U.S. patent application number 12/458998 was filed with the patent office on 2010-02-04 for novel coordination complexes and process of producing polycarbonate by copolymerization of carbon dioxide and epoxide using the same as catalyst.
Invention is credited to Anish Cyriac, Jisu Jeong, Bun Yeoul Lee, JaeKi Min, Myungahn Ok, Sujith S., JongEon Seong.
Application Number | 20100029896 12/458998 |
Document ID | / |
Family ID | 43535873 |
Filed Date | 2010-02-04 |
United States Patent
Application |
20100029896 |
Kind Code |
A1 |
Ok; Myungahn ; et
al. |
February 4, 2010 |
Novel Coordination complexes and process of producing polycarbonate
by copolymerization of carbon dioxide and epoxide using the same as
catalyst
Abstract
Provided are a complex prepared from ammonium salt-containing
ligands and having such an equilibrium structural formula that the
metal center takes a negative charge of 2 or higher, and a method
for preparing polycarbonate via copolymerization of an epoxide
compound and carbon dioxide using the complex as a catalyst. When
the complex is used as a catalyst for copolymerizing an epoxide
compound and carbon dioxide, it shows high activity and high
selectivity and provides high-molecular weight polycarbonate, and
thus easily applicable to commercial processes. In addition, after
forming polycarbonate via carbon dioxide/epoxide copolymerization
using the complex as a catalyst, the catalyst may be separately
recovered from the copolymer.
Inventors: |
Ok; Myungahn; (Daejeon,
KR) ; Jeong; Jisu; (Daejeon, KR) ; Lee; Bun
Yeoul; (Gyeonggi-do, KR) ; S.; Sujith;
(Gyeonggi-do, KR) ; Cyriac; Anish; (Gyeonggi-do,
KR) ; Min; JaeKi; (Gyeonggi-do, KR) ; Seong;
JongEon; (Incheon, KR) |
Correspondence
Address: |
CLARK & BRODY
1090 VERMONT AVENUE, NW, SUITE 250
WASHINGTON
DC
20005
US
|
Family ID: |
43535873 |
Appl. No.: |
12/458998 |
Filed: |
July 29, 2009 |
Current U.S.
Class: |
528/395 ; 556/32;
558/302; 568/716 |
Current CPC
Class: |
C07C 45/63 20130101;
C07C 45/68 20130101; C07C 45/68 20130101; C07F 15/065 20130101;
C08G 64/34 20130101; C07C 37/16 20130101; C07C 2601/14 20170501;
C07C 251/24 20130101; C07C 47/565 20130101; C07C 45/00 20130101;
C07C 45/63 20130101; C07C 249/02 20130101; C07C 37/16 20130101;
C07C 39/24 20130101; C07C 39/24 20130101; C07C 47/565 20130101 |
Class at
Publication: |
528/395 ;
568/716; 556/32; 558/302 |
International
Class: |
C08G 65/26 20060101
C08G065/26; C07F 15/06 20060101 C07F015/06; C07C 39/23 20060101
C07C039/23; C07C 249/00 20060101 C07C249/00 |
Foreign Application Data
Date |
Code |
Application Number |
Jul 30, 2008 |
KR |
10-2008-0074435 |
Dec 11, 2008 |
KR |
10-2008-0126170 |
Jun 18, 2009 |
KR |
10-2009-0054481 |
Jun 18, 2009 |
KR |
10-2009-0054569 |
Claims
1. A complex represented by Chemical Formula 1:
[L.sub.aMX.sub.b]X.sub.c [Chemical Formula 1] wherein M represents
a metal element; L represents a L-type or X-type ligand; p a
represents 1, 2 or 3, wherein when a is 1, L includes at least two
protonated groups, and when a is 2 or 3, L(s) are the same or
different, and may be linked to each other to be chelated to the
metal as a bidentate or tridentate ligand, with the proviso that at
least one L includes at least one protonated group and the total
number of protonated groups contained in L(s) represent 2 or more;
X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms; and b and c satisfy the condition of
"(b+c)=(total number of protonated groups contained in
L)+[(oxidation number of metal)-(number of X-type ligands in L)]",
and wherein the anion of Meisenheimer salt is a compound having the
following structural formula: ##STR00039## wherein R represents
methyl or H; and R' is selected from H and nitro (--NO.sub.2), with
the proviso that at least one of the five R' radicals represents
nitro (--NO.sub.2).
2. The complex according to claim 1, wherein the protonated group
contained in L represents a functional group represented by
Chemical Formula 2a, 2b or 2c, and M represents cobalt (III) or
chrome (III): ##STR00040## wherein G represents a nitrogen or
phosphorus atom; R.sup.1, R.sup.12, R.sup.13, R.sup.21, R.sup.22,
R.sup.23, R.sup.24 and R.sup.25 independently represent a
(C1-C20)alkyl, (C2-C20)alkenyl, (C1-C15)alkyl(C6-C20) aryl or
(C6-C20)ar(C1-C15)alkyl radical with or without at least one of
halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; or
a hydrocarbyl-substituted metalloid radical of a Group 14 metal,
wherein two of R.sup.11, R.sup.12 and R.sup.13, or two of R.sup.21,
R.sup.22, R.sup.23, R.sup.24 and R.sup.25 may be linked to each
other to form a ring; R.sup.31, R.sup.32 and R.sup.33 independently
represent a hydrogen radical; a (C1-C20)alkyl, (C2-C20)alkenyl,
(C1-C15)alkyl(C6-C20)aryl or (C6-C20)ar(C1-C15)alkyl radical with
or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms; or a hydrocarbyl-substituted metalloid
radical of a Group 14 metal, wherein two of R.sup.31, R.sup.32 and
R.sup.33 may be linked to each other to form a ring; X' represents
an oxygen atom, sulfur atom or N--R (wherein R represents a
hydrogen radical; or a (C1-C20)alkyl, (C2-C20)alkenyl,
(C1-C15)alkyl(C6-C20)aryl or (C6-C20)ar(C1-C15)alkyl radical with
or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms.
3. The complex according to claim 2, wherein L represents a ligand
represented by Chemical Formula 3, a represents 2 or 3, and M
represents cobalt (III) or chrome (III): ##STR00041## wherein A
represents an oxygen or sulfur atom; R.sup.1 through R.sup.5
independently represent a hydrogen radical; a (C1-C20)alkyl,
(C2-C20)alkenyl, (C1-C15)alkyl(C6-C20)aryl or
(C6-C20)aryl(C1-C15)alkyl radical with or without at least one of
halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; or
a hydrocarbyl-substituted metalloid radical of a Group 14 metal,
wherein the alkyl or alkenyl of R.sup.3 may be further substituted
by (C1-C15)alkyl(C6-C20)aryl or (C6-C20)aryl(C1-C15)alkyl, two of
R.sup.1 through R.sup.5 may be linked to each other to form a ring,
and at least one of R.sup.1 through R.sup.5 includes at least one
of Chemical Formulas 2a to 2c; and L(s) are the same or different
and may be linked to each other to be chelated to the metal as a
bidentate or tridentate ligand.
4. The complex according to claim 3, which is a complex represented
by Chemical Formula 5: ##STR00042## wherein A.sup.1 and A.sup.2
independently represent an oxygen or sulfur atom; X(s)
independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms; R.sup.41, R.sup.42, R.sup.43, R.sup.44,
R.sup.45 and R.sup.46 are independently selected from hydrogen,
tert-butyl, methyl, ethyl, isopropyl and
--[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN.sup.+R.sup.54R.sup.55R.su-
p.56}.sub.m], with the proviso that at least one of R.sup.41,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 represents
--[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN.sup.+R.sup.54R.sup.55R.su-
p.56}.sub.m] (wherein Y represents a carbon or silicon atom,
R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55 and R.sup.56
independently represent a hydrogen radical; a (C1-C20)alkyl,
(C2-C20)alkenyl, (C1-C15)alkyl(C6-C20)aryl or
(C6-C20)aryl(C1-C15)alkyl radical with or without at least one of
halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; or
a hydrocarbyl-substituted metalloid radical of a Group 14 metal,
wherein two of R.sup.54, R.sup.55 and R.sup.56 may be linked to
each other to form a ring; m represents an integer from 1 to 3; and
n represents an integer from 1 to 20); and b+c-1 represents an
integer that equals to the sum of m values of the total
--[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN.sup.+R.sup.54R.sup.55R.su-
p.56}.sub.m] radicals contained in the complex represented by
Chemical Formula 5.
5. The complex according to claim 4, wherein R.sup.41, R.sup.43,
R.sup.44 and R.sup.45 are independently selected from the group
consisting of tert-butyl, methyl, ethyl and isopropyl; R.sup.42 and
R.sup.46 independently represent
--[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2]; and b+c represents
5.
6. The complex according to claim 3, which is a complex represented
by Chemical Formula 6: ##STR00043## Wherein A.sup.1 and A.sup.2
independently represent an oxygen or sulfur atom; X(s)
independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms; R.sup.62 and R.sup.64 are independently
selected from tert-butyl, methyl, ethyl, isopropyl and hydrogen,
and R.sup.61 and R.sup.63 independently represent
--[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN.sup.+R.sup.54R.sup.55R.su-
p.56}.sub.m] (wherein Y represents a carbon or silicon atom,
R.sup.51, R.sup.52, R.sup.53, R.sup.54, R.sup.55 and R.sup.56
independently represent a hydrogen radical; a (C1-C20)alkyl,
(C2-C20)alkenyl, (C1-C15)alkyl(C6-C20) aryl or
(C6-C20)aryl(C1-C15)alkyl radical with or without at least one of
halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; or
a hydrocarbyl-substituted metalloid radical of a Group 14 metal,
wherein two of R.sup.54, R.sup.55 and R.sup.56 may be linked to
each other to form a ring; m represents an integer from 1 to 3; and
n represents an integer from 1 to 20); b+c-1 represents an integer
that equals to 2.times.m; and A.sup.3 represents a chemical bond or
divalent organic bridge group for linking the two phenyl
groups.
7. The complex according to claim 6, wherein A.sup.3 represents a
chemical bond, (C6-C30)arylene, (C1-C20)alkylene,
(C2-C20)alkenylene, (C2-C20)alkynylene, (C3-C20)cycloalkylene or
fused (C3-C20)cycloalkylene, or --Si(R.sup.87)(R.sup.88--,
--CH.dbd.N-Q-N.dbd.CH--, or the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N, wherein R.sup.87
and R.sup.88 independently represent (C1-C20)alkyl,
(C3-C20)cycloalkyl, (C1-C15)alkyl(C6-C20)aryl, or
(C6-C20)aryl(C1-C15)alkyl and Q represents a divalent organic
bridge group for linking the two nitrogen atoms.
8. The complex according to claim 7, wherein Q represents
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N.
9. The complex according to claim 8, wherein R.sup.61 and R.sup.63
independently represent
--[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2], Q in the formula of
--CH.dbd.N-Q-N.dbd.CH-- represents trans-1,2-cyclohexylene or
ethylene, and X independently represents 2,4-dinitrophenolate or
BF.sub.4.sup.-.
10. The complex according to claim 9, wherein b+c represents 5, one
of the five X radicals represents BF.sub.4, two of them represent
2,4-dinitrophenolate, and the remaining two X radicals are anions
represented by Chemical Formula 10: ##STR00044## wherein R
represents methyl or H.
11. The complex according to claim 8, which is a complex
represented by Chemical Formula 11: ##STR00045## wherein B.sup.1
through B.sup.4 independently represent (C2-C20)alkylene or
(C3-C20)cycloalkylene; R.sup.26 represents primary or secondary
(C1-C20)alkyl; R.sup.27 through R.sup.29 are independently selected
from (C1-C20)alkyl and (C6-C30)aryl; Q represents a divalent bridge
group for linking the two nitrogen atoms; and Z.sup.1 through
Z.sup.5 are independently selected from a halide ion;
BF.sub.4.sup.-; ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-;
HCO.sub.3.sup.-; and a (C6-C30)aryloxy anion; (C1-C20)carboxylic
acid anion; (C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion or anion of Meisenheimer slat with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms, wherein a part of Z.sup.1 through Z.sup.4
coordinated at the cobalt atom may be de-coordinated.
12. The complex according to claim 11, wherein B.sup.1 through
B.sup.4 independently represent (C2-C6)alkylene; R.sup.26
represents (C1-C7)alkyl; R.sup.27 through R.sup.29 independently
represent (C1-C7)alkyl; Q represents ethylene,
trans-1,2-cyclohexylene or 1,2-phenylene; Z.sup.1 through Z.sup.5
are independently selected from 2,4-dinitrophenolate and
BF.sub.4.sup.-.
13. The complex according to claim 12, wherein B.sup.1 through
B.sup.4 independently represent propylene; R.sup.26 and R.sup.27
independently represent methyl; R.sup.28 and R.sup.29 independently
represent butyl; Q represents trans-1,2-cyclohexylene; and Z.sup.1
through Z.sup.5 are independently selected from
2,4-dinitrophenolate and BF.sub.4.sup.-.
14. A method for preparing polycarbonate, comprising carrying out
copolymerization of an epoxide compound with carbon dioxide using
the complex according to claim 1 as a catalyst.
15. The method according to claim 14, wherein the epoxide compound
is selected from the group consisting of (C2-C20) alkylene oxide
substituted or unsubstituted by a halogen or alkoxy; (C4-C20)
cycloalkylene oxide substituted or unsubstituted by a halogen or
alkoxy; and (C8-C20) styrene oxide substituted or unsubstituted by
a halogen, alkoxy, alkyl or aryl.
16. A method for separately recovering a complex, comprising:
contacting a solution containing the copolymer and the catalyst and
obtained by the method for preparing polycarbonate according to
claim 14 with a solid phase selected from an inorganic material,
polymer material or a mixture thereof non-soluble in the solution
to form a complex of the solid phase and the catalyst and to
separate the copolymer solution; treating the complex with an acid
or a metal salt of a non-reactive anion in a medium that is not
capable of dissolving the solid phase to perform an acid-base
reaction or salt metathesis; and carrying out salt metathesis with
a salt containing anion X, wherein X independently represents a
halide ion; BF.sub.4.sup.-; ClO.sub.4.sup.-; NO.sub.3.sup.-;
PF.sub.6.sup.-; HCO.sub.3.sup.-; or a (C6-C20)aryloxv anion;
(C1-C20)alkvlcarboxv anion; (C1-C20)alkoxv anion;
(C1-C20)alkvlcarbonate anion; (C1-C20)alkvlsulfonate anion;
(C1-C20)alkylamide anion; (C1-C20)alkvlcarbamate anion; or anion of
Meisenheimer salt with or without at least one of halogen,
nitrogen, oxygen, silicon. sulfur and phosphorus atoms and the
anion of Meisenheimer salt is a compound having the following
structural formula: ##STR00046## wherein R represents methyl or H;
and R.sup.1 is selected from H and nitro (-NO.sub.2), with the
proviso that at least one of the five R.sup.1 radicals represents
nitro (--NO.sub.2).
17. The method according to claim 16, wherein the complex is
separately recovered by adding the solution containing the
copolymer and the catalyst to a solution containing a solid phase
selected from an inorganic material, polymer material and a mixture
thereof, followed by filtration; or by passing the solution
containing the copolymer and the catalyst through a column packed
with the solid phase.
18. The method according to claim 17, wherein the solid inorganic
material is surface-modified or non-modified silica or alumina, and
the solid polymer material has a functional group reactive to
deprotonation by alkoxy anion.
19. The method according to claim 18, wherein the functional group
reactive to deprotonation by alkoxy anion is a sulfonic acid group,
carboxylic acid group, phenol group or alcohol group.
20. The method according to claim 16, wherein the solution is
contacted with silica to form a silica-catalyst complex and to
separate the copolymer from the solution; treating the
silica-catalyst complex with an acid or a metal salt of a
non-reactive anion in a medium that is not capable of dissolving
silica to perform an acid-base reaction or salt metathesis; and
carrying out salt metathesis using a salt containing anion X.
21. The method according to claim 14, wherein the acid is
hydrochloric acid or 2,4-dinitrophenol, and the metal salt of a
non-reactive anion is DBF.sub.4 or DClO.sub.4 (wherein D represents
Li, Na or K).
22. The method according to claim 14, wherein the salt containing
anion X is a salt containing Cl anion or 2,4-dinitrophenolate
anion.
23. A method for preparing a complex represented by Chemical
Formula 1, comprising: reacting L with a metal salt so that L is
bound to the metal; and adding an acid (HX) thereto after L is
bound to the metal element and carrying out a reaction in the
presence of oxygen to oxidize the metal element and to allow the
anion X to be coordinated at the metal element (wherein L and X are
the same as defined in Chemical Formula 1):
[L.sub.aMX.sub.b]X.sub.c [Chemical Formula 1] wherein M represents
a metal element; L represents a L-type or X-type ligand; a is 1, 2
or 3, wherein when a is 1, L includes at least two protonated
groups, and when a is 2 or 3, L(s) are the same or different, and
may be linked to each other to be chelated to the metal as a
bidentate or tridentate ligand, with the proviso that at least one
L includes at least one protonated group and the total number of
protonated groups contained in L(s) is 2 or more; X(s)
independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.31 ; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms; and b and c satisfy the condition of
"(b+c)=(total number of protonated groups contained in
L)+[(oxidation number of metal)-(number of X-type ligands in L)]",
and wherein the anion of Meisenheimer is a compound having the
following structural formula: ##STR00047## wherein R represents
methyl or hydrogen; and R.sup.1 is selected from hydrogen and nitro
(--NO.sub.2), with the proviso that at least one of the five
R.sup.1 radicals represents nitro (--NO.sub.2).
