thereof
can be used, and as the σ-ligand, alkyl, aryl, alkyl, alkoxy, aryloxy, thioalkoxy,
thioaryloxy, amino, amido, carboxyl, alkyl sillyl group, halogen, etc. can be used.
EP 210,615 has disclosed a method for synthesizing syndiotactic polystyrene with
high yield by combining metallocene catalyst with the above structure as a main
catalyst with alkylaluminoxane as a cocatalyst. More particularly, main catalyst
such as cyclopentadienyltitanium trichloride or pentamethylcyclopentadienyltitanium
trichloride is activated with methylaluminoxane cocatalyst and used for polymerization
of syndiotactic polystyrene with superior stereoregularity.
Japanese Laid-Open Patent Publication No. Hei 4-314,790 has described that
when chloro group, coligand of a metallocene catalyst with the above-mentioned
structure, is substituted with alkoxy group, specifically when pentamethylcyclopentadienyltitanium
trimethoxide main catalyst and methylaluminoxane cocatalyst are used, syndiotactic
polystyrene can be obtained with much higher yield.
Canadian Laid-Open Patent Publication No. CA 2,026,552 has disclosed a method
for preparing syndiotactic polystyrene having broad molecular weight distribution
by using two or more kinds of the metallocene catalysts together in polymerization.
It is to diversify narrow molecular weight distribution obtained when only one
kind of a catalyst exists. However, in such a case, since introduced catalysts
independently participate in polymerization, produced polystyrenes are also independent
each other and thus they are difficult to be uniformly mixed in molecular unit.
U.S. Pat. No. 6,010,972 has disclosed preparation of di-nuclear half metallocene
catalyst in which two cycloalkandienyl groups are connected to both nuclei through
alkylene or sillylene bridge and styrene polymerization using the same. The result
of styrene polymerization showed high polymerization activity, superior stereoregularity
and narrow molecular weight distribution similarly to mononuclear metallocene,
indicating that even if two or more metal centers exist in one molecule, they do
not hinder a polymerization. However, since both cycloalkandienyl groups are the
same due to the used preparation process of main ligand, it is not effective for
providing various polystyrenes, one of advantages of multinuclear metallocene catalyst,
as can be seen from narrow molecular weight distribution.
EP 964,004 has disclosed preparation of multinuclear metallocene catalyst in
which
two or more half metallocenes are connected through coligand bridge having dialkoxy
group or diaryloxy group and styrene polymerization using the same. The results
of styrene polymerization also showed high polymerization activity, superior stereoregularity
and narrow molecular weight distribution. However, since the used coligand has
symmetric structure and acts as a leaving group when polymerization, produced polystyrenes
show little difference from those produced using mononuclear metallocene catalyst.
SUMMARY OF THE INVENTION
The present invention is made in consideration of the problems of the prior art,
and it is an object of the present invention to provide a novel multinuclear metallocene
catalyst capable of preparing syndiotactic polystyrene having high stereoregularity
and various molecular weight distributions with high activity, and homopolymerization
of styrene and copolymerization of styrene and olefin using the same.
It is another object of the present invention to provide a multinuclear half
metallocene
catalyst comprising at least two transition metal compounds of Group 3 to 10 in
periodic table and having cycloalkandienyl group.
It is another object of the present invention to provide a process for preparing
a multinuclear half metallocene catalyst using a bridge ligand simultaneously comprising
π-ligand cycloalkandienyl group and σ-ligand functional group.
It is another object of the present invention to provide a process for preparing
syndiotactic polystyrene having superior stereoregularity, high melting temperature
and various molecular weight distributions, and styrene polymers such as copolymer
with olefin in high yield using the metallocene catalyst.