24. A compound represented by Chemical Formula 17: ##STR00048##
wherein B.sup.1 through B.sup.4 independently represent
(C2-C20)alkylene or (C3-C20)cycloalkylene; R.sup.26 represents
primary or secondary (C1-C20)alkyl; R.sup.27 through R.sup.29 are
independently selected from (C1-C20)alkyl and (C6-C30)aryl; Q is a
divalent organic bridge group for linking the two nitrogen atoms
with each other; and Z.sup.-(s) are independently selected from
halide ions, BF.sub.4.sup.-, ClO.sub.4.sup.-, NO.sub.3.sup.-, and
PF.sub.6.sup.-.
25. The compound according to claim 24, wherein Q represents
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N.
26. The compound according to claim 25, wherein B.sup.1 through
B.sup.4 independently represent propylene; R.sup.26 and R.sup.27
independently represent methyl, and R.sup.28 and R.sup.29
independently represent butyl; Q represents
trans-1,2-cyclohexylene; and Z.sup.-(s) independently represent
iodide anion or BF.sub.4.sup.-.
27. A method for preparing a compound represented by Chemical
Formula 17, comprising: adding a diamine compound to a compound
represented by Chemical Formula 20 to perform imination and to
provide a compound represented by Chemical Formula 21; and adding a
tertiary amine compound thereto to produce a compound represented
by Chemical Formula 17: ##STR00049## wherein B.sup.1 through B4,
B.sup.9 and B.sup.10 independently represent (C2-C20)alkylene or
(C3-C20)cycloalkylene; R.sup.26 is primary or secondary
(C1-C20)alkyl; R.sup.27 through R.sup.29 are independently selected
from (C1-C20)alkyl and (C6-C30)aryl; Q is a divalent organic bridge
group for linking the two nitrogen atoms with each other;
Z.sup.-(s) are independently selected from halide ions,
BF.sub.4.sup.-, ClO.sub.4.sup.-, NO.sub.3.sup.-, and
PF.sub.6.sup.-; and X.sup.3 and X.sup.4 are independently selected
from Cl, Br and I.
28. The method according to claim 27, wherein the compound
represented by Chemical Formula 20 is obtained by reacting a
compound represented by Chemical Formula 15 with a compound
represented by Chemical Formula 16 in the presence of an acid
catalyst to form a compound represented by Chemical Formula 14, and
by attaching an aldehyde group to the compound represented by
Chemical Formula 14: ##STR00050## wherein B.sup.9 and B.sup.10
independently represent (C2-C20)alkylene or (C3-C20)cycloalkylene;
R.sup.26 represents primary or secondary (C1-C20)alkyl; R.sup.27 is
selected from (C1-C20)alkyl and (C6-C30)aryl; and X.sup.3 and
X.sup.4 are independently selected from Cl, Br and I.
29. A phenol derivative represented by Chemical Formula 14:
##STR00051## wherein B.sup.9 and B.sup.10 independently represent
(C2-C20)alkylene or (C3-C20)cycloalkylene; R.sup.26 represents
primary or secondary (C1-C20)alkyl; R.sup.27 is selected from
(C1-C20)alkyl and (C6-C30)aryl; and X.sup.3 and X.sup.4 are
independently selected from Cl, Br and I.
30. A method for preparing a phenol derivative represented by
Chemical Formula 14, comprising: reacting a phenol compound
represented by Chemical Formula 15 with tertiary alcohol compound
represented by Chemical Formula 16 in the presence of an acid
catalyst: ##STR00052## wherein B.sup.9 and B.sup.10 independently
represent (C2-C20)alkylene or (C3-C20)cycloalkylene; R.sup.26
represents primary or secondary (C1-C20)alkyl; R.sup.27 is selected
from (C1-C20)alkyl and (C6-C30)aryl; and X.sup.3 and X.sup.4 are
independently selected from Cl, Br and I.
31. The method according to claim 30, wherein B.sup.9 and B.sup.10
independently represent (C2-C6)alkylene; R.sup.26 represents
primary or secondary (C1-C7)alkyl; and R.sup.27 represents
(C1-C7)alkyl.
32. The method according to claim 31, wherein B.sup.9 and B.sup.10
independently represent propylene; and R.sup.26 and R.sup.27
independently represent methyl.
33. The method according to claim 30, wherein the acid catalyst is
selected from AlCl.sub.3, inorganic acid and solid acid catalysts.
Description
TECHNICAL FIELD
[0001] The present invention relates to a novel catalyst for use in
preparing polycarbonate from an epoxide compound and carbon dioxide
and a method for preparing polycarbonate using the same. More
particularly, the present invention relates to a catalyst for
preparing the above polymer, which includes a complex having such
an equilibrium structural formula that the metal center of the
complex takes a negative charge of 2 or higher, as well as to a
method for preparing polycarbonate via copolymerization of carbon
dioxide and epoxide using the same complex as a catalyst. In
addition, the present invention relates to a method including
carrying out polymerization using the above catalyst, and
separately recovering the catalyst from the solution in which the
resultant copolymer and the catalyst are dissolved.
BACKGROUND ART
[0002] Aliphatic polycarbonate is an easily biodegradable polymer
and is useful for packaging or coating materials, etc. Processes
for preparing polycarbonate from an epoxide compound and carbon
dioxide is highly eco-friendly in that they use no harmful
compound, phosgene, and adopt easily available and inexpensive
carbon dioxide.
[0003] Since 1960's, many researchers have developed various types
of catalysts to prepare polycarbonate from an epoxide compound and
carbon dioxide. Recently, we have developed a catalyst for carrying
out carbon dioxide/epoxide copolymerization. The catalyst includes
a complex having an onium salt and a metal center with a Lewis acid
group in one molecule. Use of the catalyst allows the growth point
of the polymer chain to be positioned always in the vicinity of the
metal in the polymerization medium for carrying out epoxide/carbon
dioxide copolymerization, regardless of the concentration of the
catalyst. In this manner, the catalyst shows high activity even
under a high ratio of monomer/catalyst, exhibits high
cost-efficiency by virtue of a decrease in catalyst need, and
provides polycarbonate with a high molecular weight. Moreover, the
catalyst realizes polymerization activity even at high temperature
to increase the conversion, permits easy removal of the
polymerization reaction heat, and thus is easily applicable to
commercial processes [see, Korean Patent Application
No.10-2007-0043417 (May 4, 2007, Title: COORDINATION COMPLEXS
CONTAINING TWO COMPONENTS IN A MOLECULE AND PROCESS OF PRODUCING
POLYCARBONATE BY COPOLYMERIZATION OF CARBON DIOXIDE AND EPOXIDE
USING THE SAME); International Patent Application No.
PCT/KR2008/002453; Eun Kyung Noh, Sung Jae Na, Sujith S, Sang-Wook
Kim, and Bun Yeoul Lee* J. Am. Chem. Soc. 2007, 129, 8082-8083
(Apr. 7, 2007)]. Further, when the complex having an onium salt and
a metal center with a Lewis acid group in one molecule is used as a
catalyst for carbon dioxide/epoxide copolymerization, the catalyst
is easily separated and reutilized from the copolymer after the
polymerization. Thus, such a method for separately recovering the
catalyst has been described in a patent application and a journal
[Korean Patent Application No. 10-2008-0015454 (Feb. 20, 2008,
Title: METHOD FOR RECOVERING CATALYST FROM PROCESS FOR PREPARING
COPOLYMER); Bun Yeol Lee, Sujith S, Eun Kyung Noh, Jae Ki Min, "A
PROCESS PRODUCING POLYCARBONATE AND A COORDINATION COMPLEXES USED
THEREFOR" PCT/KR2008/002453 (Apr. 30, 2008); Sujith S, Jae Ki Min,
Jong Eon Seong, Sung Jea Na, and Bun Yeoul Lee* "A HIGHLY ACTIVE
AND RECYCLABLE CATALYTIC SYSTEM FOR CO.sub.2/(PROPYLENE OXIDE)
COPOLYMERIZATION" Angew. Chem. Int Ed., 2008, 47, 7306-7309].
[0004] The complex of the above studies mainly includes
Salen-cobalt compound
([H.sub.2Salen=N,N'-bis(3,5-dialkylsalicylidene)-1,2-cyclohexane-
diamine]) (see the following chemical formula), obtained from a
Schiff base ligand of a salicylaldehyde compound and a diamine
compound. The complex is a tetradentate (or quadradendate) cobalt
compound-based complex in which trivalent cobalt atom is
coordinated with two nitrogen imine ligands and two phenolate
ligands at the same time:
##STR00001##
[0005] The complex may be referred to as a tetradentate (or
quadradendate) Schiff base complex, and may be prepared according
to the following reaction scheme:
##STR00002##
[0006] The above tetradentate (or quadradentate) Schiff-base cobalt
or chrome complex has been developed intensively as a carbon
dioxide/epoxide copolymerization catalyst. (Cobalt-based catalyst:
(a) Lu, X.-B.; Shi, L.; Wang, Y.-M.; Zhang, R.; Zhang, Y.-J.; Peng,
X.-J.; Zhang, Z.-C.; Li, B. J Am. Chem. Soc. 2006, 128,1664. (b)
Cohen, C. T. Thomas, C. M. Peretti, K. L. Lobkovsky, E. B. Coates,
G. W. Dalton Trans. 2006, 237. (c) Paddock, R. L. Nguyen, S. T.
Macromolecules 2005, 38, 6251. Chrome-based catalyst: (a)
Darensbourg, D. J.; Phelps, A. L.; Gall, N. L.; Jia, L. Acc. Chem.
Res. 2004, 37, 836. (b) Darensbourg, D. J.; Mackiewicz, R. M. J.
Am. Chem. Soc. 2005, 127,14026.).
DISCLOSURE
[Technical Problem]
[0007] We have studied about the characteristics and structures of
the tetradentate (or quadradentate) complex having the above
described structure and unexpectedly found that the complex shows
significantly different activities and selectivities depending on
the R group. In order word, when R is a sterically hindered group
such as t-butyl, the compound shows commonly expectable activity
and selectivity. However, when R has decreased steric hindrance, or
R is a radical such as methyl, the complex provides an activity
(TOF, turnover frequency) of 26000 h.sup.-1, which is about 20
times higher than the activity (1300 h.sup.-1) of the corresponding
t-butyl group-containing complex. In addition, the methyl
group-containing complex provides an increase in selectivity from
84% to 99% or higher. Based on these findings, we have conducted
several types of structural analysis including .sup.1H MNR,
.sup.13C MNR, .sup.15N MNR, .sup.19F NMR, IR, IAP-AES, elemental
analysis, electrochemical analysis, etc. As a result, we have found
that when R is a less sterically hindered radical, such as methyl,
another complex (i.e. bidentate complex) having a different
structure in which the metal is not coordinated with the adjacent
nitrogen is obtained, and the complex has high activity and
selectivity.
[0008] Therefore, an object of the present invention is to provide
a method for copolymerizing carbon dioxide and epoxide using a
complex coordinated with monodentate, bidentate or tridentate
ligands having at least one protonated group rather than the
existing tetradentate (or quadradentate) complex.
[0009] Another object of the present invention is to provide a
method for the formation of a copolymer using the above complex as
a catalyst, and for the separation and recovery of the catalyst
from the mixed solution of the resultant copolymer and the
catalyst.
[0010] Still another object of the present invention is to provide
the above-described novel complex.
[Technical Solution]
[0011] To achieve the object of the present invention, the present
invention provides a novel complex coordinated with monodentate,
bidentate or tridentate ligands having at least one protonated
group, and a method for preparing a carbon dioxide/epoxide
copolymer using the same complex as a catalyst.
[0012] Hereinafter, the present invention will be explained in more
detail.
[0013] The present invention provides a novel complex as a catalyst
for preparing a carbon dioxide/epoxide copolymer. The complex is
coordinated with monodentate, bidentate or tridentate ligands
having at least one protonated group. The complex is represented by
Chemical Formula 1:
[L.sub.aMX.sub.b]X.sub.c [Chemical Formula 1]
[0014] wherein
[0015] M represents a metal element;
[0016] L represents a L-type or X-type ligand;
[0017] a represents 1, 2 or 3, wherein when a is 1, L includes at
least two protonated groups, and when a is 2 or 3, L(s) are the
same or different, and may be linked to each other to be chelated
to the metal as a bidentate or tridentate ligand, with the proviso
that at least one L includes at least one protonated group and the
total number of protonated groups contained in L(s) is 2 or
more;
[0018] X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms; and
[0019] b and c satisfy the condition of "(b+c)=(total number of
protonated groups contained in L)+[(oxidation number of
metal)-(number of X-type ligands in L)]".
[0020] The anion of Meisenheimer salt is a compound having the
following structural formula:
##STR00003##
[0021] wherein
[0022] R represents methyl or H; and
[0023] R' is selected from H and nitro (--NO.sub.2), with the
proviso that at least one of the five R' radicals represents nitro
(--NO.sub.2).
[0024] In Chemical Formula 1, L-type and X-type ligands are
described in detail in [Gray L. Spessard and Gary L. Miessler,
Organometallic Chemistry, published by Prentice Hall, p. 46].
L-type ligands mean neutral ligands and particularly include
non-paired electron pair donors, such as phosphine, pi-bond donors,
such as ethylene, or sigma-bond donors, such as hydrogen. L-type
ligands are bound to the metal by donating non-paired electron
pairs, and binding of the L-type ligands has no effect on the
oxidation number of the metal. X-type ligands include anionic
ligands, such as chlorine or methyl. Binding of such X-type ligands
is regarded as binding between X.sup.- anion and M.sup.+ cation,
and affects the oxidation number of the metal.
[0025] The complex used as a carbon dioxide/epoxide
copolymerization catalyst herein is a complex coordinated with
monodentate, bidentate or tridentate ligands having at least one
protonated group (i.e. complex represented by Chemical Formula 1),
and having such an equilibrium structural formula that the metal
center takes a negative charge of 2 or higher. The carbon
dioxide/epoxide copolymerization catalysts developed to date are
tetradentate (or quadradentate) Schiff-base complexes wherein "four
groups are bound to one metal atom", and thus are clearly different
from the complex disclosed herein.
[0026] According to one embodiment of the present invention, there
is provided a complex represented by Chemical Formula 1, wherein
the protonated group contained in L represents a functional group
represented by Chemical Formula 2a, 2b or 2c, and M represents
cobalt (III) or chromium (III):
##STR00004##
[0027] wherein
[0028] G represents a nitrogen or phosphorus atom;
[0029] R.sup.11, R.sup.12, R.sup.13, R.sup.21, R.sup.22, R.sup.23,
R.sup.24 and R.sup.25 independently represent a (C1-C20)alkyl,
(C2-C20)alkenyl, (C1-C15)alkyl(C6-C20)aryl or
(C6-C20)aryl(C1C15)alkyl radical with or without at least one of
halogen, nitrogen, oxygen, silicon, sulfur and phosphorus atoms; or
a hydrocarbyl-substituted metalloid radical of a Group 14 metal,
wherein two of R.sup.11, R.sup.12 and R.sup.3, or two of R.sup.21,
R.sup.22, R.sup.23, R.sup.24 and R.sup.25 may be linked to each
other to form a ring;
[0030] R.sup.31, R.sup.32 and R.sup.33 independently represent a
hydrogen radical; (C1-C20)alkyl, (C2-C20)alkenyl,
(C1-C15)alkyl(C6-C20)aryl or (C6-C20)aryl(C1-C15)alkyl radical with
or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms; or a hydrocarbyl-substituted metalloid
radical of a Group 14 metal, wherein two of R.sup.31, R.sup.32 and
R.sup.33 may be linked to each other to form a ring;
[0031] X' represents an oxygen atom, sulfur atom or N--R (wherein R
represents a hydrogen radical; or a (C1-C20)alkyl, (C2-C20)alkenyl,
(C1-C15)alkyl(C6-C20)aryl or (C6-C20)ar(C1-C15)alkyl radical with
or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms; and
[0032] the alkyl of the alkyl, alkenyl, alkylaryl or aralkyl
radicals may be linear or branched.
[0033] According to another embodiment of the present invention,
there is provided a complex represented by Chemical Formula 1,
wherein L represents a ligand represented by Chemical Formula 3, a
represents 2 or 3, and M represents cobalt (III) or chromium
(III):
##STR00005##
[0034] wherein
[0035] A represents an oxygen or sulfur atom;
[0036] R.sup.1 through R.sup.5 independently represent a hydrogen
radical; linear or branched (C1-C20)alkyl, (C2-C20)alkenyl,
(C1-C15)alkyl(C6-C20)aryl or (C6-C20)aryl(C1-C15)alkyl radical with
or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms; or a hydrocarbyl-substituted metalloid
radical of a Group 14 metal, wherein the alkyl or alkenyl of
R.sup.3 may be further substituted by a (C1-C15)alkyl(C6-C20)aryl
or (C6-C20)aryl(C1-C15)alkyl, two of R.sup.1 through R.sup.5 may be
linked to each other to form a ring, and at least one of R.sup.1
through R.sup.5 include at least one of Chemical Formulas 2a to
2c;
[0037] a represents 2 or 3; and
[0038] L(s) are the same or different and may be linked to each
other to be chelated to the metal as a bidentate or tridentate
ligand.