In order to achieve these objects, the present invention provides a multinuclear
half metallocene catalyst represented by the following Chemical Formula 1, 2 or
3:
##STR1##
In the Chemical Formulae 1, 2 and 3,
M
1, M
2, M
3 and M
4 are,
independently or simultaneously in the same formula, transition atoms of group
3 to 10 in periodic table;
Cp
1, Cp
2, Cp
3 and Cp
4 are,
independently or simultaneously in the same formula, cycloalkandienyl ligand represented
by the following Chemical Formula 4, 5, 6, 7 or 8:
##STR2##
(In the Chemical Formulae 4, 5, 6, 7 and 8,
r
1, r
2, r
3, r
4, r
5,
r
6, r
7, r
8, r
9, r
10, r
11,
r
12 and r
13 are, independently or simultaneously in the same
formula, a hydrogen atom, halogen, C1-20 alkyl, cycloalkyl, alkenyl, alkylsillyl,
haloalkyl, alkoxy, alkylsiloxy, amino, alkoxyalkyl, thioalkoxyalkyl, alkylsilloxyalkyl,
aminoalkyl, alkylphosphinoalkyl, C6-40 aryl, arylalkyl, alkylaryl, arylsillyl,
arylalkylsillyl, haloaryl, aryloxy, aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl,
arylsilloxy, arylalkylsilloxy, arylsilloxoalkyl, arylsilloxoaryl, arylamino, arylaminoalkyl,
arylaminoaryl or arylphosphinoalkyl group, and each of m and n is an integer of
1 or more);
X
a, X
b, X
c, X
d, X
e,
X
f, X
g, X
h and X
i are σ-ligand
functional groups, and independently or simultaneously in the same formula, a hydrogen
atom halogen, hydroxy, C1-20 alkyl, cycloalkyl, alkylsillyl, alkenyl, alkoxy, alkenyloxy,
thioalkoxy, alkylsilloxy, amide, alkoxyalcohol, alcoholamine, carboxyl, sulfonyl,
C6-40 aryl, alkylaryl, arylalkyl, arylsillyl, haloaryl, aryloxy, arylalkoxy, thioaryloxy,
arylsilloxy, arylalkylsilloxy, arylamide, arylalkylamide, aryloxoalcohol, alcoholarylamine
or aryl aminoaryloxy group;
R
1, R
2, R
3 and R
4 are
bridges connecting the transition metal M
1, M
2, M
3 or
M
4 with the cycloalkandienyl ligand Cp
1, Cp
2,
Cp
3 or Cp
4, and independently or simultaneously in the same
formula, C1-20 alkyl, cycloalkyl, alkenyl, alkylsillyl, haloalkyl, alkoxy, alkylsilloxy,
amino, dialkylether, dialkylthioether, alkylsilloxyalkyl, alkylaminoalkyl, alkylphosphinoalkyl,
C6-40 aryl, arylalkyl, alkylaryl, arylsillyl, arylalkylsillyl, haloaryl, aryloxy,
aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl, arylsilloxy, arylalkylsilloxy, arylsilloxoalkyl,
arylsilloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl or arylphosphinoalkyl group;
Z is a carbon, silicon or germanium,
Q is a nitrogen, phosphorous, C-r
14, Si-r
15 or Ge-r
16,
Y
1, Y
2 and Y
3 are σ-ligand
functional groups, and independently or simultaneously in the same formula, oxygen,
sulfur, carboxyl, sulfonyl group, N-r
17 or P-r
18;
In the C-r
14, Si-r
15, Ge-r
16, N-r
17
and P-r
18, each of r
14, r
15, r
16, r
17
and r
18 is selected from a group consisting of hydrogen, halogen,
C1-20 alkyl, cycloalkyl, alkenyl, alkylsillyl, haloalkyl, alkoxy, alkylsilloxy,
amino, alkoxyalkyl, thioalkoxyalkyl, alkylsilloxyalkyl, aminoalkyl, alkylphosphinoalkyl,
aryl, arylalkyl, alkylaryl, arylsillyl, arylalkylsillyl, haloaryl, aryloxy, aryloxoalkyl,
thioaryloxoalkyl, aryloxoaryl, arylsilloxy, arylalkylsilloxy, arylsilloxoalkyl,
arylsilloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl and arylphosphinoalkyl;
p is an integer of 1 to 3, and q is an integer of 0 to 2, and p+q=3.
The present invention also provides a process for preparing styrene polymer comprising
the step of polymerizing styrene monomers in the presence of a catalyst system comprising
a) a multinuclear half metallocene compound catalyst represented by the above
Chemical Formula 1, 2 or 3, and
b) a cocatalyst selected from a group consisting of
i) alkylaluminoxane;
ii) a mixture of alkylaluminoxane and alkylaluminum; and
iii) a mixture of week coordinate Lewis acid and alkylaluminum.
DETAILED DESCRIPTION AND THE PREFERRED EMBODIMENTS
The present invention will now be explained in detail.
The present invention provides a multinuclear half metallocene catalyst satisfying
the above Chemical Formula 1, 2 or 3 as a main catalyst used for preparing styrene
polymer and preparation thereof, and a process for preparing styrene polymer using
the catalyst as a main catalyst.
The metallocene catalyst of the present invention satisfying the above Chemical
Formula 1, 2 or 3 is a multinuclear half metallocene compound in which two or more
transition metals of group 3 to 10 in periodic table are connected through a bridge
simultaneously containing cycloalkandienyl group and one or more functional groups.
Therefore, each metal center makes different cationic polymerization active kinds
and thus polymers with various molecular weights are uniformly mixed in molecular
unit, making molecular weight control of polymers easy, as well as providing styrene
polymer having high polymerization activity, superior stereoregularity and high
melting temperature, which is advantages of the existing mononuclear metallocene.
Therefore, difficulty in processibility of polymer due to narrow molecular weight
distribution, which is a disadvantage of the metallocene catalyst, can be overcome
and polymers with various physical properties can be provided.
The multinuclear half metallocene catalyst can be prepared by reacting a ligand
simultaneously containing cycloalkandienyl group and at least one functional groups
with a half metallocene compound having a leaving group to introduce functional
group of the ligand into a transition metal, and i) converting the cycloalkandienyl
group into an alkali metal salt thereof and reacting it with another transition
metal compound having a leaving group, or ii) introducing alkylsillyl group or
alkyl tin group into the cycloalkandienyl group and reacting it with a transition
metal compound.
In addition, the ligand simultaneously containing cycloalkandienyl group and
at
least one functional groups can be prepared by i) reacting an alkali metal salt
of a cycloalkandienyl group with an organic compound simultaneously containing
a leaving group and a functional group, or ii) reacting an alkali metal salt of
an organic compound containing a functional group with a ketone compound having
cycloalkandienyl backbone.
The alkali metal salt of cycloalkandienyl group includes cyclopentadienyl lithium,
cyclopentadienyl sodium, cyclopentadienyl potassium, cyclopentadienyl magnesium,
methylcyclopentadienyl lithium, methylcyclopentadienyl sodium, methylcyclopentadienyl
potassium, tetramethylcyclopentadienyl lithium, tetramethylcyclopentadienyl sodium,
tetramethylcyclopentadienyl potassium, indenyl lithium, indenyl sodium, indenyl
potassium, fluorenyl lithium, etc. These salts can be prepared by reacting a ligand
having a cycloalkandienyl structure with n-butyllithium, s-butyllithium, t-butyllithium,
methyllithium, sodium methoxide, sodium ethoxide, potassium t-butoxide, potassium
hydroxide, methylmagnesium chloride, ethylmagnesium bromide, dimethylmagnesium,
lithium, sodium, potassium, etc.
In addition, the organic compound simultaneously containing a leaving group and
a functional group includes 2-bromo-1-ethanol, 4-bromo-1-butanol, 5-bromo-1-pentanol,
6-bromo-1-hexanol, 9-bromo-1-nonanol, 10-bromo-1-decanol, 4-hydroxybenzylbromide,
(2-bromoethyl)-methyl-N-ethanolamine, (2-bromoethyl)-N,N-diethanolamine 4-bromophenol,
4-bromo-2,6-dimethylphenol, 4-(4-bromophenyl)phenol, 4-bromobenzylalcohol, 4-bromoaniline,
4-bromobenzylamine, 4-bromobutyric acid, 6-bromohexyl, 4-bromo benzoic acid, etc.
The ketone compound capable of having cycloalkandienyl backbone includes 2-cyclopentene-1-one,
3-methyl-2-cyclopentene-1-one, 3,4-dimethyl2-cyclopenten-1-one, 2,3,4-trimethyl-2-cyclopenten-1-one,
2,3,4,5-tetramethyl-2-cyclopenten-1-one, 3-ethyl-2-cyclopenten-1-one, 3-t-butyl-2-cyclopenten-1-one,
3,4-diphenyl-2-cyclopenten-1-one, 1-indanone, 2-indanone, 4,5,6,7-tetrahydro-1-indanone,
4,5,6,7-tetrahydro-2-indanone, etc.
The half metallocene compound having a leaving group includes cyclopentadienyltitanium
trichloride, cyclopentadienylmethoxytitanium dichloride, cyclopentadienylmethoxytitanium
monochloride, cyclopentadienyltitanium trimethoxide, methylcyclopentadienyltitanium
trichloride, methylcyclopentadienylmethoxytitaium dichloride, methylcyclopentadienylmethoxytitaium
monochloride, methylcyclopentadienyltitanium trimethoxide, pentamethylcyclopentadienyltitanium
trichloride, pentamethylcyclopentadienylmethoxytitanium dichloride, pentamethylcyclopentadienylmethoxytitanium
monochloride, pentamethylcyclopentadienyltitanium trimethoxide, indenyltitanium
trichloride, indenylmethoxytitanium dichloride, indenyldimethoxytitanium monochloride,
indenyltitanium dichloride, indenyldimethoxytitanium monochloride, indenyltitanium
trimethoxide, etc.
The transition metal compound having a leaving group includes titanium tetrachloride,
titanium tetrachloride ditetrahydrofuran, zirconium tetrachloride, hafnium tetrachloride,
vanadium tetrachloride, titanium tetraiodide titanium tetrabromide, titanium tetrafluoride,
vanadium chloride oxide, titanium tetraisopropoxide, chlorotitanium triisopropoxide,
dichlorotitanium diisoproxide, trichlorotitanium monoisopropoxide, chlorotitanium
triphenoxide, chlorotitanium tributoxide, chlorotitanium triethoxide, etc.
The alkylsillyl group or alkyl tin group that can be substituted for the cycloalkandienyl
group includes trimethylsillyl, triethylsillyl, butyldimethylsillyl, phenyldimethylsillyl,
trimethyl tin, triethyl tin, tributyl tin, etc.
In the multinuclear half metallocene catalyst for preparing styrene polymer,
represented
by the above Chemical Formula 1, 2 or 3, prepared by the above process, n and m
preferably satisfy 1≦n or m≦10.
And, M
1 to M
4 are preferably group 4 transition metal
on periodic table, and more preferably titanium, zirconium or hafnium.