[0039] According to still another embodiment of the present
invention, there is provided a complex having two ligands L
represented by Chemical Formula 4:
##STR00006##
[0040] wherein
[0041] B.sup.1 through B.sup.4 independently represent
(C2-C20)alkylene or (C3-C20)cycloalkylene;
[0042] R.sup.26 represents primary or secondary (C1-C20)alkyl;
[0043] R.sup.27 through R.sup.29 are independently selected from
(C1-C20)alkyl and (C6-C30)aryl;
[0044] Q represents a divalent organic bridge group for linking the
two nitrogen atoms with each other; and
[0045] the alkylene or alkyl may be linear or branched.
[0046] More particularly, in Chemical Formula 4, Q represents
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N.
[0047] Preferably, in Chemical Formula 4, B.sup.1 through B.sup.4
independently represent propylene, R.sup.26 and R.sup.27
independently represent methyl, R.sup.28 and R.sup.29 independently
represent butyl, and Q represents trans-1,2-cyclohexylene.
[0048] The ligand represented by Chemical Formula 4 may be formed
from a phenol derivative represented by Chemical Formula 14, which
is prepared from the reaction between a phenol compound represented
by Chemical Formula 15 and substituted by an alkyl group at the C2
position and a tertiary alcohol compound represented by Chemical
Formula 16 in the presence of an acid catalyst:
##STR00007##
[0049] In Chemical Formulas 14 to 16, B.sup.9 and B.sup.10
independently represent (C2-C20)alkylene or (C3-C20)cycloalkylene,
preferably propylene. R.sup.26 represents primary or secondary
(C1-C20)alkyl. When R.sup.26 is a tertiary alkyl, the reaction
provides a low yield due to the production of byproducts caused by
various side reactions, and thus requires a purification process
for removing the byproducts. In addition, cobalt complexes obtained
from such a tertiary alkyl-containing phenol compound have a
different structure and low activity. Thus, primary or secondary
(C1-C20)alkyl is preferred. More particularly, R.sup.26 represents
primary or secondary (C1-C7)alkyl. Herein, the term `primary alkyl`
includes normal alkyl, neo-alkyl or iso-alkyl. The terms `secondary
alkyl` and `tertiary alkyl` are also referred to as `sec-alkyl` and
`tert-alkyl`, respectively.
[0050] R.sup.27 is selected from (C1-C20)alkyl and (C6-C30)aryl,
more particularly (C1-C7)alkyl, and preferably methyl. The term
`alkyl` includes a linear or branched alkyl group.
[0051] X.sup.3 and X.sup.4 is independently selected from Cl, Br
and I.
[0052] Herein, the term `aryl` includes an aromatic ring, such as
phenyl, naphthyl, anthracenyl or biphenyl, wherein a carbon atom in
the aromatic ring may be substituted by a hetero atom, such as N, O
and S.
[0053] As the acid catalyst, AlCl.sub.3 or an inorganic acid, such
as phosphoric acid or sulfuric acid, may be used. A solid acid
catalyst may be used to permit recycle of the catalyst after the
reaction. Particular examples of the solid acid catalyst include
Nafion NR50, Amberlyst-15, H-ZSM5, H-Beta, HNbMoO.sub.6, or the
like (see, Kazunari Domen et. al, J. AM. CHEM. SOC. 2008, 130,
7230-7231).
[0054] The tertiary alcohol compound represented by Chemical
Formula 16 may be prepared by various organic reactions. For
example, the tertiary alcohol compound may be obtained according to
Reaction Scheme 7:
##STR00008##
[0055] wherein
[0056] X.sup.3, X.sup.4 and R.sup.27 are the same as defined in
Chemical Formula 16.
[0057] The present invention also provides a ligand compound
represented by Chemical Formula 17 prepared from a phenol
derivative represented by Chemical Formula 14:
##STR00009##
[0058] In Chemical Formula 17, B.sup.1 through B.sup.4
independently represent (C2-C20)alkylene or (C3-C20)cycloalkylene,
preferably propylene. The alkylene may be linear or branched.
[0059] In Chemical Formula 17, R.sup.26 represents primary or
secondary (C1-C20)alkyl. When R.sup.26 is tertiary alkyl, the
reaction provides a low yield due to the production of byproducts
caused by various side reactions, and thus requires a purification
process for removing the byproducts. In addition, cobalt complexes
obtained from such a tertiary alkyl-containing phenol compound have
a different structure and low activity. Thus, primary or secondary
(C1-C20)alkyl is preferred. More particularly, R.sup.26 represents
primary or secondary (C1-C7)alkyl. Most preferably, R.sup.26
represents methyl.
[0060] In Chemical Formula 17, R.sup.27 through R.sup.29 are
independently selected from (C1-C20)alkyl and (C6-C30)aryl groups.
More particularly, R.sup.27 through R.sup.29 are independently
selected from (C1-C7)alkyl groups. Preferably, R.sup.27 represents
methyl and R.sup.28 and R.sup.29 independently represent butyl.
[0061] In Chemical Formula 17, Q represents a divalent organic
bridge group for linking the two nitrogen atoms with each other.
Particularly, Q represents (C6-C30)arylene, (C1-C20)alkylene,
(C2-C20)alkenylene, (C2-C20)alkynylene, (C3-C20)cycloalkylene or
fused (C3-C20)cycloalkylene, wherein the arylene, alkylene,
alkenylene, alkynylene, cycloalkylene or fused cycloalkylene may be
further substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N. More
particularly, Q is selected from ethylene, trans-1,2-cyclohexylene
and 1,2-phenylene.
[0062] In Chemical Formula 17, Z.sup.-(s) are independently
selected from halide ions, BF.sub.4.sup.-, ClO.sub.4.sup.-,
NO.sub.3.sup.-, and PF.sub.6.sup.-, more particularly iodide ion
and BF.sub.4.sup.-.
[0063] More preferably, the ligand compound represented by Chemical
Formula 17 may be a ligand compound represented by Chemical Formula
18:
##STR00010##
[0064] In Chemical Formula 18, m and n independently represent an
integer from 1 to 19, preferably from 1 to 5, and more preferably
2.
[0065] In Chemical Formula 18, R.sup.26 represents primary or
secondary (C1-C20)alkyl. When R.sup.26 is a tertiary alkyl, the
reaction provides a low yield due to the production of byproducts
caused by various side reactions, and thus requires a purification
process for removing the byproducts. In addition, cobalt complexes
obtained from such a tertiary alkyl-containing compound have a
different structure and low activity. Thus, primary or secondary
(C1-C20)alkyl is preferred. More particularly, R.sup.26 represents
primary or secondary (C1-C7)alkyl. Most preferably, R.sup.26
represents methyl.
[0066] In Chemical Formula 18, R.sup.27 through R.sup.29 are
independently selected from (C1-C20)alkyl and (C6-C30)aryl groups.
More particularly, R.sup.27 through R.sup.29 are independently
selected from (C1-C7)alkyl groups. Preferably, R.sup.27 represents
methyl and R.sup.28 and R.sup.29 independently represent butyl.
[0067] In Chemical Formula 18, Q represents a divalent organic
bridge group for linking the two nitrogen atoms with each other.
Particularly, Q represents (C6-C30)arylene, (C1-C20)alkylene,
(C2-C20)alkenylene, (C2-C20)alkynylene, (C3-C20)cycloalkylene or
fused (C3-C20)cycloalkylene, wherein the arylene, alkylene,
alkenylene, alkynylene, cycloalkylene or fused cycloalkylene may be
further substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N. More
particularly, Q is selected from ethylene, trans-1,2-cyclohexylene
and 1,2-phenylene.
[0068] In Chemical Formula 18, Z.sup.-(s) are independently or
simultaneously selected from halide ions, BF.sub.4.sup.-,
ClO.sub.4.sup.-, NO.sub.3.sup.-, and PF.sub.6.sup.-, more
particularly iodide ion and BF.sub.4.sup.-.
[0069] A method for preparing the compound represented by Chemical
Formula 17 or 18 includes:
[0070] adding a diamine compound to a compound represented by
Chemical Formula 20 to perform imination and to produce a compound
represented by Chemical Formula 21; and
[0071] adding a tertiary amine compound thereto to produce a
compound represented by Chemical Formula 17:
##STR00011##
[0072] In Chemical Formulas 17, 20 and 21, B.sup.1 through B.sup.4,
B.sup.9 and B.sup.10 independently represent (C2-C20)alkylene or
(C3-C20)cycloalkylene, preferably (C2-C6)alkylene, more preferably
propylene;
[0073] R.sup.26 represents primary or secondary (C1-C20)alkyl,
preferably primary or secondary (C1-C7)alkyl, more preferably
methyl;
[0074] R.sup.27 through R.sup.29 are independently selected from
(C1-C20)alkyl and (C6-C30)aryl groups, preferably (C1-C7)alkyl
groups. More preferably, R.sup.27 represents methyl and R.sup.28
and R.sup.29 independently represent butyl;
[0075] Q represents a divalent organic bridge group for linking the
two nitrogen atoms with each other, preferably Q represents
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N, and more
preferably, Q represents trans-1,2-cyclohexylene;
[0076] Z.sup.-(s) are independently selected from halide ions,
BF.sub.4.sup.-, ClO.sub.4.sup.-, NO.sub.3.sup.- and PF.sub.6.sup.-,
more particularly iodide ion and BF.sub.4.sup.-; and
[0077] X.sup.3 and X.sup.4 are independently selected from Cl, Br
and I.
[0078] The compound represented by Chemical Formula 20 may be
prepared by reacting the compound represented Chemical Formula 15
with the compound represented by Chemical Formula 16 in the
presence of an acid catalyst to form the compound represented by
Chemical Formula 14, and by attaching an aldehyde group at the
compound represented by Chemical Formula 14. The acid catalyst may
be selected from AlCl.sub.3, inorganic acids and solid acid
catalysts.
[0079] According to one embodiment of the complex represented by
Chemical Formula 1, there is provided a complex represented by
Chemical Formula 5:
##STR00012##
[0080] wherein
[0081] A.sup.1 and A.sup.2 independently represent an oxygen or
sulfur atom;
[0082] X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms;
[0083] R.sup.41, R.sup.42, R.sup.43, R.sup.44, R.sup.45 and
R.sup.46 are independently selected from H, tert-butyl, methyl,
ethyl, isopropyl and
-[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN.sup.+R.sup.54R.sup.55R.sup-
.56}.sub.m], with the proviso that at least one of R.sup.4 ,
R.sup.42, R.sup.43, R.sup.44, R.sup.45 and R.sup.46 represents
-[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN+R.sup.54R.sup.55R.sup.56}.-
sub.m] (wherein Y represents a carbon or silicon atom, R.sup.51,
R.sup.52, R.sup.53, R.sup.54, R.sup.55 and R.sup.56 independently
represent a hydrogen radical; (C1-C20)alkyl, (C2-C20)alkenyl,
(C1-C15)alkyl(C6-C20) aryl or (C6-C20)ar(C1-C15)alkyl radical with
or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms; or a hydrocarbyl-substituted metalloid
radical of a Group 14 metal, wherein two of R.sup.54, R.sup.55 and
R.sup.56 may be linked to each other to form a ring; m represents
an integer from 1 to 3; and n represents an integer from 1 to 20);
and
[0084] b+c-1 represents an integer that equals to the sum of m
values of the
total-[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN.sup.+R.sup.54R.su-
p.55R.sup.56}.sub.m] radicals contained in the complex represented
by Chemical Formula 5.
[0085] Preferably, in the complex represented by Chemical Formula
5, R.sup.41, R.sup.43, R.sup.44 and R.sup.45 are independently
selected from tert-butyl, methyl, ethyl and isopropyl; R.sup.42 and
R.sup.46 independently represent
--[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe}(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2]; and b+c represents
5.
[0086] According to another embodiment of the complex represented
by Chemical Formula 1, there is provided a complex represented by
Chemical Formula 6:
##STR00013##
[0087] wherein
[0088] A.sup.1 and A.sup.2 independently represent an oxygen or
sulfur atom;
[0089] X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms;
[0090] R.sup.62 and R.sup.64 are independently selected from
tert-butyl, methyl, ethyl, isopropyl and hydrogen, and R.sup.61 and
R.sup.63 independently represent
-[YR.sup.51.sub.3-m{(CR.sup.52R.sup.53).sub.nN+R.sup.54R.sup.55R.sup.56}m-
] (wherein Y represents a carbon or silicon atom, R.sup.51,
R.sup.52, R.sup.53, R.sup.54, R.sup.55 and R.sup.56 independently
represent a hydrogen radical; (C1-C20)alkyl, (C2-C20)alkenyl,
(C.sub.1-C15)alkyl(C6-C20)aryl or (C6-C20)ar(C1-C15)alkyl radical
with or without at least one of halogen, nitrogen, oxygen, silicon,
sulfur and phosphorus atoms; or a hydrocarbyl-substituted metalloid
radical of a Group 14 metal, wherein two of R.sup.54, R.sup.55 and
R.sup.56 may be linked to each other to form a ring; m represents
an integer from 1 to 3; and n represents an integer from 1 to
20);
[0091] b+c-1 represents an integer that equals to 2.times.m;
and
[0092] A.sup.3 represents a chemical bond or divalent organic
bridge group for linking the two benzene rings.
[0093] More particularly, A.sup.3 represents a chemical bond,
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, or --Si(R.sup.87)(R.sup.88)--,
--CH.dbd.N-Q-.dbd.CH-- or the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N, wherein R.sup.87
and R.sup.88 independently represent (C1-C20)alkyl,
(C3-C20)cycloalkyl, (C1-C15)alkyl(C6-C20)aryl, or
(C6-C20)ar(C1-C15)alkyl, and Q includes a divalent organic bridge
group for linking the two nitrogen atoms. Particularly, Q
represents (C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N. Preferably,
R.sup.61 and R.sup.63 independently represent
--[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2], Q in the formula of
--CH.dbd.N-Q-N.dbd.CH-- represents trans-1,2-cyclohexylene or
ethylene, and X(s) independently represent 2,4-dinitrophenolate or
BF.sub.4.sup.-.
[0094] According to one embodiment of the complex represented by
Chemical Formula 6, there is provided a complex represented by
Chemical Formula 7:
##STR00014##
[0095] wherein
[0096] A.sup.1 and A.sup.2 independently represent an oxygen or
sulfur atom;
[0097] X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms;
[0098] R.sup.72 and R.sup.74 are independently selected from
tert-butyl, methyl, ethyl, isopropyl and hydrogen;
[0099] R.sup.71 and R.sup.73 independently represent
-[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2]; and
[0100] b+c represents 5.
[0101] According to another embodiment of the complex represented
by Chemical Formula 6, there is provided a complex represented by
Chemical Formula 8:
##STR00015##
[0102] wherein
[0103] A.sup.4 represents a carbon or silicon atom;
[0104] A.sup.1 and A.sup.2 independently represent O or S;
[0105] X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms;
[0106] R.sup.82 and R.sup.84 are independently selected from
tert-butyl, methyl, ethyl, isopropyl and hydrogen;
[0107] R.sup.81 and R.sup.83 independently represent
--[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2];R.sup.85 and
R.sup.86 independently represent (C1-C20)alkyl, (C3-C20)cycloalkyl,
(C1-C15)alkyl(C6-C20)aryl or (C6-C20)ar(C1-C15)alkyl; and
[0108] b+c represents 5.
[0109] According to still another embodiment of the complex
represented by Chemical Formula 6, there is provided a complex
represented by Chemical Formula 9:
##STR00016##
[0110] wherein
[0111] X(s) independently represent a halide ion; BF.sub.4.sup.-;
ClO.sub.4.sup.-; NO.sub.3.sup.-; PF.sub.6.sup.-; HCO.sub.3.sup.-;
or a (C6-C20)aryloxy anion; (C1-C20)alkylcarboxy anion;
(C1-C20)alkoxy anion; (C1-C20)alkylcarbonate anion;
(C1-C20)alkylsulfonate anion; (C1-C20)alkylamide anion;
(C1-C20)alkylcarbamate anion; or anion of Meisenheimer salt with or
without at least one of halogen, nitrogen, oxygen, silicon, sulfur
and phosphorus atoms;
[0112] R.sup.92 and R.sup.94 are independently selected from
methyl, ethyl, isopropyl and hydrogen, preferably methyl;
[0113] R.sup.91 and R.sup.93 independently represent
--[CH{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2] or
--[CMe{(CH.sub.2).sub.3N.sup.+Bu.sub.3}.sub.2];
[0114] Q represents a divalent organic bridge group for linking the
two nitrogen atoms;
[0115] b+c represents 5; and
[0116] the alkyl in the alkylcarboxy anion, alkoxy anion,
alkylcarbonate anion, alkylsulfonate anion, alkylamide anion and
alkylcarbamate anion may be linear or branched.
[0117] Preferably, in the complex represented by Chemical Formula
9, Q represents trans-1,2-cyclohexylene or ethylene, and X(s)
independently represent 2,4-dinitrophenolate or BF.sub.4.sup.-. One
of the five X radicals represents BF.sub.4.sup.-, two of them
represent 2,4-dinitrophenolate, and the remaining two X radicals
represent anions represented by Chemical Formula 10:
##STR00017##
[0118] wherein
[0119] R represents methyl or H.