And, the ligand having cycloalkandienyl backbone includes cyclopentadienyl group,
indenyl group, fluorenyl group, 4,5,6,7-tetrahydroindenyl group, 2,3,4,5,6,7,8,9-octahydrofluorenyl
group, etc.
The C1-20 alkyl, cycloalkyl, alkenyl, alkylsillyl, haloalkyl, alkoxy, alkylsilloxy,
amino, alkoxyalkyl, thioalkoxyalkyl, alkylsilloxyalkyl, aminoalkyl, alkylphosphinoalkyl
group include methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopropyl, cyclobutyl,
cyclopentyl, cyclohexyl, allyl, 2-butenyl, 2-pentenyl, methylsillyl, dimethylsillyl,
trimethylsillyl, ethylsillyl, dietylsillyl, triethylsillyl, propylsillyl, dipropylsillyl,
tripropylsillyl, butylsillyl, di-butylsillyl, tri-butylsillyl, butyldimethylsillyl,
trifluoromethyl, methoxy, ethoxy, propoxy, butoxy, pentoxy, hexyloxy, methylsilloxy,
dimethylsilloxy, trimethylsilloxy, ethylsilloxy, dietylsilloxy, triethylsilloxy,
butyldimethylsilloxy, dimethylamino, diethylamino, dipropylamino, dibutylamino,
pyrrolidine, piperidine, methoxyethyl, methoxypropyl, methoxybutyl, thiomethoxyethyl,
thiomethoxybutyl, trimethylsilloxyethyl, dimethylaminoethyl, diethylphosphinobutyl
group, etc.
And, the C6-40 aryl, arylalkyl, alkylaryl, arylsillyl, arylalkylsillyl, haloaryl,
aryloxy, aryloxoalkyl, thioaryloxoalkyl, aryloxoaryl, arylsilloxy, arylalkylsilloxy,
arylsilloxoalkyl, arylsilloxoaryl, arylamino, arylaminoalkyl, arylaminoaryl, arylphosphinoalkyl
group include phenyl, biphenyl, terphenyl, naphtyl, fluorenyl, benzyl, phenylethyl,
phenylpropyl, tollyl, xylyl, butylphenyl, phenylsillyl, phenyldimethylsillyl, diphenylmethylsillyl,
triphenylsillyl, chlorophenyl, pentafluorophenyl, phenoxy, naphthoxy, phenoxyethyl,
biphenoxybutyl, thiophenoxyethyl, phenoxyphenyl, naphthoxyphenyl, phenylsilloxy,
triphenylsillyl phenyldimethylsilloxy, triphenylsilloxethyl, diphenylsilloxphenyl,
aniline, toluidine, benzylamino, phenylaminoethyl, phenylmethylaminophenyl, diethylphosphinobutyl, etc.
Syndiotactic styrene polymer and styrene copolymer with various physical
properties can be obtained using the multinuclear half metallocene catalyst for
preparing styrene polymers represented by the above Chemical Formula 1, 2 or 3
as a main catalyst together with a cocatalyst in a styrene homopolymerization or
copolymerization with olefin.
The cocatalyst used together with the multinuclear half metallocene catalyst
includes alkylaluminoxane of the following Chemical Formula 9 and week coordinate
Lewis acid, and they are used together with alkylaluminum of the Chemical Formula
10.
##STR3##
In the Chemical Formula 9,
R
5 is hydrogen, substituted or unsubstituted C1-20 alkyl,
substituted or unsubstituted C3-20 cycloalkyl, C6-40 aryl, alkylaryl or arylalkyl
group, and
n is an integer of 1 to 100.
##STR4##
In the Chemical Formula 10,
R
6, R
7 and R
8 are independently or
simultaneously hydrogen, halogen, substituted or unsubstituted C1-20 alkyl, substituted
or unsubstituted C3-20 cycloalkyl, C6-40 aryl, alkylaryl or arylalkyl group; and
at least one of the R
6, R
7 and R
8 contain an alkyl group.
The compound of the above Chemical Formula 9 may be linear, circular or network
structure, and specifically, the examples include methylaluminoxane, modified methylaluminoxane,
ethylaluminoxane, butylaluminoxane, hexylaluminoxane, decylaluminoxane, etc.
The compound of the above Chemical Formula 10 includes trimethylaluminum, dimethylaluminum
chloride, dimethylaluminum methoxide, methylaluminum dichloride, triethylaluminum,
diethylaluminum chloride, diethylaluminum methoxide, ethylaluminum dichloride,
tri-n-propylaluminum, di-n-propylaluminum chloride, n-propylaluminum chloride,
triisopropylaluminum, tri-n-butylaluminum, tri-isobutylaluminum, di-isobutylaluminum
hydride, etc.