[0120] According to one embodiment of the complex represented by
Chemical Formula 9, there is provided a complex represented by
Chemical Formula 11:
##STR00018##
[0121] wherein
[0122] B.sup.1 through B.sup.4 independently represent
(C2-C20)alkylene or (C3-C20)cycloalkylene;
[0123] R.sup.26 represents primary or secondary (C1-C20)alkyl;
[0124] R.sup.27 through R.sup.29 are independently selected from
(C1-C20)alkyl and (C6-C30)aryl;
[0125] Q represents a divalent bridge group for linking the two
nitrogen atoms;
[0126] Z.sup.1 through Z.sup.5 are independently selected from a
halide ion; BF.sub.4.sup.-; ClO.sub.4.sup.-; NO.sub.3.sup.-;
PF.sub.6.sup.-; HCO.sub.3.sup.-; and a (C6-C30)aryloxy anion;
(C1-C20)carboxylic acid anion; (C1-C20)alkoxy anion;
(C1-C20)alkylcarbonate anion; (C1-C20)alkylsulfonate anion;
(C1-C20)alkylamide anion; (C1-C20)alkylcarbamate anion or anion of
Meisenheimer salt with or without at least one of halogen,
nitrogen, oxygen, silicon, sulfur and phosphorus atoms, wherein a
part of Z.sup.1 through Z.sup.4 coordinated at the cobalt atom may
be de-coordinated; and
[0127] the alkylene and alkyl may be linear or branched.
[0128] Preferably, in Chemical Formula 11, Q represents
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N.
[0129] Particularly, in Chemical Formula 11, B.sup.1 through
B.sup.4 independently represent (C2-C6)alkylene, preferably
propylene; R.sup.26 represents (C1-C7)alkyl; R.sup.27 through
R.sup.29 independently represent (C1-C7)alkyl, preferably R.sup.26
and R.sup.27 independently represent methyl, and R.sup.28 and
R.sup.29 independently represent butyl; Q represents ethylene,
trans-1,2-cyclohexylene or 1,2-phenylene, and more preferably
trans-1,2-cyclohexylene; and Z.sup.1 through Z.sup.5 are
independently selected from 2,4-dinitrophenolate and
BF.sub.4.sup.-.
[0130] According to one embodiment of the complex represented by
Chemical Formula 11, there is provided a complex represented by
Chemical Formula 12:
##STR00019##
[0131] wherein
[0132] p and q independently represent an integer from 1 to 19;
[0133] R.sup.26 represents primary or secondary (C1-C20)alkyl;
[0134] R.sup.27 through R.sup.29 are independently selected from
(C1-C20)alkyl and (C6-C30)aryl;
[0135] Q represents a divalent organic bridge group for linking the
two nitrogen atoms; and
[0136] Z.sup.1 through Z.sup.5 are independently selected from a
halide ion; BF.sub.4.sup.-; ClO.sub.4.sup.-; NO.sub.3.sup.-;
PF.sub.6.sup.-; HCO.sub.3.sup.-; and a (C6-C30)aryloxy anion;
(C1-C20)carboxylic acid anion; (C1-C20)alkoxy anion;
(C1-C20)alkylcarbonate anion; (C1-C20)alkylsulfonate anion;
(C1-C20)alkylamide anion; (C1-C20)alkylcarbamate anion or anion of
Meisenheimer salt with or without at least one of halogen,
nitrogen, oxygen, silicon, sulfur and phosphorus atoms, wherein a
part of Z.sup.1 through Z.sup.4 coordinated at the cobalt atom may
be de-coordinated.
[0137] Particularly, in Chemical Formula 12, Q represents
(C6-C30)arylene, (C1-C20)alkylene, (C2-C20)alkenylene,
(C2-C20)alkynylene, (C3-C20)cycloalkylene or fused
(C3-C20)cycloalkylene, wherein the arylene, alkylene, alkenylene,
alkynylene, cycloalkylene or fused cycloalkylene may be further
substituted by a substituent selected from halogen atoms,
(C1-C7)alkyl, (C6-C30)aryl and nitro groups, or may further include
at least one hetero atom selected from O, S and N. Preferably, Q
represents ethylene, trans-1,2-cyclohexylene or 1,2-phenylene, and
more preferably trans-1,2-cyclohexylene.
[0138] Particularly, in Chemical Formula 12, p and q independently
represent an integer from 1 to 5, preferably 2; R.sup.26 represents
primary or secondary (C1-C7)alkyl; R.sup.27 through R.sup.29
independently represent (C1-C7)alkyl, preferably R.sup.26 and
R.sup.27 independently represent methyl, and R.sup.28 and R.sup.29
independently represent butyl; and Z.sup.1 through Z.sup.5 are
independently selected from 2,4-dinitrophenolate and
BF.sub.4.sup.-.
[0139] In another aspect, the present invention provides a method
for preparing polycarbonate, including: carrying out
copolymerization of carbon dioxide and an epoxide compound selected
from the group consisting of C2-C20 alkylene oxide substituted or
unsubstituted by halogen or alkoxy; C4-C20 cycloalkene oxide
substituted or unsubstituted by halogen or alkoxy; and C8-C20
styrene oxide substituted or unsubstituted by halogen, alkoxy or
alkyl, in the presence of a complex selected from the complexes
represented by Chemical Formulas 1, 5, 6, 7, 8, 9, 10 and 11 and
the complexes containing ligands selected from Chemical Formulas
2a, 2b, 2c, 3 and 4, as a catalyst.
[0140] Cobalt (III) complexes obtained from Salen-type ligands
containing four quaternary ammonium salts may have different
structures depending on the structures of the ligands. Such a
different coordination structure is distinguished from a general
structure coordinated with the four ligands in that it is not
coordinated with imine. Instead of imine, the counter anion of the
quaternary ammonium salt is coordinated. This has been demonstrated
herein through .sup.1H, .sup.13C, .sup.15N NMR spectrometry, IR
spectrometry, DFT calculation, and cyclic voltammetry (CV). Such a
different coordination structure is formed when the metal
coordination portion of the Salen ligand is less sterically
hindered as a whole, for example, when the substituent at
3-position of salicylaldehyde as a component of the Salen ligand is
less sterically hindered (e.g. methyl), and when ethylene diamine
as another component of the Salen ligand is not substituted, or
when only one or two hydrogen atoms attached to the four carbon
atoms are substituted (e.g. cyclohexane diamine). On the other
hand, when the metal coordination portion of the Salen ligand is
highly sterically hindered as a whole, for example, when a bulky
substituent, such as tert-butyl, is attached to 3-position of
salicylaldehyde, or when all of the hydrogen atoms attached to the
four carbon atoms of ethylene diamine are substituted with methyl
groups, a conventionally available imine-coordinated tetradentate
compound is obtained.
[0141] The following Reaction Scheme illustrates different
coordination systems depending on the structures of Salen
ligands:
TABLE-US-00001 ##STR00020## R.sup.1 R.sup.2 *N R 7 H H .sup.15N H 5
--(CH.sub.2).sub.4-- H 9 --(CH.sub.2).sub.4--
--[(CH.sub.2).sub.4NBu.sub.3].sup.+[BF.sub.4].sup.- 10
--(CH.sub.2).sub.4-- Me ##STR00021## R.sup.1 R.sup.2 R.sup.3
R.sup.4 *N R R' 8 H H H H .sup.15N H .sup.tBu 6
--(CH.sub.2).sub.4-- H H H .sup.tBu 11 Me Me Me Me Me Me X=
2,4-dinitrophenolate
[0142] The compounds (5, 7 and 10) with a different coordination
system having no coordination with imine unexpectedly show high
activity in copolymerizing carbon dioxide/epoxide. On the contrary,
the conventional imine-coordinated tetradentate compounds (6, 8 and
11) have no activity or show low activity. It has been demonstrated
through NMR and CV studies that the conventional imine-coordinated
tetradentate compounds are more easily reduced into cobalt (II)
compounds, as compared to the compounds with a different
coordination system having no coordination with imine. Such cobalt
(II) compounds having no activity in carbon dioxide/epoxide
copolymerization.
[0143] In the compounds with a different coordination system having
no coordination with imine, the anion coordination state is related
with the temperature, solvent and ligand structure. Particularly,
the anion coordination state has been demonstrated through NMR
spectrometry in THF-d.sub.8 similar to the polymerization medium.
In the compounds [5, 7 and 10 wherein X=2,4-dinitrophenolate (also
referred to as DNP)], two DNP ligands are always coordinated to
cobalt and the remaining two DNP ligands continuously undergo
conversion/reversion between the coordinated state and the
non-coordinated state. In general, it is known that diamagnetic
hexa-coordinated cobalt (III) compounds are not active in ligand
substitution (Becker, C. A. L.; Motladiile, S. Synth. React Inorg.
Met-Org. Chem. 2001, 31, 1545.). However, in the compounds with a
different coordination system having no coordination with imine
disclosed herein, cobalt is negatively charged so that negatively
charged ligands may be de-coordinated. The de-coordinated
negatively charged ligands are bound to the cation of the
quaternary ammonium salt, and thus may not be released away from
cobalt. Basically, non-coordinated anions are thermodynamically
unstable species and tend to form coordination bonds back to
cobalt. The combination of the above two types of tendencies
contributes to the phenomenon in which two DNP ligands continuously
undergo conversion/reversion between the coordinated state and the
non-coordinated state. Several species of tetra-coordinated cobalt
(III) compounds having negatively charged cobalt have been reported
[(a) Collins, T. J.; Richmond, T. G.; Santarsiero, B. D.; Treco B.
G. R. T. J. Am. Chem. Soc. 1986, 108, 2088. (b) Gray, H. B.;
Billig, E. J. Am. Chem. Soc. 1963, 85, 2019.]. It has been also
reported that addition of anionic or neutral ligands to such
compounds causes easy conversion among the tetra-coordinated
system, penta-coordinated system and hexa-coordinated system [(a)
Langford, C. H.; Billig, E.; Shupack, S. I.; Gray, H. B. J. Am.
Chem. Soc. 1964, 86, 2958; (b) Park, J.; Lang, K.; Abboud, K. A.;
Hong, S. J. Am. Chem. Soc. 2008, 130, 16484.]. It may be stated
that such unexpectedly high activity of the compounds with a
different coordination system having no coordination with imine
disclosed herein results from the fact that the two anionic ligands
continuously undergo conversion/reversion between the coordinated
state and the non-coordinated state. The following Reaction Scheme
illustrates the mechanism of the growth of a polymer chain in
carbon dioxide/epoxide copolymerization. In this mechanism, it is
important that the carbonate anion formed at the end of the chain
attacks the coordinated epoxide from the rear side. The
above-mentioned continuous conversion/reversion between the
coordinated state and the non-coordinated state allows a way of
attacking the carbonate anion-coordinated epoxide from the rear
side. In general, a nucleophilic attack occurs by an attack on a
leaving group from the rear side. Thus, it is thought that
difference in activities depends on how easily the anion,
undergoing continuous conversion/reversion between the coordinated
state and the non-coordinated state, can be de-coordinated from
cobalt. According to NMR spectrometric analysis, binding affinities
of the anions undergoing continuous conversion/reversion between
the coordinated state and the non-coordinated state are in order of
5>10>7. Activities thereof are in reverse order.
##STR00022##
[0144] In the carbon dioxide/epoxide copolymerization reaction
catalyzed with the compound with a different coordination system
having no coordination with imine, the ratio of [water]/[catalyst]
in the polymerization system plays an important role in realizing
the catalytic activity. Even when water is removed by purifying
epoxide and carbon dioxide thoroughly, the ratio of
[water]/[catalyst] may be significantly high under such a
polymerization condition that a relatively small amount of catalyst
is added (i.e. under a ratio of [epoxide]/[catalyst] of 100,000 or
150,000). To obtain high activity (TON), it is required to realize
the polymerization under a high [epoxide]/[catalyst] ratio, such as
100,000 or 150,000. Therefore, it is required for the catalyst to
have low sensitivity to water so as to provide a commercially
useful catalyst. In the case of a catalyst having a structure of 5,
7 or 10, induction time varies greatly depending on the degree of
dewatering in the polymerization system. In other words, when the
polymerization is carried out in the dry winter season, it is
initiated after about 1-3 hours. However, when the polymerization
is carried out in the wet and hot summer season, it is initiated
sometimes after 12 hours. Once the polymerization is initiated,
similar catalytic activities (TOF) are provided in the winter and
summer seasons. In .sup.1H NMR spectrometric study, it is observed
that DNP contained in the compound attacks propylene oxide and the
reaction rate rapidly decreases in the presence of a certain amount
of water. It is estimated that such a decrease in the reaction rate
results from the hydrogen bonding of water with the anion that
undergoes continuous conversion/reversion between the coordinated
state and the de-coordinated state, followed by degradation of the
nucleophilic attacking capability.
##STR00023##
[0145] Such a great variation in the induction time depending on a
degree of dewatering loads a difficulty on commercialization
because of the requirement of optimization in the dewatering
degree. When compound 14 in the above reaction scheme is used as a
catalyst, the above problem is partially solved. Compound 14 may be
obtained under a condition of very low [propylene oxide]/[catalyst]
ratio (1,000 or lower). In this case, the amount of water remaining
in propylene oxide is not significantly higher than the amount of
catalyst. In other words, compound 14 is consistently obtained by
controlling the [water]/[catalyst] ratio at a very low level.
Compound 14 may be stored to be used as a catalyst. In the case of
compound 14, the anion undergoing continuous conversion/reversion
between the coordinated state and the de-coordinated state has
already been reacted with propylene oxide. Thus, compound 14 has
reduced sensitivity to water and the polymerization is realized
under a consistent induction time (1-2 hours). In addition,
compound 14 shows polymerization activity (TOF, 80,000 h.sup.-1) in
a short induction time (70 minutes) even under a high
[epoxide]/[catalyst] ratio of 150,000, and thus provides a higher
TON (20,000). In the case of compound 10, it is not capable of
realizing polymerization activity under a [epoxide]/[catalyst]
ratio of 150,000.
[0146] The compound with a different coordination system having no
coordination with imine disclosed herein allows production of a
compound (e.g. compound 14) having a structure in which the two DNP
ligands are converted into the anions of the Meisenheimer salt by
reacting with propylene oxide. In the case of the compound with a
different coordination structure having no coordination with imine
disclosed herein, two DNP ligands are strongly coordinated to
cobalt and the remaining two DNP ligands undergo continuous
conversion/reversion between the coordinated state and the
de-coordinated state. Therefore, the latter two DNP ligands may be
reacted rapidly with propylene oxide to provide compound 14 after 1
hour. On the other hand, in the case of an imine-coordinated
tetradentate Salen-Co(III) compound (compound 6, 8 or 11), reaction
with propylene oxide does not provide a compound (e.g. compound
14), in which only two DNP ligands are converted into the anions of
Meisenheimer salt, but causes further conversion of the remaining
DNP ligands into the anions of Meisenheimer salt. Especially,
during the reaction with propylene oxide, reduction into a cobalt
(II) compound may also significantly occur as mentioned above. As a
result, it is not possible to obtain a compound (e.g. compound 14),
in which two DNP ligands are maintained and the remaining two DNP
ligands are converted into the anions of Meisenheimer salt. In
addition, compound 14 may be prepared by the following anion
substitution reaction. In the anion substitution reaction, it is a
specific feature that one of the substituted anions of Meisenheimer
salt is converted into DNP. When an imine-coordinated tetradentate
Salen-Co (III) compound (e.g. compound 6, 8 or 11) is subjected to
the same anion substitution reaction, cobalt reduction becomes a
main reaction.
##STR00024##
[0147] Particular examples of the epoxide compound that may be used
herein include ethylene oxide, propylene oxide, butene oxide,
pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene
oxide, tetradecene oxide, hexadecene oxide, octadecene oxide,
butadiene monoxide, 1,2-epoxide-7-octene, epifluorohydrin,
epichlorohydrin, epibromohydrin, isopropyl glycidyl ether, butyl
glycidyl ether, t-butyl glycidyl ether, 2-ethylhexyl glycidyl
ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide,
cyclooctene oxide, cyclododecene oxide, alpha-pinene oxide,
2,3-epoxide norbornene, limonene oxide, dieldrin, 2,3-epoxidepropyl
benzene, styrene oxide, phenylpropylene oxide, stilben oxide,
chlorostilben oxide, dichlorostilben oxide,
1,2-epoxide-3-phenoxypropane, benzyloxymethyl oxirane,
glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxidepropyl ether,
ethoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl
naphthyl ether, or the like. The epoxide compounds may be used
alone or in combination of 24 kinds of compounds to perform
copolymerization with carbon dioxide.
[0148] The epoxide compound may be used in the polymerization using
an organic solvent as a reaction medium. Particular examples of the
solvent that may be used herein include aliphatic hydrocarbons,
such as pentane, octane, decane and cyclohexane, aromatic
hydrocarbons, such as benzene, toluene and xylene, and halogenated
hydrocarbons, such as chloromethane, methylene chloride,
chloroform, carbon tetrachloride, 1,1-dichloroethane,
1,2-dichloroethane, ethyl chloride, trichloroethane,
1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane,
1-chloro-2-methylpropane, chlorobenzene and bromobenzene. Such
solvents may be used alone or in combination. More preferably, bulk
polymerization using the monomer itself as a solvent may be
performed.