And the weak coordinate Lewis acid cocatalyst may be ionic or neutral type, and
specifically, the examples include trimethylammonium, tetraphenylborate, tributylammonium,
tetraphenylborate, trimethylammonium tetrakis(pentafluorophenyl)borate, tetramethylammonium
tetrakis(pentafluorophenyl)borate, N,N-dimethylanilinium tetraphenylborate, dimethylanilinium
tetrakis(pentafluorophenyl)borate, pyridinium tetraphenylborate, pyridinium tetrakis(pentafluorophenyl)borate,
silver tetrakis(pentafluorophenyl)borate, ferro-cerium tetrakis(pentafluoropehnyl)borate,
triphenylcarbenium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate, sodium tetrakis(3,5-bis(trifluoromethyl)phenyl)borate,
tris(pentafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,5-bis(trifluoromethyl)phenyl)borane,
tris(2,4,6-trifluorophenyl)borane, etc.
In styrene polymerization or copolymerization with olefin using the metallocene
catalyst, the amount of the cocatalyst used together is not specifically limited
but may differ according to the kinds.
The mole ratio of alkylaluminoxane and metallocene catalyst is 1:1 to 10
6:1,
and preferably 10:1 to 10
4:1. And, the mole ratio of alkylaluminum that
can be used together with alkylaluminoxane and metallocene catalyst is 1:1 to 10
4:1.
The mole ratio of week coordinate Lewis acid and metallocene catalyst is 0.1:1
to 50:1, and the mole ratio of alkylaluminum and metallocene catalyst is 1:1 to
3000:1, and preferably 50:1 to 1000:1.
Monomers that can be polymerized with the catalyst system of the present
invention include styrene or its derivatives or olefin, and styrene or its derivatives
can be homopolymerized, or styrene and its derivatives can be copolymerized, or
styrene or its derivatives can be copolymerized with olefin.
Styrene derivatives have substituents on a benzene ring, and the substituents
include halogen, C1-10 alkyl, alkoxy, ester, thioalkoxy, sillyl, tin, amine, phosphine,
halogenated alkyl, C2-20 vinyl, aryl, vinylaryl, alkylaryl, aryl alkyl group, etc.
Examples include chlorostyrene, bromostyrene, fluorostyrene, p-methylstyrene, m-methylstyrene,
ethylstyrene, n-butylstyrene, p-t-butylstyrene, dimethylstyrene, methoxystyrene,
ethoxystyrene, butoxystyrene, methyl-4-styrenylester, thiomethoxystyrene, trimethylsillylstyrene,
triethylsillylstyrene, t-butyldimethylsillylstyrene, trimethyltin styrene, dimethylaminostyrene,
trimethylphosphinostyrene, chloromethylstyrene, bromomethylstyrene, 4-vinylbiphenyl,
p-divinylbenzene, m-divinylbenzene, trivinylbenzene, 4,4′-divinylbiphenyl,
vinylnaphthalene, etc.
And, the olefins that can be used in copolymerization include C2-20 olefin,
C3-20 cycloolefin or cyclodiolefin, C4-20 diolefin, etc., and examples include
ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1decene, cyclopentene,
cyclohexene, cyclopentadiene, cyclohexadiene, norbonene, methyl-2-norbonene, 1,3-butadiene,
1,4-pentadiene, 2-methyl-1,3-butadiene, 1,5-hexadiene, etc.
Polymerization using the catalyst system of the present invention
can be conducted in a slurry phase, liquid phase, gas phase or massive phase. When
a polymerization is conducted in a slurry phase or liquid phase, solvent can be
used as a polymerization medium, and the used solvents include C4-20 alkane or
cycloalkane solvent such as butane, pentane, hexane, heptane, octane, decane, dodecane,
cyclopentane, methylcyclopentane, cyclohexane, etc.; C6-20 aromatic arene solvent
such as benzene, toluene, xylene, mesitylene, etc.; and C1-20 halogen alkane or
halogen arene solvent such as dichloromethane, chloromethane, chloroform, carbon
tetrachloride, chloroethane, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, chlorobenzene,
1,2-dichlorobenzene, 1,2,4-trichlorobenzene, etc.
Polymerization temperature is -80 to 200° C., and preferably
0 to 150° C., and polymerization pressure is suitably 1 to 1000 atm including
the pressure of comonomers for styrene homopolymerization or copolymerization with olefin.
According to the present invention, polymer can be prepared by i) introducing
a solvent and monomers or monomers only into a reactor and elevating a temperature,
and then introducing alkylaluminum, cocatalyst and main catalyst metallocene compound
in this order, or ii) activating a main catalyst with alkylaluminum and cocatalyst,
and then introducing it into a reactor containing monomers, or iii) previously
adding alkylaluminum to monomers, and then introducing a main catalyst activated
with a cocatalyst. And, the activation by contacting a main catalyst with a cocatalyst
is preferably conducted at 0 to 150° C. for 1 to 60 minutes.
The amount of the main catalyst metallocene compound is not specifically limited,
but is suitably 10
-8 to 1.0 M on the basis of concentration of central
metal in reaction system, and ideally 10
-7 to 10
-2 M.