[0149] The molar ratio of the epoxide compound to the catalyst,
i.e., epoxide compound: catalyst molar ratio may be
1,000-1,000,000, preferably 50,000-200,000. Herein, the catalyst
may realize a conversion ratio (i.e., moles of the epoxide compound
consumed per mole of cobalt per hour) of 500 turnover/hr or higher.
Carbon dioxide may be used at a pressure ranging from ambient
pressure to 100 atm, preferably from 5 atm to 30 atm. The
polymerization temperature may be 20.degree. C.-120.degree. C.,
suitably 50.degree. C.-90.degree. C.
[0150] To perform polymerization of polycarbonate, batch
polymerization, semi-batch polymerization, or continuous
polymerization may be used. When using a batch or semi-batch
polymerization process, polymerization may be performed for 1-24
hours, preferably 1.54 hours. A continuous polymerization process
may also be performed for an average catalyst retention time of
1.5-4 hours.
[0151] According to one embodiment of the present invention, it is
possible to obtain polycarbonate having a number average molecular
weight (M.sub.n) of 5,000-1,000,000 and a polydispersity
(M.sub.w/M.sub.n) of 1.054.0. Herein, Mn means a number average
molecular weight as measured by GPC with calibration using
single-molecular weight distribution polystyrene standards. The
polydispersity (M.sub.w/M.sub.n) means a ratio of a weight average
molecular weight to a number average molecular weight as measured
by GPC in the same manner as described above.
[0152] The resultant polycarbonate polymer includes at least 80% of
carbonate bonds, sometimes at least 95% carbonate bonds. The
carbonate material is easily degradable polymer leaving no residue
and soot upon the combustion, and is useful as a packaging, heat
insulating, coating material, etc.
[0153] The present invention provides a method for separately
recovering a catalyst from a solution containing a copolymer and
the catalyst, including:
[0154] contacting a solution containing the copolymer and the
catalyst obtained from the above method with a solid inorganic
material, polymer material or a mixture thereof non-soluble in the
solution to form a complex of the solid inorganic material or
polymer material and the catalyst and to separate the copolymer
therefrom; and
[0155] treating the complex of the solid inorganic material or
polymer material and the catalyst with an acid or a metal salt of a
non-reactive anion in a medium that is not capable of dissolving
the solid inorganic material or polymer material to allow the
catalyst to be dissolved into the medium and to separately recover
the catalyst.
[0156] The expression "solution containing the copolymer and the
catalyst" may be a solution obtained after the polymerization and
still containing unreacted carbon dioxide and epoxide, a solution
obtained after removing carbon dioxide only, or a solution obtained
after removing both carbon dioxide and epoxide and further
introducing another solvent thereto for the post-treatment.
Preferred solvents that may be used for the post-treatment include
methylene chloride, THF, etc.
[0157] To contact the solution containing the copolymer and the
catalyst with the solid inorganic material, polymer material or a
mixture thereof, the solid inorganic material, polymer material or
a mixture thereof may be added to the solution containing the
copolymer and the catalyst, followed by filtration, or the solution
containing the copolymer and the catalyst may be passed through a
column packed with the solid inorganic material, polymer material
or a mixture thereof. The solid inorganic material may be
surface-modified or non-modified silica or alumina. The solid
polymer material may be a polymer material having a functional
group capable of inducing deprotonation by alkoxy anion. More
particularly, the functional group capable of inducing
deprotonation by alkoxy anion may be a sulfonic acid, carboxylic
acid, phenol or alcohol group.
[0158] The solid polymer material may have a number average
molecular weight of 500-10,000,000 and is preferably crosslinked.
However, non-crosslinked polymers may be used as long as they are
not dissolved in the solution containing the copolymer and the
catalyst. Particular examples of the "solid polymer material having
a functional group capable of inducing deprotonation by alkoxy
anion" include a homopolymer or copolymer containing a
constitutional unit represented by any one of Chemical Formulas 13a
to 13e in its polymer chain. Such a polymer material functioning as
a support may be non-crosslinked as long as it is not dissolved in
the above-mentioned solution. Preferably, the polymer material is
suitably crosslinked to provide decreased solubility.
##STR00025##
[0159] The present invention also provides a method for separately
recovering a catalyst from a solution containing a copolymer and
the catalyst, including:
[0160] contacting a solution containing the copolymer and the
catalyst obtained from a carbon dioxide/epoxide copolymerization
process using the above catalyst with silica to form a
silica-catalyst complex and to separate the copolymer therefrom;
and
[0161] treating the silica-catalyst complex with an acid or a metal
salt of a non-reactive anion in a medium that is not capable of
dissolving silica to allow the catalyst to be dissolved into the
medium and to separately recover the catalyst. The acid may be
2,4-dinitrophenol, and the metal salt of a non-reactive anion may
be MBF.sub.4 (wherein M represents Li, Na or K).
[0162] Reaction Scheme 1 shows a mechanism of separation and
recovery of the catalyst. When polymerizing epoxide with carbon
dioxide in the presence of the complex as a catalyst, the anion of
the ammonium salt nucleophililically attacks the activated epoxide
coordinated to the metal, thereby initiating the polymerization
reaction. The alkoxy anion formed by the nucleophilic attack reacts
with carbon dioxide to form a carbonate anion, which, in turn,
attacks nucleophilically the epoxide coordinated to the metal to
form a carbonate anion. As a result of the repetition of the above
process, a polymer chain is formed. In this case, the anions of the
ammonium salts contained in the catalyst are partially or totally
converted into the carbonate anion or alkoxide anion containing the
polymer chain. When removing carbon dioxide after the
polymerization, the carbonate anions are converted into alkoxide
anions. Then, the solution containing the catalyst and the
copolymer is allowed to be in contact with the "polymer material
having a functional group capable of inducing deprotonation by
alkoxy anion" or a solid material (e.g. silica, alumina) having a
surface hydroxyl group on the surface. As a result, the polymer
chain receives protons through an acid-base reaction as shown in
Reaction Scheme 1 so that it is maintained in the solution, while
the catalyst forms a complex with the solid inorganic material or
polymer material. Since the complex is insoluble in the solution,
it may be easily separated from the solution via filtering.
##STR00026##
[0163] After the separation via filtering, the catalyst may be
recovered and recycled from the complex of the solid inorganic
material or polymer material with the catalyst. The complex of the
solid inorganic material or polymer material with the catalyst is
not dissolved in general solvents. However, when the recovered
complex is treated with an acid or a metal salt of a non-reactive
anion in a medium that is not capable of dissolving the inorganic
material or polymer material, the catalyst may be dissolved into
the medium via an acid-base reaction or salt metathesis. The
resultant mixture may be filtered to allow the catalyst to be
isolated from the solid inorganic material or polymer material, and
then the catalyst may be separated and recovered. Herein, the acid
used for the above treatment has a pKa value equal to or lower than
the pKa value of the anion formed on the support. Preferably, the
acid may be one whose conjugate base shows excellent activity in
the polymerization in view of the reutilization. Particular
examples of such acids include HCl and 2,4-dinitrophenol. Chloride
anions and 2,4-dinitrophenolate anions are known to have high
activity and high selectivity in the polymerization. Particular
examples of the salt of a non-reactive anion include DBF.sub.4 or
DClO.sub.4 (wherein D represents Li, Na or K). Upon the treatment
with the salt of a non-reactive anion, a compound containing the
non-reactive anion is dissolved out. The non-reactive anion may be
replaced by the chloride anion and 2,4-dinitrophenolate anion
having high activity and high selectivity via salt metathesis.
Recovery of the catalyst may be carried out in a suitable solvent
in which the catalyst is dissolved but the inorganic material or
polymer material is not dissolved. Particular examples of such
solvents include methylene chloride, ethanol or methanol.
[0164] It is possible to reduce the metal content of the resin to
15 ppm or lower by removing the catalyst through the above method
after the polymerization. Therefore, the present invention also
provides a copolymer separated from the solution containing the
copolymer and the catalyst and having a metal content of 15 ppm or
lower. If the catalyst is not removed from the resin in the above
manner, the resin may still contain a metal compound that causes
coloration. This is not favorable to commercialization. In
addition, most transition metals are toxic. Thus, when the metal is
not removed from the resin, the resin is significantly limited in
its application. Further, when the polymer solution is not treated
in the above manner so that the polymer chain has no proton at the
end thereof, the polymer may be easily converted into single
molecules via the so-called backbite reaction as shown in Reaction
Scheme 2, under the condition of a slightly increased temperature
or long-term storage. This may cause a severe problem when
processing the resin and result in a significant degradation in the
durability of the resin. Under these circumstances, the resin is
not commercially acceptable. However, when treating the polymer
solution in the above manner after the polymerizaiton, the polymer
chain is provided with proton at the end thereof, and the alkoxide
anion is converted into an alcohol group, which has weaker
nucleophilic reactivity than alkoxide anion. Therefore, the
backbite reaction of Reaction Scheme 2 does not occur so that the
resin may provide good processability and durability.
##STR00027##
[0165] The complex disclosed herein may be prepared by providing an
ammonium salt-containing ligand and coordinating the ligand to
cobalt as shown in Reaction Scheme 3. A typical method for
attaching the ligand to the metal include reacting cobalt acetate
[Co(OAc).sub.2] with the ligand to de-coordinate the acetate ligand
and to remove acetic acid, thereby providing a cobalt (II)
compound, and then oxidizing the cobalt (II) compound with oxygen
as an oxidizing agent in the presence of a suitable acid (HX,
wherein X is the same as X in Chemical Formula 1) to obtain a
cobalt (III) compound. The ammonium salt-containing ligand may be
prepared according to the known method developed by the present
inventors (J. Am. Chem. Soc. 2007, 129, 8082; Angew Chem. Int. Ed.,
2008, 47, 7306-7309).
##STR00028##
[Advantageous Effects]
[0166] The complex disclosed herein is prepared from a ligand
containing a protonated group so that it takes a negative
divalently or higher valently charged form. The complex may be used
in carbon dioxide/epoxide copolymerization as a catalyst to realize
high activity and high selectivity consistently. In addition, when
carrying out carbon dioxide/epoxide copolymerization using the
complex disclosed herein as a catalyst, the catalyst having
protonated ligands is separated and recovered after the
copolymerization so that it may be recycled. In this manner, it is
possible to reduce the cost required for the catalyst and to
realize high cost efficiency when preparing the copolymer. It is
also possible to obtain a high-purity copolymer by removing the
catalyst, i.e., metal compound from the copolymer. Therefore, it is
possible to extend applications of the copolymer and to enhance the
durability and processability of the copolymer.
DESCRIPTION OF DRAWINGS
[0167] The above and other objects, features and advantages of the
present invention will become apparent from the following
description of preferred embodiments given in conjunction with the
accompanying drawings, in which:
[0168] FIG. 1 shows .sup.1H NMR spectra of compounds 7 and 8 in
DMSO-d.sub.6 as a solvent, wherein the signals labeled with X
correspond to DNP signals and the 2D spectrum in the box is
.sup.1H-.sup.1H COSY NMR spectrum of compound 7 at 20.degree.
T.
[0169] FIG. 2 shows .sup.13C NMR spectra of compounds 7 and 8 in
DMSO-d.sub.6 as a solvent.
[0170] FIG. 3 shows .sup.15N NMR spectra of compounds 7 and 8 in
DMSO-d.sub.6 as a solvent.
[0171] FIG. 4 shows .sup.1H NMR spectra of compounds 7 and 8 in
THF-d.sub.8 and CD.sub.2Cl.sub.2 as a solvent.
[0172] FIG. 5 shows IR spectra of compounds 7 and 8.
[0173] FIG. 6 shows the most stable conformation of compound 7
obtained by DFT calculation, wherein only the oxygen atoms of DNP
ligands coordinated to the metal are shown for the purpose of
simplicity.
[0174] FIG. 7 is a reaction scheme illustrating a change in the
state of DNP at room temperature depending on the solvent, in the
case of a compound with a different coordination system having no
coordination with imine (X=DNP).
[0175] FIG. 8 shows VT .sup.1H NMR spectrum of compound 7 in
THF-d.sub.8.
[0176] FIG. 9 is .sup.1H NMR spectrum illustrating the reaction
between compound 10 or 8 and propylene oxide, wherein the signals
marked with "*" correspond to new signals derived from the anion of
Meisenheimer salt.
BEST MODE
[0177] Hereinafter, the embodiments of the present invention will
be described in detail with reference to examples. However, the
following examples are for illustrative purposes only and not
intended to limit the scope of this disclosure.
EXAMPE 1
Preparation of
3-methyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sal-
icylaldehyde compound
[0178] The title compound is prepared by hydrolyzing the ligand
represented by Chemical Formula 19a. The compound represented by
Chemical Formula 19a is obtained by the known method developed by
the present inventors (Angew. Chem. Int. Ed., 2008, 47,
7306-7309).
##STR00029##
[0179] The compound represented by Chemical Formula 19a (0.500 g,
0.279 mmol) was dissolved in methylene chloride (4 mL), and then
aqueous Hl solution (2N, 2.5 mL) was added thereto and the
resultant mixture was agitated for 3 hours at 70.degree. C. The
aqueous layer was removed, the methylene chloride layer was washed
with water and dried with anhydrous magnesium chloride, and the
solvents were removed under reduced pressure. The resultant product
was purified by silica gel column chromatography eluting with
methylene chloride/ethanol (10:1) to obtain 0.462 g of
3-methyl-5-[{I.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-salicylald-
ehyde (yield 95%). The compound was dissolved in ethanol (6 mL),
and AgBF.sub.4 (0.225 g, 1.16 mmol) was added thereto, andthe
resultant mixture was stirred f filteration. The solvents were
removed under reduced pressure and the resultant product was
purified by silica gel column chromatography eluting with methylene
chloride/ethanol (10:1) to obtain 0.410 g of
3-methyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sal-
icylaldehyde compound (yield 100%).
[0180] .sup.1H NMR (CDCl.sub.3): .delta. 11.19 (s, 1H, OH), 9.89
(s, 1H, CHO), 7.48 (s, 1H, m-H), 7.29 (s, 1H, m-H), 3.32-3.26 (m,
4H, --NCH.sub.2), 3.10-3.06 (m, 12H, --NCH.sub.2), 2.77 (septet,
J=6.8 Hz, 1H, --CH--), 2.24 (s, 3H, --CH.sub.3), 1.76-1.64 (m, 8H,
--CH.sub.2), 1.58-1.44 (m, 16H, --CH.sub.2), 1.34-1.29 (m, 8H,
--CH.sub.2), 0.90 (t, J=7.6 Hz, 18H, CH.sub.3) ppm. .sup.13C
{.sup.1} NMR (CDCl.sub.3): .delta. 197.29, 158.40, 136.63, 133.48,
130.51, 127.12, 119.74, 58.23, 40.91, 32.51, 23.58, 19.48, 18.82,
15.10, 13.45 ppm.
EXAMPLE 2
Preparation of
3-t-butyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sa-
licylaldehyde compound
[0181] The title compound is prepared from the compound represented
by Chemical Formula 19b in the same manner as described in Example
1. The compound represented by Chemical Formula 19a is also
obtained by the known method developed by the present inventors
(Angew. Chem. Int. Ed., 2008, 47, 7306-7309).
##STR00030##
[0182] .sup.1H NMR (CDCl.sub.3): .delta. 11.76 (s, 1H, OH), 9.92
(s, 1H, CHO), 7.53 (s, 1H, m-H), 7.35 (s, 1H, m-H), 3.36-3.22 (m,
16H, --NCH.sub.2), 2.82 (br, 1H, --CH--), 1.78-1.70 (m, 4H,
--CH.sub.2), 1.66-1.46 (m, 16H, --CH.sub.2), 1.42 (s, 9H,
--C(CH.sub.3).sub.3), 1.38-1.32 (m, 12H, butyl --CH.sub.2), 0.93
(t, J=7.6 Hz, 18H, CH.sub.3) ppm. .sup.13C {.sup.1H} NMR
(CDCl.sub.3): .delta. 197.76, 138.70, 133.50, 132.63, 131.10,
120.40, 58.55, 41.45, 34.99, 32.28, 29.31, 23.72, 19.59,
19.00,13.54 ppm.
EXAMPLE 3
Preparation of Complex 7
[0183] Reaction Scheme 4 schematically illustrates one embodiment
of the method for preparing the complex disclosed herein.
##STR00031##
[0184] Ethylene diamine dihydrochloride (10 mg, 0.074 mmol), sodium
t-butoxide (14 mg) and
3-methyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sal-
icylaldehyde compound (115 mg) obtained from Example 1 are weighed
with vials in a dry box, and ethanol (2 mL) was added thereto,
followed by stirring at room temperature for overnight. The
reaction mixture was filtered and solvent were removed under
reduced pressure. The resultant product was redissolved into
methylene chloride and filtered once again. The solvents were
removed under reduced pressure, and Co(OAc).sub.2 (13 mg, 0.074
mmol) and ethanol (2 mL) are added thereto. The reaction mixture
was stirred for 3 hours at room temperature and then the solvents
were removed under reduced pressure. The resultant compound was
washed with diethyl ether (2 mL) twice to obtain a solid compound.
The solid compound was dissolved into methylene chloride (2 mL) and
2,4-dinitrophenol (14 mg, 0.074 mmol) was added thereto, and the
resultant mixture was stirred for 3 hours in the presence of
oxygen. Then, sodium 2,4-dinitrophenolate (92 mg, 0.44 mmol) was
added to the reaction mixture and the stirring continued for
overnight at room temperature. The reaction mixture was filtered
over a pad of Celite and the solvents were removed to obtain the
product as a dark brown solid compound (149 mg, yield 100%).