Syndiotactic styrene polymers and copolymers obtained by polymerization
using the catalyst system can be controlled in a molecular weight range of 1000
to 10,000,000 and in a molecular weight distribution range of 1.1 to 100 by controlling
the kinds and the amounts of a main catalyst and cocatalyst, reaction temperature,
reaction pressure and concentration of monomers.
The present invention will be explained in more detailed with reference to the
following Examples. However, these are to illustrate the present invention and
the present invention is not limited to them.
EXAMPLE
Example 1
Synthesis of (O
iPr)
3Ti[Cp(CH
2)
6O]TiCp*(OMe)
2
(Preparation of (C
5H
4)(CH
2)
6OH)
To a 250 ml Schlenk flask containing 1.81 g (10 mmol) of Br(CH
2)
6OH,
30 ml of tetrahydrofuran (THF) were added to dissolve, and temperature of a reaction
vessel was lowered to -78° C. using dry ice/acetone mixed refrigerant. Then,
1.2 equivalents of NaCp in THF solution were slowly injected using a syringe. After
agitating reaction solution at this temperature for 30 minutes, temperature was
slowly elevated to maintain a room temperature. The reaction solution was agitated
overnight to obtain a light purple solution.
To the reaction mixture, 30 ml of NH
4Cl saturated aqueous solution
were poured to terminate a reaction, and then organic solution was extracted twice
with 50 ml of diethyl ether. Obtained organic solution was treated with anhydrous
magnesium sulfate (MgSO
4) to remove moisture, and solution was filtered
and then solvent was removed in a rotary evaporator. The solution was dried under
vacuum to obtain 1.41 g of (C
5H
4)(CH
2)
6OH
(yield 85%).
(Preparation of (C
5H
4)(CH
2)6OTiCp*(OMe)
2)
0.831 g (5 mmol) of the obtained (C
5H
4)(CH
2)
6OH
were dissolved in 30 ml of methylene chloride (CH
2Cl
2), and
1.1 equivalent of triethylamine (0.767 ml) were added thereto. Then, temperature
of a reaction vessel was lowered to -78° C., and the same equivalent of Cp*Ti(OMe)
2Cl
(1.40 g) methylene chloride solution dissolved in another flask were slowly dropped
thereto with a cannula. White precipitates were immediately observed.
After elevating a temperature of the reaction mixture to a room temperature,
the reaction mixture was agitated overnight to obtain yellow reaction solution.
After removing solvent under reduced pressure, obtained orange-yellow products
were extracted with 30 ml of n-hexane. The products were filtered through celite
545 filter, and triethylamine hydrogen chloride salt and solvent were separated
to obtain clear yellow solution. Solvent was removed again from the solution under
vacuum, and the solution was dried for a long time to obtain 1.64 g of orange-yellow
products (C
5H
4)(CH
2)
6OTiCp*(OMe)
2
(yield 80%).
(Preparation of (O
iPr)
3Ti[Cp(CH
2)
6O]TiCp*(OMe)
2 catalyst)
After dissolving 0.821 g (2 mmol) of (C
5H
4)(CH
2)
6OTiCp*(OMe)
2
synthesized above in 30 ml of diethyl ether, temperature of a reaction vessel was
lowered to -78° C. The same equivalents of n-butyllithium in hexane solution
were slowly injected with a syringe. Temperature of the reaction vessel was slowly
elevated to a room temperature to confirm that light yellow precipitates were produced.
After agitating it overnight, temperature of the reaction vessel was lowered again
to -78° C., and the same equivalents of ClTi(O
iPr)
3 (0.521
g) diethylether solution dissolved in another flask were slowly dropped thereto
with a cannula. After removing refrigerating vessel, temperature of a reaction
mixture was slowly elevated to maintain a room temperature. At this temperature,
the reaction mixture was reacted for one day.
Solvents were completely removed from the reactant, and the reactant was
extracted again with 20 ml of n-hexane. It is filtered through celite 545 filter
and LiCl and solution were separated to obtain clear light green solution. Solvent
was removed from the solution under vacuum and the solution was dried for a long
time to obtain 0.888 g of (O
iPr)
3Ti[Cp(CH
2)
6O]TiCp*(OMe)
2
(yield 80%).
Example 2
Synthesis of (O
iPr)
3Ti[Cp(CH
2)
9O]TiCp*(OMe)
2 catalyst
(O
iPr)
3Ti[Cp(CH
2)
9O]TiCp*(OMe)
2
catalyst was prepared by the same method as in Example 1, except that Br(CH
2)
9OH
was used instead of Br(CH
2)
6OH.
Example 3
Synthesis of (O
iPr)
3Ti[Cp(CH
2)
12O]TiCp*(OMe)
2 catalyst
(OiPr)
3Ti[Cp(CH
2)
12O]TiCp*(OMe)
2
catalyst was prepared by the same method as in Example 1, except that Br(CH
2)
12OH
was used instead of Br(CH
2)
6OH.