[0185] .sup.1H NMR (DMSO-d.sub.6, 40.degree. C.): .delta. 8.84 (br,
2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 8.09 (br, 2H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 8.04 (s, 1H, CH.dbd.N), 7.12 (s,
2H, m-H), 6.66 (br, 2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 4.21 (br,
2H, ethylene-CH.sub.2), 3.35-2.90 (br, 16H, NCH.sub.2), 2.62 (s,
3H, CH.sub.3), 1.91 (s, 1H, CH), 1.68-1.42 (br, 20H, CH.sub.2),
1.19 (br, 12H, CH.sub.2), 0.83 (br, 18H, CH.sub.3) ppm. .sup.1H NMR
(THF-d.sub.8, 20.degree. C.): .delta. 8.59 (br, 1H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 8.10 (br, 1H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 7.93 (s, 1H, CH.dbd.N), 7.88 (br,
1H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 7.05 (s, 1H, m-H), 6.90 (s,
1H, m-H), 4.51 (s, 2H, ethylene-CH.sub.2), 3.20-2.90 (br, 16H,
NCH.sub.2), 2.69 (s, 3H, CH.sub.3), 1.73 (s, 1H, CH), 1.68-1.38
(br, 20H, CH.sub.2), 1.21 (m, 12H, CH.sub.2), 0.84 (t, J=6.8 Hz,
18H, CH.sub.3) ppm. .sup.1H NMR (CD.sub.2Cl.sub.2, 20.degree. C.):
.delta. 8.43 (br, 1H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 8.15 (br,
1H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 7.92 (br, 1H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 7.79 (s, 1H, CH.dbd.N), 6.87 (s,
1H, m-H), 6.86 (s, 1H, m-H), 4.45 (s, 2H, ethylene-CH.sub.2), 3.26
(br, 2H, NCH.sub.2), 3.0-2.86 (br, 14H, NCH.sub.2), 2.65 (s, 3H,
CH.sub.3), 2.49 (br, 1H, CH), 1.61-1.32 (br, 20H, CH.sub.2),
1.31-1.18 (m, 12H, CH.sub.2), 0.86 (t, J=6.8 Hz, 18H, CH.sub.3)
ppm. .sup.13C{.sup.1H} NMR (DMSO-d.sub.6, 40.degree. C.): .delta.
170.33, 165.12, 160.61, 132.12 (br), 129.70, 128.97, 127.68 (br),
124.51 (br), 116.18 (br), 56.46, 40.85, 31.76, 21.92, 18.04, 16.16,
12.22 ppm. .sup.15N{.sup.1H} NMR (DMSO-d.sub.6, 20.degree. C.):
.delta. -156.32, -159.21 ppm. .sup.15N{.sup.1H} NMR (THF-d.sub.8,
20.degree. C.): .delta. -154.19 ppm. .sup.19F{.sup.1H} NMR
(DMSO-d.sub.6, 20.degree. C.): 67 -50.63, -50.69 ppm.
EXAMPLE 4
Preparation of Complex 8
[0186] Complex 8 is prepared from
3-t-butyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sa-
licylaldehyde obtained from Example 2 in the same manner as
described in Example 3.
[0187] .sup.1H NMR (DMSO-d.sub.6, 40.degree. C.): .delta. 8.82 (br,
2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 7.89 (br, 3H,
(NO.sub.2).sub.2C.sub.6H.sub.3O, CH.dbd.N), 7.21 (s, 1H, m-H), 7.19
(s, 1H, m-H), 6.46 (br, 4H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 4.12
(s, 2H, ethylene-CH.sub.2), 3.25-2.96 (br, 16H, NCH.sub.2), 1.90
(s, 1H, CH), 1.71 (s , 9H, C(CH.sub.3).sub.3), 1.67-1.32 (br, 20H,
CH.sub.2), 1.32-1.15 (m, 12H, CH.sub.2), 0.88 (t, J=7.2 Hz, 18H,
CH.sub.3) ppm. .sup.1H NMR (THF-d.sub.8, 20.degree. C.): .delta.
7.78 (s, 1H, CH.dbd.N), 7.31 (s, 1H, m-H), 7.12 (s, 1H, m-H), 4.19
(br, 2H, ethylene-CH.sub.2), 3.43-2.95 (br, 16H, NCH.sub.2), 2.48
(br, 1H, CH), 1.81-1.52 (br, 20H, CH.sub.2), 1.50 (s, 9H,
C(CH.sub.3).sub.3), 1.42-1.15 (br, 12H, CH.sub.2), 0.89 (t, J=6.8
Hz, 18H, CH.sub.3) ppm. .sup.1H NMR (CD.sub.2Cl.sub.2,20.degree.
C): .delta. 7.47. (s, 1H, CH.dbd.N), 7.10 (s, 1H, m-H), 7.07 (s,
1H, m-H), 4.24 (s, 2H, ethylene-CH.sub.2), 3.31 (br, 2H,
NCH.sub.2), 3.09-2.95 (br, 14H, NCH.sub.2), 2.64 (br, 1H, CH),
1.68-1.50 (br, 20H, CH.sub.2), 1.49 (s, 9H, C(CH.sub.3).sub.3),
1.39-1.26 (m, 12H, CH.sub.2), 0.93 (t, J=6.8 Hz, 18H, CH.sub.3)
ppm. .sup.13C{.sup.1H} NMR(DMSO-d.sub.6, 40.degree. C.): .delta.
166.57, 166.46, 161.55, 142.16, 129.99, 129.26, 128.39, 128.13,
127.63, 124.18, 118.34, 56.93, 41.64, 34.88, 32.27, 29.63, 22.37,
18.64, 18.51, 12.70 ppm. .sup.15N{.sup.1H} NMR (DMSO-d.sub.6):
-163.43 ppm. .sup.15N{.sup.1H} NMR (THF-d.sub.8, 20.degree. C.):
.delta. -166.80 ppm. .sup.19F{.sup.1H} NMR (DMSO-d.sub.6,
20.degree. C.): .delta. -50.65, -50.70 ppm.
EXAMPLE 5
Preparation of Complex 9
[0188] Complex 9 is prepared according to Reaction scheme 5.
##STR00032##
Preparation of compound 17
[0189] First, 1-chloro-4-iodobutane (1.00 g, 4.57 mmol) was
dissolved into a mixture solvent of diethyl ether/pentane (2:3) to
obtain a concentration of 0.10 M, the resultant mixture was cooled
to -78.degree. C. t-butyl lithium (3.690 g, 9.610 mmol, 1.7M
solution in pentane) was added gradually to the cooled solution of
1-chloro-4-iodobutane and stirred for 2 hours.
1,5-dichloropentane-3-one (838 mg, 4.580 mmol) dissolved in diethyl
ether (8 mL) was added gradually to the reaction mixture. The
reaction mixture was stirred for additional 4 hours at -78.degree.
C., and then ice water (50 mL) was added to quench the reaction
path, followed by extraction with diethyl ether. The organic layer
was collected and dried over anhydrous magnesium sulfate and
filtered, the solvents were removed under reduced pressure. The
obtained crude product was purified by column chromatography using
silica gel (hexane:ethyl acetate=5:1) to obtain 820 mg of compound
17 (yield 65%).
[0190] .sup.1H NMR (CDCl.sub.3): .delta. 3.52 (t, J=6.4 Hz, 6H,
CH.sub.2Cl), 1.80-1.73 (m, 6H, CH.sub.2), 1.56-1.52 (m, 4H,
CH.sub.2), 1.42 (s, 4H, CH.sub.2) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta. 73.58, 45.69, 44.95, 38.29, 36.48, 32.94,
26.96, 20.88 ppm.
Preparation of compound 18
[0191] Under nitrogen atmosphere, compound 17 (1.122 g, 4,070
mmol), o-cresol (3.521 g, 32.56 mmol), and aluminum trichloride
(0.597 g, 4,477 mmol) were added to a round bottom flask and
stirred for overnight. Diethyl ether (20 mL) and water (20 mL) were
added thereto the reaction flask, and the aqueous phase was
repeatedly extracted with diethyl ether (three times). The organic
phases are combined and dried over anhydrous magnesium sulfate,
filtered and removed the solvents under reduced pressure. The
resultant oily product was purified by column chromatography using
silica gel (hexane:ethyl acetate=10:1) to obtain 907 mg of compound
18 (yield 61%).
[0192] IR (KBr): 3535 (OH) cm.sup.-1. .sup.1H NMR (CDCl.sub.3):
.delta.7.02 (d, J=2.0 Hz, 1H, m-H), 6.99 (dd, J=8.8 Hz, 2.0 Hz, 1H,
m-H), 6.73 (d, J=8.0 Hz, 1H, o-H), 4.67 (s, 1H, OH), 3.53-3.46 (m,
6H, CH.sub.2Cl), 2.27 (s, 3H, CH.sub.3), 1.79-1.44 (m, 6H,
CH.sub.2), 1.67-1.62 (m, 2H, CH.sub.2), 1.58-1.53 (m, 4H,
CH.sub.2), 1.28-1.20 (br, 2H, CH.sub.2) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta. 151.81, 137.96, 128.89, 124.87, 114.70,
60.83, 46.05, 45.04, 42.09, 36.69, 35.07, 27.26, 21.40, 21.02,
16.54, 14.49 ppm. HRMS (FAB): m/z calcd (M.sup.+
C.sub.18H.sub.27Cl.sub.3O) 364.1131, found 365.1206
Preparation of compound 19
[0193] Compound 18 (907 mg, 2.48 mmol), paraformaldehyde (298 mg,
9.920 mmol), magnesium dichloride (944 mg, 9.92 mmol) and
triethylamine (1.051 g, 10.42 mmol) were introduced into a flask,
and tetrahydrofuran (50 mL) was added as the solvent. The reaction
mixture was refluxed for 5 hours under nitrogen atmosphere. The
reaction mixture was cooled to room temperature, and methylene
chloride (50 mL) and water (50 mL) were added thereto to extract
the organic layer. The organic layer was collected and dried over
anhydrous magnesium sulfate, filtered and removed the solvents. The
resultant product was purified by column chromatography using
silica gel (hexane:ethyl acetate=20:1) to obtain 540 mg of compound
19 (yield 58%).
[0194] IR (KBr): 2947 (OH), 1650 (C.dbd.O) cm.sup.-1. .sup.1H NMR
(CDCl.sub.3): .delta. 11.05 (s, 1H, OH), 9.78 (s, 1H, CH.dbd.O),
7.25 (s. 1H, m-H), 7.19 (s, 1H, m-H), 3.44-3.39 (m, 6H,
CH.sub.2Cl), 2.19 (s, 3H, CH.sub.3), 1.74-1.43 (m, 12H, CH.sub.2),
1.20-1.11 (br, 2H, CH.sub.2) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta. 196.79, 158.07, 136.98, 135.85, 128.95,
126.85, 119.52, 45.77, 44.88, 42.12, 36.50, 34.64, 33.09, 27.07,
20.85, 15.71 ppm. HRMS (FAB): m/z calcd (M.sup.+
C.sub.19H.sub.27Cl.sub.3O) 393.1151, found 393.1155
Preparation of compound 20
[0195] Compound 19 (520 mg, 1.304 mol) and sodium iodide (2.932 g,
19.56 mmol) were introduced into a flask, and acetonitrile (2 mL)
was added as the solvent, followed by refluxing for 12 hours. Then,
the solvent is removed under reduced pressure, methylene chloride
(5 mL) and water (5 mL) are added thereto to extract the organic
layer. The organic layer is dried over anhydrous magnesium sulfate
and the solvent is removed under reduced pressure. The resultant
product is purified through a column (hexane:ethyl acetate=20:1) to
obtain 759 mg of compound 20 (yield 87%).
[0196] IR (KBr): 2936 (OH), 1648 (C.dbd.O) cm.sup.-1. .sup.1H NMR
(CDCl.sub.3): .delta. 11.06 (s, 1H, OH), 9.80 (s, 1H, CH.dbd.O),
7.25 (s. 1H, m-H), 7.17 (d, J=2.8 Hz, 1H, m-H), 3.21-3.14 (m, 6H,
CH.sub.2Cl), 2.27 (s, 3H, CH.sub.3), 1.79-1.53 (m, 12H, CH.sub.2),
1.28-1.19 (br, 2H, CH.sub.2) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta. 196.81, 158.20, 137.00, 135.90, 128.90,
126.98, 119.54, 42.17, 38.45, 36.11, 33.93, 27.83, 24.50, 15.84,
7.96, 7.14 ppm.
Preparation of compound 21
[0197] Compound 20 (680 mg, 1.018 mmol) and cyclohexyl diamine (58
mg, 0.509 mmol) were dissolved in methylene chloride (5 mL) and the
reaction mixture was stirred for 12 hours. The resultant product
was purified by passing through a short pad of silica eluting with
methylene chloride to obtain the product as a pure yellow solid
(560 mg, yield 78%).
[0198] IR (KBr): 2933 (OH), 1629 (C.dbd.N) cm.sup.-1. .sup.1H NMR
(CDCl.sub.3): .delta. 13.45 (s, 2H, OH), 8.34 (s, 2H, CH.dbd.N),
7.05 (s, 2H, m-H), 6.941 (d, J=1.6 Hz, 2H, m-H), 3.39-3.36 (m, 2H,
cyclohexyl-CH), 3.17-3.09 (m, 12H, CH.sub.21), 2.26 (s, 6H,
CH.sub.3), 1.96-1.89 (m, 4H, cyclohexyl-CH.sub.2), 0.96-1.43 (m,
32H, cyclohexyl-CH.sub.2 and CH.sub.2), 1.18-1.20 (br, 4H,
CH.sub.2) ppm. .sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta.164.97,
157.2, 135.58, 131.25, 127.12, 125.50, 117.65, 72.89, 42.00, 38.71,
36.14, 34.18, 33.73, 27.91, 24.57, 24.50, 16.32, 8.26, 7.18
ppm.
Preparation of compound 22
[0199] Compound 21 (364 mg, 0.257 mmol) was dissolved in
acetonitrile (5 mL), and added tributylamine (291 mg, 1.57 mmol).
The reaction mixture was reflux for 2 days under nitrogen
atmosphere. The reaction mixture was cooled to room temperature,
the solvents were removed under reduced pressure, and diethyl ether
(10 mL) was added. The resultant slurry was stirred for 10 minutes
to obtain the product in solid form. Diethyl ether was decanted and
the above process was repeated twice. The yellow solid was
collected by filtration followed by washing with diethyl ether. The
residual solvents were completely by applying vacuum to obtain 579
mg of compound 22 (yield 89%).
[0200] IR (KBr): 2959 (OH), 1627 (C.dbd.N) cm.sup.-1. .sup.1H NMR
(CDCl.sub.3): .delta.. 13.46 (s, 2H, OH), 8.58 (s, 2H, CH.dbd.N),
7.18(s, 2H, m-H), 7.07 (s, 2H, m-H), 3.42 (br, 2H, cyclohexyl-CH),
3.32 (br, 16H, NCH.sub.2), 3.16 (br, 32H, NCH.sub.2), 2.10 (s, 6H,
CH.sub.3), 1.74-1.20 (br, 108H, cyclohexyl-CH.sub.2, CH.sub.2),
0.86 (t, 18H, CH.sub.3), 0.75 (t, 36H, CH.sub.3) ppm.
.sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta.164.78, 157.27, 134.04,
130.82, 127.22, 125.15, 117.46, 71.01, 9.96, 59.63, 59.00, 58.86,
53.52, 43.03, 34.89, 33.90, 33.68, 24.16, 24.05, 23.07, 22.78,
20.69,19.68, 19.53, 17.64, 15.79, 13.58 ppm.
Preparation of compound 23
[0201] Compound 22 (455 mg, 0.180 mmol) and silver tetrafluoro
borate (211 mg, 1.08 mmol) were introduced into a flask, and
methylene chloride (12 mL) is added as a solvent. The flask was
wrapped with aluminum foil and the reaction mixture was stirred at
room temperature for 1 day. The reaction mixture was filtered over
a pad of celite to remove solid, and the remaining solution was
removed under reduced pressure. The product was purified by column
chromatography using silica gel (methylene chloride:ethanol=5:1) to
obtain 322 mg of yellow compound 23 (yield 78%).
[0202] IR (KBr): 2961 (OH), 1628 (C.dbd.N) cm.sup.-1. .sup.1H NMR
(CDCl.sub.3): .delta.. 13.64 (s, 2H, OH), 8.52 (s, 2H, CH.dbd.N),
7.27(s, 2H, m-H), 7.16 (s, 2H, m-H), 3.44 (br, 2H, cyclohexyl-CH),
3.30-3.10 (br, 48H, NCH.sub.2), 2.24 (s, 6H, CH.sub.3), 1.95-1.29
(br, 108H, cyclohexyl-CH.sub.2, CH.sub.2), 0.99 (t, 18H, CH.sub.3),
0.90 (t, 36H, CH.sub.3) ppm.
Preparation of complex 9
[0203] Compound 23 (59 mg, 0.026 mmol) and Co(OAc).sub.2 (4.6 mg,
0.026 mmol) were introduced into a vial in a glove box, ethanol (1
mL) was added and the reaction mixture was stirred for 12 hours.
The solvent was removed under reduced pressure and the resultant
product was washed twice with diethyl ether to obtain a red solid.
2,4-dinitrophenol (5.0 mg, 0.026 mmol) was added to and the
reaction mixture and stirred for 3 hours in the presence of oxygen
atmosphere. sodium 2,4-dinitrophenolate (27 mg, 0.13 mmol) was
added to the reaction flask and stirred for further 12 hours. The
resultant solution was filtered over a pad of celite, removed the
solvents under reduced pressure to obtain 73 mg of a dark red
solid.
[0204] IR (KBr): 2961 (OH), 1607 (C.dbd.N) cm.sup.-1. .sup.1H NMR
(DMSO-d.sub.6, 38.degree. C.): .delta. 8.68 (br, 4H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), .delta.. 8.05 (br, 4H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 7.85 4H, m-H), 6.76 (br, 4H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 3.58 (br , 2H, cyclohexyl-CH),
3.09 (br, 48H. NCH.sub.2), 2.63 (s, 6H, CH.sub.3), 1.53-1.06 (br,
108H, cyclohexyl-CH.sub.2, CH.sub.2), 0.93-0.85 (m, 54H, CH.sub.3)
ppm.
EXAMPLE 6
Preparation of complex 10
[0205] Complex 10 is prepared according to Reaction Scheme 6.
##STR00033## ##STR00034##
Preparation of compound 24
[0206] First, 1,7-dichloroheptan-4-one (17.40 g, 95.04 mmol) was
dissolved into diethyl ether (285 mL) under nitrogen atmosphere.
The reaction mixture was cooled to -78.degree. C., MeLi (1.5 M
solution in diethyl ether 80.97 g, 142.56 mmol) was added drop wise
using a syringe under nitrogen atmosphere. The reaction mixture was
stirred for 2 hours at -78.degree. C. water (170 mL) was added at
-78.degree. C. to quench the reaction. The product was extracted
using diethyl ether. The aqueous layer was repeatedly extracted
with diethyl ether (2 times). Collected the organic phases and
dried over anhydrous magnesium sulfate, followed by filtration and
the solvents were removed under reduced pressure to obtain 17.99 g
of compound 24 (yield 95%). The resultant product may be used
directly for the subsequent reaction without further
purification.
[0207] .sup.1H NMR (CDCl.sub.3): .delta..3.59 (t, J=6.4 Hz, 4H,
CH.sub.2Cl), 1.90-1.86 (m, 4H, CH.sub.2),1.64-1.60 (m, 4H,
CH.sub.2), 1.23 (s, 3H, CH.sub.3) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta..72.32, 45.88, 39.51, 27.60, 27.23 ppm.
Preparation of compound 25
[0208] Under nitrogen atmosphere, o-cresol (78.17 g, 722.82 mmol),
compound 24 (17.99 g, 90.35 mmol) and AlCl.sub.3 (13.25 g, 99.39
mmol) were mixed in a round bottom flask and stirred overnight.
Diethyl ether (500 mL) and water (300 mL) were added to quench the
reaction. The organic layer was collected and the aqueous layer was
further extracted three times with diethyl ether (300 mL) and
collected the organic layer. The organic layer was dried over
anhydrous magnesium sulfate, followed by filtration, and then the
solvent were removed by a rotary evaporator under reduced pressure.
The excess o-cresol was removed by vacuum distillation (2 mm Hg) at
85.degree. C. The obtained product can be used for subsequent
reaction without further purification. In this manner, 25.40 g of
compound 25 was obtained (yield 97%).
[0209] .sup.1H NMR (CDCl.sub.3): .delta..7.01 (d, J=2.0 Hz, 1H,
m-H), 6.97 (dd, J=8.0 Hz, 2.0 Hz, 1H, m-H), 6.72 (d, J=8.0 Hz, 1H,
o-H), 4.85 (s, 1H, OH), 3.45 (t, J=6.4 Hz, 4H, CH.sub.2Cl), 2.27
(s, 3H, CH.sub.3), 1.86-1.44 (m, 8H, CH.sub.2), 1.30 (s, 3H,
CH.sub.3) ppm. .sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta..151.79,
138.67, 129.06, 125.02, 123.45, 114.85, 46.20, 41.12, 39.95, 28.09,
24.22, 16.58 ppm.
Preparation of compound 26
[0210] Compound 25 (25.40 g, 87.83 mmol) was dissolved in
tetrahydrofuran (650 mL) under nitrogen atmosphere.
Paraformaldehyde (10.55 g, 351.32 mmol), magnesium chloride (33.52
g, 351.32 mmol) and triethylamine (37.31 g, 368.89 mmol) were
introduced, into a flask under nitrogen atmosphere, and a refluxed
for 5 hours under nitrogen atmosphere. The solvent was removed by a
rotary evaporator under reduced pressure and methylene chloride
(500 mL) and water (300 mL) were added. The resultant mixture was
filtered over a pad of Celite to obtain a methylene chloride layer.
The aqueous layer was further extracted three times with methylene
chloride (300 mL) and combined organic layers, dried over anhydrous
magnesium sulfate and filtered, the solvents were removed by a
rotary evaporator under reduced pressure to obtain an oily
compound. The remaining trace amount of triethylamine is removed by
a vacuum pump. The resultant compound has high purity as determined
by NMR analysis and can be used for the subsequent reaction without
further purification. In this manner, 26.75 g of compound 26 was
obtained (yield 96%).
[0211] .sup.1H NMR (CDCl.sub.3): .delta..11.14 (s, 1H, OH), 9.87
(s, 1H, CH.dbd.O), 7.33 (d, J=2.4 Hz, 1H, m-H), 7.26 (d, J.dbd.2.4
Hz, 1H, m-H), 3.47 (t, J=6.4 Hz, 4H, CH.sub.2Cl), 2.30 (s, 3H,
CH.sub.3), 1.90-1.40 (m, 8H, CH.sub.2), 1.35 (s, 3H, CH.sub.3) ppm.
.sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta..196.87, 158.22, 137.56,
136.11, 128.91, 119.69, 45.88, 40.67, 39.98, 27.96, 24.06, 15.81
ppm.
Preparation of compound 27
[0212] Compound 26 (26.75 g, 84.32 mmol) was dissolved in
acetonitrile (107 mL). Sodium iodide (126.39 g, 843.18 mmol) was
added and the resulting mixture was refluxed for overnight. After
cooling the reaction mixture to room temperature, water (300 mL)
was added. The resultant solution was extracted three times with
diethyl ether (300 mL) to collect the organic layer. The organic
layer was dried over anhydrous magnesium sulfate, followed by
filtration; the solvents were removed by a rotary evaporator under
reduced pressure. The resultant product was purified through silica
gel column chromatography eluting with hexane-toluene (5:1) as
eluent to obtain the compound 27 (22.17 g, yield 83%).
[0213] .sup.1H NMR (CDCl.sub.3): .delta..11.14 (s, 1H, OH), 9.87
(s, 1H, CH.dbd.O), 7.33 (d, J=2.4 Hz, 1H, m-H), 7.25 (d, J=2.4 Hz,
1H, m-H), 3.14-3.09 (m, 4H, CH.sub.21), 2.30 (s, 3H, CH.sub.3).
1.871.43 (m, 8H, CH.sub.2), 1.34 (s, 3H, CH.sub.3) ppm.
.sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta..196.85, 158.20, 137.50,
136.09, 128.85, 126.93, 119.62, 44.28, 39.95, 28.66, 24.16, 15.81,
7.99 ppm.
Preparation of compound 28
[0214] Compound 27 (8.56 g, 17.01 mmol) was dissolved in methylene
chloride (97 mL) under nitrogen atmosphere.
(.+-.)-trans-1,2-diaminocyclohexane (0.97 g, 8.50 mmol) was added
and stirred for overnight. Solvents were removed under reduced
pressure to obtain the pure compound (9.00 g, yield 98%).
[0215] .sup.1H NMR (CDCl.sub.3): .delta..13.48 (s, 1H, OH), 8.31
(s, 1H, CH.dbd.N), 7.04 (d, J=1.6 Hz, 1H, m-H), 6.91 (d, J=1.6 Hz,
1H, m-H), 3.38-3.35 (m, 1H, cyclohexyl-CH), 3.08-3.03 (m, 4H,
CH.sub.2l), 2.25 (s, 3H, CH.sub.3), 1.96-1.89 (m, 2H,
cyclohexyl-CH.sub.2), 1.96-1.43 (m, 10H, cyclohexyl-CH.sub.2 and
CH.sub.2), 1.26 (s, 3H, CH.sub.3) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta..165.01, 157.31, 136.12, 131.35, 126.93,
125.54, 117.67, 72.94, 44.47, 39.79, 33.73, 28.72, 24.57, 24.32,
16.28, 8.38, 8.26 ppm.
Preparation of Compound 29
[0216] Compound 28 (0.855 g, 0.79 mmol) was dissolved in
acetonitrile (8.5 mL) under nitrogen atmosphere, tributyl amine
(1.17 g, 6.32 mmol) was added and the resulting solution was
refluxed for 48 hours. Solvents were removed by a rotary evaporator
under reduced pressure. Diethyl ether (20 mL) was added to the
obatained slurry and titurated for 15 minutes to precipitate the
product as solid. The ether layer was decanted and the above
process was repeated twice to obtain beige solid compound. The
solid compound was added gradually to solution of AgBF.sub.4 (0.642
g, 3.30 mmol) in ethanol (40 mL) with stirring. The reaction
mixture was agitated for 24 hours under light-shielded atmosphere,
and the resultant Agl was removed by filteration over a pad of
celite. The solvents were removed under vacuum. Then, the resultant
compound was dissolved in methylene chloride (6 mL), and further
filtered through a Celite pad to remove floating materials. The
resultant product was purified by column chromatography using
silica, eluting with mthylene chloride-ethanol (5:1) as eluent to
obtain the purified compound (1.23 g, yield 90%).
[0217] .sup.1H NMR (CDCl.sub.3): 6.13.55 (s, 1H, OH), 8.42 (s, 1H,
CH.dbd.N), 7.12 (s, 1H, m-H), 7.08 (s, 1H, m-H), 3.38 (br, 1H,
cyclohexyl-CH), 3.06 (br, 16H, NCH.sub.2), 2.20 (s, 3H, CH.sub.3),
1.88-1.84 (br, 2H, cyclohexyl-CH.sub.2), 1.68-1.26 (br, 36H),
0.87-0.86 (br, 18H, CH.sub.3) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta..165.23, 157.79, 135.21, 131.17, 127.18,
125.76, 117.91, 72.05, 59.16, 58.63, 40.16, 38.10, 37.71, 26.45,
24.91, 23.90, 20.31, 19.80, 17.30, 16.01, 13.97, 13.80, 13.79
ppm.
Preparation of complex 10
[0218] Compound 29 (100 mg, 0.06 mmol) and Co(OAc).sub.2 (10.7 mg,
0.06 mmol) were introduced into a flask and ethanol (3 mL) was
added as the solvent. The reaction mixture was stirred at room
temperature for 3 hours and removed the solvents under reduced
pressure. The obtained product was triturated 2 times with diethyl
ether to obtain the red solid compound. The residual solvents were
removed completely by applying reduced pressure. Methylene chloride
(3 mL) was added to dissolve the compound. Then, 2,4-dinitrophenol
(11.1 mg, 0.06 mmol) was introduced and the reaction mixture was
stirred for 3 hours under oxygen atmosphere. Under oxygen
atmosphere, sodium-2,4-dinitrophenolate (74.5 mg, 0.30 mmol) was
introduced and the mixture was stirred for overnight. The resultant
solution was filtered over a pad of celite and the solvents were
removed under reduced pressure to obtain the complex 10 (137 mg,
yield 100%).
[0219] .sup.1H NMR (DMSO-d.sub.6, 38.quadrature.): .delta.. 8.65
(br, 2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), .delta..7.88 (br, 3H,
(NO.sub.2).sub.2C.sub.6H.sub.3O, CH.dbd.N), 7.31 (br, 2H, m-H),
6.39 (br, 2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 3.38 (br, 1H,
cyclohexyl-CH), 3.08 (br, 16H, NCH.sub.2), 2.64 (s, 3H, CH.sub.3),
2.06-1.85 (br, 2H, cyclohexyl-CH.sub.2), 1.50-1.15 (br, 36H), 0.86
(br, 18H, CH.sub.3) ppm.
EXAMPLE 7
Preparation of complex 11
[0220]
3-methyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH-
.sub.3C}]-salicylaldehyde compound (493 mg 0.623 mmol) and
2,3-diamino-2,3-dimethylbutane (36 mg, 0.311 mmol) were introduced
into a flask. Ethanol (4 mL) was added as the solvent, molecular
sieves (180 mg) were introduced and the resultant mixture was
subjected to reflux for 12 hours under nitrogen atmosphere. The
mixture was filtered through a Celite pad to remove the molecular
sieves and removed the solvents under reduced pressure to obtain
the product as yellow solid. Co(OAc).sub.2 (55 mg, 0.31 mmol) was
added to the flask and ethanol (10 mL) as the solvent. The
resulting mixture was stirred for 5 hours at room temperature.
Solvents were removed under reduced pressure, and the resulting
compound was triturated twice with diethyl ether to obtain the red
color compound. 2,4-dinitrophenol (57 mg, 0.311 mmol) was added and
the mixture was dissolved in methylene chloride (10 mL) and stirred
for 12 hours in the presence of oxygen. Sodium-2,4-dinitrophenolate
(320 mg, 1.56 mmol) was added and the resulting reaction mixture
was stirred for further 12 hours. The solution was filtered over a
pad of celite and the solvents were removed under reduced pressure
to obtain 736 mg of a dark red solid product.
[0221] .sup.1H NMR (DMSO-d.sub.6, 38.degree. C.): .delta. 8.62 (br,
4H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 7.87 (br, 4H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 7.72 (br, 2H, CH.dbd.N), 7.50
(br, 2H, m-H), 7.35 (br, 2H, m-H) 6.47 (br, 4H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 3.11 (br, 32H, NCH.sub.2), 2.70
(s, 6H, CH.sub.3), 1.66-1.22 (br, 82H), 0.88 (br, 36H, CH.sub.3)
ppm. .sup.13C{.sup.1H} NMR (DMSO-d.sub.6): .delta. 164.67, 159.42,
132.30, 129.71, 128.86 (br), 128.46 (br), 127.42 (br), 124.05 (br),
118.84, 73.92, 57.74, 57.19, 25.94, 23.33, 22.61, 21.05,18.73,
16.68, 16.43, 12.93 ppm.
EXAMPLE 8
Preparation of complex 12
[0222] Salen ligand (500 mg, 0.301 mmol) obtained from
3-methyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sal-
icylaldehyde compound and Co(OAc).sub.2 (53 mg, 0.30 mmol) were
introduced into a flask, and added ethanol (15 mL) as solvent, the
resulting solution was stirred for 3 hours under nitrogen
atmosphere. The solvent was removed under reduced pressure, and the
resultant compound was triturated twice with diethyl ether to
obtain red color compound. The compound was dissolved in methylene
chloride (10 mL). Then, HBF.sub.4 (49 mg, 0.30 mmol) was added to
the resultant solution in the presence of oxygen, followed by
stirring for additional 3 hours. After that, the solvents were
removed under reduced pressure to obtain 520 mg of a pure compound.
Complex 12 was prepared according to the known method developed by
the present inventors (Angew. Chem. Int. Ed., 2008, 47,
7306-7309).
EXAMPLE 9
Preparation of complex 13
[0223] Complex 13 was obtained with a Salen ligand obtained from
3-t-butyl-5-[{BF.sub.4.sup.-Bu.sub.3N.sup.+(CH.sub.2).sub.3}.sub.2CH}]-sa-
licylaldehyde compound in the same manner as described in Example
8.
[0224] .sup.1H NMR (DMSO-d.sub.6, 40.degree. C.): .delta. 7.68 (s,
1H, CH.dbd.N), 7.36 (s, 1H, m-H), 7.23 (s, 1H, m-H), 3.61 (br, 1H,
NCH), 3.31-2.91 (br, 16H, NCH.sub.2), 2.04 (br, 1H,
cyclohexyl-CH.sub.2), 1.89 (br, 1H, cyclohexyl-CH.sub.2), 1.74 (s,
9H, C(CH.sub.3).sub.3), 1.68-1.35 (br, 20H, CH.sub.2), 1.32-1.18
(br, 12H, CH.sub.2), 0.91 (t, J=7.2 Hz, 18H, CH.sub.3) ppm.
.sup.13C{.sup.1H} NMR d.sub.6): .delta. 161.66, 160.42, 140.90,
129.71, 128.38, 127.31, 117.38, 67.40, 55.85, 33.89, 31.11, 28.70,
27.70 (br), 22.58, 21.29, 19.47, 17.45, 15.21, 11.69 ppm.
EXAMPLE 10
Preparation of complex 14
[0225] Compound 10 was dissolved in propylene oxide, and the
solution was allowed to stand for 1 hour and then removed the
solvents under vacuum to obtain the complex 14.