Example 4
Synthesis of (O
iPr)
3Ti[Cp(C
6H
4)2)]TiCp*(OMe)
2 catalyst
(Preparation of (C
5H
4)(C
6H
4)
2OH)
To a 250 ml schlenk flask containing 2.49 g (10 mmol) of 4-Br(C
6H
4)
2OH,
30 ml of diethyl ether were added to dissolve, and temperature of a reaction vessel
was lowered to -78° C. Then, 2 equivalents of n-butyllithium in hexane solution
were slowly injected using a syringe and temperature of a reaction mixture was
slowly elevated to a room temperature. The reactant was agitated for 4 hours and
temperature of a reaction vessel was lowered to -78° C. again, and then 20
ml of 1 equivalent of 2-cyclopenten-1-one (0.821 g) THF solution previously prepared
in another flask were dropped thereto using a cannula. The reaction mixture was
agitated at this temperature for 30 minutes, and then temperature was elevated
to a room temperature and agitated overnight. To a reaction mixture, 30 ml of ammonium
chloride (NH
4Cl) saturated aqueous solution were poured to terminate
a reaction, and then organic solution part was extracted twice with 50 ml of diethyl ether.
Solvents were completely removed from the obtained organic solution using
a rotary evaporator, and obtained oily compound was dissolved in 20 ml of carbon
dichloride solvent. Catalytic amount (0.1 g) of para-toluenesulfonic acid were
added in solid phase to the solution, and the solution was agitated at room temperature
for 1 hour. After washing the reaction mixture with water, organic solution parts
were extracted with 30 ml of methylene chloride to gather them, and moisture was
removed with anhydrous magnesium sulfate (MgSO
4). After filtering the
solution, solvent was removed in a rotary evaporator, and the solution was dried
under vacuum to obtain yellow solid compound.
The obtained compound was dissolved in 20 ml of n-hexane, and cooled at 20°
C. overnight to obtain 1.76 g of ivory-colored solid compound (C
5H
4)(C
6H
4)
2OH
(yield 75%).
(Preparation of (C
5H
4)C
6H
4)
2OTiCp*(OMe)
2
The obtained (C
5H
4)C
6H
4)
2OH
was reacted with the same equivalent of Cp*Ti(OMe)
2Cl by the same method
as in Example 1 to obtain orange product (C
5H
4)(C
6H
4)
2OTiCp*(OMe)
2.
(Preparation of (O
iPr)
3Ti[CP(C
6H
4)
2O]TiCp*(OMe)
2 catalyst)
The synthesized (C
5H
4)(C
6H
4)
2OTiCp*(OMe)
2
was reacted with the same equivalent of ClTi(OiPr)
3 by the same method
as in Example 1 to obtain (O
iPr)
3Ti[Cp(C
6H
4)
2O]TiCp*(OMe)
2.
Example 5
Synthesis of (O
iPr)
3Ti[(C
5Me
4)(C
6H
4)
2O]TiCp*(OMe)
2
(O
iPr)
3Ti[(C
5Me
4)(C
6H
4)
2O]TiCp*(OMe)
2
catalyst was prepared by the same method as in Example 4, except that 2,3,4,5-tetramethylcyclopent-2-enone
is used instead of 2-cyclopenten-1-one.
Example 6
Synthesis of (O
iPr)
3Ti[CpC
6H
4O]TiCp*(OMe)
2 catalyst
(O
iPr)
3Ti[CpC
6H
4O]TiCp*(OMe)
2
catalyst was prepared by the same method as in Example 4, except that 4-BrC
6H
4OH
was used instead of 4-Br(C
6H
4)
2OH.
Example 7
Synthesis of (O
iPr)
3Ti[Cp(2,6-Me
2C
6H
2)OTiCp*(OMe)
2 catalyst
(O
iPr)
3Ti[Cp(2,6-Me
2C
6H
2)OTiCp*(OMe)
2
catalyst was prepared by the same method as in Example 4, except that 4-Br(2,6-Me
2C
6H
2)OH
was used instead of 4-Br(C
6H
4)
2OH.
Example 8
Synthesis of (O
iPr)
3Ti[CpC
6H
4S]TiCp*(OMe)
2 catalyst
(O
iPr)
3Ti[CpC
6H
4S]TiCp*(OMe)
2
catalyst was prepared by the same method as in Example 4, except that 4-BrC
6H
4SH
was used instead of 4Br(C
6H
4)
2OH.
Example 9
Synthesis of (O
iPr)
3Ti[CpC
6H
4CH
2O]TiCp*(OMe)
2 catalyst
(O
iPr)
3Ti[CpC
6H
4CH
2O]TiCp*(OMe)
2
catalyst was prepared by the same method as in Example 4, except that 4-BrC
6H
4CH
2OH
was used instead of 4Br(C
6H
4)
2OH.
Example 10
Preparation of Styrene Homopolymer (Liquid Phase Polymerization)
Liquid phase styrene homopolymerization was conducted using each of the multinuclear
half metallocene catalysts synthesized in Examples 1 to 9.
To a polymerization reactor under high purity nitrogen atmosphere, 50 ml of purified
heptane was added and temperature was elevated to 50° C. 50 ml of styrene,
2.5 ml (1.0 M) of triisobutylaluminum, and 2.5 ml of methylaluminoxane (2.1 M toluene
solution, Akzo Company product) were sequentially introduced.
5 ml of toluene solution in which each of the metallocene catalysts was dissolved
were added thereto, while vigorously agitating. After agitating for 30 minutes,
10 wt % of chloric acid-ethanol solution was added to terminate a reaction, and
the reactant was filtered to obtain white solid precipitate. The precipitate was
washed with ethanol and dried in a 50° C. vacuum oven overnight to obtain
final styrene polymer. Results of polymerization and physical properties of polymers
for each catalyst are shown in Table 1.
In addition, each of the polymers was refluxed in methylethylketone for 12 hours
and extracted to obtain polymers that remain undissolved. As result of analyzing
the polymers by carbon atom nuclear magnetic resonance spectroscopy, they were
confirmed to have syndiotactic structure.
| TABLE 1 |
| Results of liquid phase styrene homopolymerization |
| |
|
Activity |
|
|
|
|
| |
|
(kgPS/ |
|
Molecular |
Molecular |
Melting |
| |
Yieild |
molTi · |
Syndiotacticity |
weight |
weight |
point |
| |
(g) |
h) |
(%) |
(×103) |
distribution |
(° C.) |
| |
| Catalyst of Example 1 |
19.2 |
1456 |
92 |
205 |
14.5 |
269 |
| (OiPr)3Ti[Cp(CH2)6O]TiCp*(OMe)2 |
| Catalyst of Example 2 |
22.0 |
1760 |
93 |
220 |
15.6 |
270 |
| (OiPr)3Ti[Cp(CH2)9O]TiCp*(OMe)2 |
| Catalyst of Example 3 |
22.5 |
1800 |
93 |
225 |
15.2 |
270 |
| (OiPr)3Ti[Cp(CH2)12O]TiCp*(OMe)2 |
| Catalyst of Example 4 |
22.7 |
1816 |
94 |
240 |
16.8 |
271 |
| (OiPr)3Ti[Cp(C6H4)2O]TiCp*(OMe)2 |
| Catalyst of Example 5 |
26.5 |
2120 |
97 |
310 |
11.5 |
272 |
| (OiPr)3Ti[(C5Me4)(C6H4)2O]TiCp*(OMe)2 |
| Catalyst of Example 6 |
20.3 |
1624 |
94 |
250 |
15.7 |
271 |
| (OiPr)3Ti[CpC6H4O]TiCp*(OMe)2 |
| Catalyst of Example 7 |
21.1 |
1688 |
95 |
274 |
15.3 |
272 |
| (OiPr)3Ti[Cp(2,6-Me2C6H2)O]TiCp*(OMe)2 |
| Catalyst of Example 8 |
14.6 |
1168 |
93 |
210 |
17.8 |
269 |
| (OiPr)3Ti[CpC6H4S]TiCp*(OMe)2 |
| Catalyst of Example 9 |
19.8 |
1584 |
94 |
238 |
16.2 |
270 |
| (OiPr)3Ti[CpC6H4CH2O]TiCp*(OMe)2 |
Example 11
Preparation of Styrene Homopolymer (Massive Phase Polymerization)
Massive phase styrene polymerization was conducted using the catalysts of
Examples 3, 4, 5 and 7 having high liquid phase polymerization activity as that
of Example 10 out of the multinuclear half metallocene catalysts synthesized in
Examples 1 to 9.
To a polymerization reactor under high purity nitrogen atmosphere, 100 ml of
purified
styrene were added and temperature was elevated to 50° C. Then, 5 ml of triisobutylaluminum
(1.0 M toluene solution) and 5 ml of methylaluminoxane (2.1 M toluene solution,
Akzo Company product) were sequentially introduced therein.
5 ml (50 μmol of Ti) of toluene solution in which the metallocene is dissolved
were added thereto while vigorously agitating. After agitating for 1 hour, 10 wt
% of chloric acid-ethanol solution was added to terminate a reaction, and the reactant
was filtered, washed with ethanol, and dried at a vacuum oven of 50° C. to
obtain a final styrene polymer.
Results of polymerization and physical properties of polymers for each catalyst
are shown in Table 2.
And, each polymer was refluxed in methylethylketone for 12 hours and extracted
to obtain polymers that remained undissolved. As results of analyzing the polymers
with carbon atom nuclear magnetic resonance spectroscopy, they were confirmed to
have syndiotactic structures.
| |
TABLE 2 |
| |
| |
|
Activity |
|
|
|
|
| |
|
(kgPS/ |
|
Molecular |
Molecular |
Melting |
| |
Yield |
molTi · |
Syndiotacticity |
weight |
weight |
point |
| |
(g) |
h) |
(%) |
(×103) |
distribution |
(° C.) |
| |
| |