[0226] .sup.1H NMR (DMSO-d.sub.6): .delta. 8.59 (s, 1H,
(NO.sub.2).sub.2C.sub.6H.sub.3O), 8.42 (s, 1H, spiro-Meisenheimer
anion), 7.74 (s, 1H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 7.39-6.98(m,
3H, m-H, CH.dbd.N), 6.81 (s, 1H, spiro-Meisenheimer anion), 6.29
(s, (NO.sub.2).sub.2C.sub.6H.sub.3O), 5.35 (s, 1H,
spiro-Meisenheimer anion), 4.43-4.29 (m, 1H, spiro-Meisenheimer
anion), 4.21-3.99 (m, 2H, spiro-Meisenheimer anion), 3.21 (br, 1H,
NCH), 3.09 (br, 16H, NCH.sub.2), 2.93 (m, 3H, spiro-Meisenheimer
anion), 2.62 (s, 3H, CH.sub.3), 1.98 (br, 1H, cyclohexyl-CH.sub.2),
1.62-1.39 (br, 20H, CH.sub.2), 1.39-1.15 (br, 15H, CH.sub.2,
CH.sub.3), 0.91 (br, 18H, CH.sub.3) ppm.
EXAMPLE 11
Preparation of complex 35a
##STR00035##
[0227] Preparation of 1 ,7-d ichloro4-methvlheptan4-ol
[0228] Under nitrogen atmosphere, 1,7-dichloro4-methylheptan4-one
(17.40 g, 95.04 mmol) was dissolved in diethyl ether (285 mL). The
reaction mixture was cooled to -78.degree. C. and MeLi (1.5 M
solution in diethyl ether, 80.97 g, 142.56 mmol) was added dropwise
using a syringe under nitrogen atmosphere. The resulting mixture
was stirred for 2 hours at -78.degree. C. Water (170 mL) was added
at -78.degree. C. to quench the reaction path. The reaction mixture
was extracted three times with diethyl ether (300 mL) and collected
the organic phases. Combined the organic layers and dried over
anhydrous magnesium sulfate, followed by filtration, and the
solvents were removed by a rotary evaporator under reduced pressure
to obtain 17.99 g (yield 95%) of the title compound, which may be
used for the subsequent reaction without further purification.
[0229] .sup.1H NMR (CDCl.sub.3): .delta.. 3.59 (t, J=6.4 Hz, 4H,
CH.sub.2Cl), 1.90-1.86 (m, 4H, CH.sub.2), 1.64-1.60 (m, 4H,
CH.sub.2), 1.23 (s, 3H, CH.sub.3) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta.. 72.32, 45.88, 39.51, 27.60, 27.23.
Preparation of complex 35a
[0230] Under nitrogen atmosphere, o-cresol (78.17 g, 722.82 mmol),
1,7-dichloro-4-methylheptane4-ol (17.99 g, 90.35 mmol) and
AlCl.sub.3 (13.25 g, 99.39 mmol) were mixed in a round bottom flask
and stirred overnight. Next, diethyl ether (500 mL) and water (300
mL) are introduced thereto to quench the reaction. The organic
layers were collected, and the aqueous layer was further extracted
three times with diethyl ether (300 mL). Combined the organic
phases and dried over anhydrous magnesium sulfate, followed by
filtration, and the solvents were removed by a rotary evaporator
under reduced pressure. The excess o-cresol was removed by vacuum
distillation (2 mmHg) at an oil bath temperature of 85.degree. C.
The compound remaining in the flask has a purity sufficient to be
used for the subsequent reaction without further purification. In
this manner, 25.40 g of complex 35a is obtained (yield 97%).
[0231] .sup.1H NMR (CDCl.sub.3): .delta.. 7.01 (d, J=2.0 Hz, 1H,
m-H), 6.97 (dd, J=8.0 Hz, 2.0 Hz, 1H, m-H), 6.72 (d, J=8.0 Hz, 1H,
o-H), 4.85 (s, 1H, OH), 3.45 (t, J=6.4 Hz, 4H, CH.sub.2Cl), 2.27
(s, 3H, CH.sub.3), 1.86-1.44 (m, 8H, CH.sub.2), 1.30 (s, 3H,
CH.sub.3) ppm. .sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta.. 151.79,
138.67, 129.06, 125.02, 123.45, 114.85, 46.20, 41.12, 39.95, 28.09,
24.22, 16.58
EXAMPLE 12
Preparation of complex 39a
##STR00036##
[0232] Preparation of complex 36a
[0233] Complex 35a (25.40 g, 87.83 mmol) was dissolved in
tetrahydrofuran (650 mL) under nitrogen atmosphere.
Paraformaldehyde (10.55 g, 351.32 mmol), magnesium chloride (33.52
g, 351.32 mmol) and triethylamine (37.31 g, 368.89 mmol) were
introduced, into a flask under nitrogen atmosphere, and a refluxed
for 5 hours under nitrogen atmosphere. The solvent was removed by a
rotary evaporator under reduced pressure and methylene chloride
(500 mL) and water (300 mL) were added. The resultant mixture was
filtered over a pad of Celite to obtain a methylene chloride layer.
The aqueous layer was further extracted three times with methylene
chloride (300 mL) and combined organic layers, dried over anhydrous
magnesium sulfate and filtered, the solvents were removed by a
rotary evaporator under reduced pressure to obtain an oily
compound. The remaining trace amount of triethylamine is removed by
a vacuum pump. The resultant compound has high purity as determined
by NMR analysis and can be used for the subsequent reaction without
further purification. In this manner 26.75 g of complex 36a was
obtained (yield 96%).
[0234] .sup.1H NMR (CDCl.sub.3): .delta.. 11.14 (s, 1H, OH), 9.87
(s, 1H, CH.dbd.O), 7.33 (d, J=2.4 Hz, 1H, m-H), 7.26 (d, J=2.4 Hz,
1H, m-H), 3.47 (t, J=6.4 Hz, 4H, CH.sub.2Cl), 2.30 (s, 3H,
CH.sub.3), 1.90-1.40 (m, 8H, CH.sub.2), 1.35 (s, 3H, CH.sub.3) ppm.
.sup.13C{.sup.1H} NMR (CDCl.sub.3):.delta.. 196.87, 158.22, 137.56,
136.11, 128.91, 119.69, 45.88, 40.67, 39.98, 27.96, 24.06,
15.81.
Preparation of complex 37a
[0235] Complex 36a (26.75 g, 84.32 mmol) was dissolved in
acetonitrile (107 mL). Sodium iodide (126.39 g, 843.18 mmol) was
added to the solution and the resulting solution was refluxed for
overnight. After cooling the mixture to room temperature, water
(300 mL) was added to quench the reaction path. The resultant
solution was extracted three times with diethyl ether (300 mL) and
collected the organic layes. The collected organic layer was dried
over anhydrous magnesium sulfate, followed by filtration, and the
solvents were removed by a rotary evaporator under reduced
pressure. The resultant compound was purified by column
chromatography using silica gel, eluting with hexane-toluene (5:1)
as eluent to obtain pure complex 37a (22.17 g, yield 83%).
[0236] .sup.1H NMR (CDCl.sub.3): .delta.. 11.14 (s, 1H, OH), 9.87
(s, 1H, CH.dbd.O), 7.33 (d, J=2.4 Hz, 1H, m-H), 7.25 (d, J=2.4 Hz,
1H, m-H), 3.14-3.09 (m, 4H, CH.sub.2l), 2.30 (s, 3H, CH.sub.3),
1.87-1.43 (m, 8H, CH.sub.2), 1.34 (s, 3H, CH.sub.3) ppm.
.sup.13C{.sup.1H} NMR (CDCl.sub.3): .delta.. 196.85, 158.20,
137.50, 136.09, 128.85, 126.93, 119.62, 44.28, 39.95, 28.66, 24.16,
15.81, 7.99.
Preparation of complex 38a
[0237] Complex 37a (8.56 g, 17.01 mmol) was dissolved in methylene
chloride (97 mL) under nitrogen atmosphere.
(.+-.)-trans-1,2-diaminocyclohexane (0.97 g, 8.50 mmol) was added
and stirred for overnight. The solvents were removed under reduced
pressure to obtain pure complex 38a (9.00 g, yield 98%).
[0238] .sup.1H NMR (CDCl.sub.3): .delta.. 13.48 (s, 1H, OH), 8.31
(s, 1H, CH.dbd.N), 7.04 (d, J=1.6 Hz, 1H, m-H), 6.91 (d, J=1.6 Hz,
1H, m-H), 3.38-3.35 (m, 1H, cyclohexyl-CH), 3.08-3.03 (m, 4H,
CH.sub.2l), 2.25 (s, 3H, CH.sub.3), 1.96-1.89 (m, 2H,
cyclohexyl-CH.sub.2), 1.96-1.43 (m, 10H, cyclohexyl-CH.sub.2 and
CH.sub.2), 1.26 (s, 3H, CH.sub.3) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta.. 165.01, 157.31, 136.12, 131.35, 126.93,
125.54, 117.67, 72.94, 44.47, 39.79, 33.73, 28.72, 24.57,
24.32,16.28, 8.38, 8.26.
Preparation of complex 39a
[0239] Complex 38a (0.855 g, 0.79 mmol) is dissolved into
acetonitrile (8.5 mL) under nitrogen atmosphere, tributyl amine
(1.17 g, 6.32 mmol) was added and the resulting solution was
refluxed for 48 hours. Solvents were removed by a rotary evaporator
under reduced pressure. Diethyl ether (20 mL) was added to the
obatained slurry and titurated for 15 minutes to precipitate the
product as solid. The ether layer was decanted and the above
process was repeated twice to obtain beige solid compound. The
solid compound was added gradually to solution of AgBF.sub.4 (0.642
g, 3.30 mmol) in ethanol (40 mL) with stirring. The reaction
mixture was agitated for 24 hours under light-shielded atmosphere,
and the resultant Agl was removed by filteration over a pad of
celite. The solvents were removed under vacuum. Then, the resultant
compound was dissolved in methylene chloride (6 mL), and further
filtered through a Celite pad to remove floating materials. The
resultant product was purified by column chromatography using
silica, eluting with mthylene chloride-ethanol (5:1) as eluent to
obtain the 39a (1.23 g, yield 90%).
[0240] .sup.1H NMR (CDCl.sub.3): .delta.. 13.55 (s, 1H, OH), 8.42
(s, 1H, CH.dbd.N), 7.12 (s, 1H, m-H), 7.08 (s, 1H, m-H), 3.38 (br,
1H, cyclohexyl-CH), 3.06 (br, 16H, NCH.sub.2), 2.20 (s, 3H,
CH.sub.3), 1.88-1.84 (br, 2H, cyclohexyl-CH.sub.2), 1.68-1.26 (br,
36H), 0.87-0.86 (br, 18H, CH.sub.3) ppm. .sup.13C{.sup.1H} NMR
(CDCl.sub.3): .delta.. 165.23, 157.79, 135.21, 131.17, 127.18,
125.76, 117.91, 72.05, 59.16, 58.63, 40.16, 38.10, 37.71, 26.45,
24.91, 23.90, 20.31, 19.80,17.30,16.01, 13.97, 13.80, 13.79
EXAMPLE 13
Preparation of complex 40a
##STR00037##
[0241] Preparation of complex 40a
[0242] Complex 39a (100 mg, 0.06 mmol) and Co(OAc).sub.2 (10.7 mg,
0.06 mmol) were introduced into a flask and ethanol (3 mL) was
added as the solvent. The reaction mixture was stirred at room
temperature for 3 hours and removed the solvents under reduced
pressure. The obtained product was triturated 2 times with diethyl
ether to obtain the red solid compound. The residual solvents were
removed completely by applying reduced pressure. Methylene chloride
(3 mL) was added to dissolve the compound. Then, 2,4-dinitrophenol
(11.1 mg, 0.06 mmol) was introduced and the reaction mixture was
stirred for 3 hours under oxygen atmosphere. Under oxygen
atmosphere, sodium-2,4-dinitrophenolate (74.5 mg, 0.30 mmol) was
introduced and the mixture was stirred for overnight. The resultant
solution was filtered over a pad of celite and the solvents were
removed under reduced pressure to obtain the complex 40a (138 mg,
yield 100%).
[0243] .sup.1H NMR (DMSO-d.sub.6, 38.degree. C.): .delta.. 8.65
(br, 2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), .delta.. 7.88 (br, 3H,
(NO.sub.2).sub.2C.sub.6H.sub.3O, CH.dbd.N), 7.31 (br, 2H, m-H),
6.39 (br, 2H, (NO.sub.2).sub.2C.sub.6H.sub.3O), 3.38 (br, 1H,
cyclohexyl-CH), 3.08 (br, 16H, NCH.sub.2), 2.64 (s, 3H, CH.sub.3),
2.06-1.85 (br, 2H, cyclohexyl-CH.sub.2), 1.50-1.15 (br, 36H), 0.86
(br, 18H, CH.sub.3) ppm.
EXAMPLE 14
Structural Analysis of Complexes
[0244] Complexes 7 and 8 obtained from Examples 3 and 4 are
subjected to intensive structural analysis.
[0245] (1) .sup.1H, .sup.13C and .sup.15N NMR Spectra and IR
Spectrum
[0246] FIGS. 1, 2, 3, 4 and 5 show .sup.1H NMR spectrum, .sup.13C
NMR spectrum and .sup.15N NMR spectrum of compounds 7 and 8 in
DMSO-d.sub.6 as a solvent, and .sup.1H NMR spectra of compounds 7
and 8 in THF-d.sub.8 and CD.sub.2Cl.sub.2 as solvents. It can be
seen that the two compounds show clearly different behaviors. In
the case of complex 8 prepared from a ligand wherein R is t-butyl,
sharp signals appear in both .sup.1H NMR spectrum and .sup.13C NMR
spectrum. This is a typical behavior of tetradentate Salen-Co (III)
compound. In the .sup.15N NMR spectrum, only one signal appears at
-163.43 ppm regardless of temperature.
[0247] In the .sup.1H NMR spectrum and .sup.13C NMR spectrum of
complex 7 (Example 3) prepared from a ligand wherein R is methyl, a
very complex and broad signal appears at room temperature, a simple
and broad signal is obtained at 40.degree. C., and a sharp signal
is obtained at 80.degree. C. The ratio of [DNP]/[Salen-unit]
obtained from integration of the .sup.1H NMR spectrum is near 4.0
rather than 5.0 observed in the case of complex 8. As determined by
.sup.15N NMR, two signals appear at -156.32 and -159.21 ppm under
room temperature, a broad signal including two fused signals
appears at 40.degree. C, and only one sharp signal appears at
80.degree. C.
[0248] Complexes 7 and 8 show significantly different behaviors as
determined by .sup.1H NMR spectrometry in THF-d.sub.8 or
CD.sub.2Cl.sub.2 (FIG. 4). In the .sup.1H NMR spectrum of complex
8, a set of Salen-unit signals appears and a very broad DNP signal
appears. Especially, some signals appear at an abnormal range, -2
to 0 ppm. This suggests that some paramagnetic compounds are
present. In the case of .sup.1H NMR spectrum of complex 7, only one
set of Salen-unit signals appears, which has a significantly
different chemical shift from complex 8. Broad DNP signals are
observed at 7.88, 8.01 and 8.59 ppm. However, the ratio of
[DNP]/[Salen-unit] integration is about 2.0, and only two DNP
signals are observed among the four DNP signals observed in
DMSO-d.sub.6 with the remaining two non-observed. As determined in
CD.sub.2Cl.sub.2, .sup.1H NMR spectrometric behaviors of complexes
7 and 8 are similar to those in THF-d.sub.8.
[0249] In the .sup.15N NMR spectrum in THF-d.sub.8, a sharp signal
appears at -166.80 ppm (complex 8) or -154.32 ppm (complex 7). It
is not reasonable to regard such a difference in chemical shift
values of 12.5 ppm as a difference caused merely by the effect of
substituents. It is reported that chemical shift values in the
.sup.15N NMR spectrum of imine compounds
(--N.dbd.C--C.sub.4H.sub.4--X) and hydrazone compounds
(N--N.dbd.C--C.sub.4H.sub.4--X) follow the Hammeft type equation
with a gradient of about 10. Considering a difference caused by the
methyl and t-butyl substituents, the two substituents contribute a
difference in chemical shift values of 1 ppm or less (Neuvonen, K.;
Fulop, F.; Neuvonen, H.; Koch, A.; Kleinpeter, E.; Pihlaja, K. J.
Org. Chem. 2003, 68, 2151). In addition, in the case of
dipyrrolmethene ligand and zinc (II) compounds obtained therefrom,
substitution of hydrogen with ethyl provides a difference in
chemical shift values of 2 ppm in .sup.15N NMR spectrometry (Wood,
T. E.; Berno, B.; Beshara, C. S.; Thompson, Alison, J. Org. Chem.
2006, 71, 2964). In fact, when viewed from the state of ligands
used for preparing complexes 7 and 8, chemical shift difference is
as low as 2.86 ppm. Therefore, it can be thought that the value of
chemical shift of 12.5 ppm as observed herein results from
different structures of the two complexes, i.e. complexes 7 and 8.
When observing .sup.15N NMR spectrum in THF-d.sub.8 while varying
temperature, complex 7 shows a relatively broadened signal as the
temperature decreases, resulting in a full width at half maximum
(FWHM) of 10 ppm at -75.degree. C. On the other hand, complex 8
shows a relatively sharp signal at -75.degree. C as determined by a
FWHM of 1.5 ppm. The above results suggest that complex 8 has a
general structure of rigid Salen-Co (III) compounds to which all of
the four ligands of Salen are coordinated, while complex 7 has a
more flexible structure different therefrom.
[0250] As shown in FIG. 5, the two complexes show clearly different
signals in a range of 1200-1400 cm.sup.-1corresponding to the
symmetric vibration of --NO.sub.2 in IR spectra.
[0251] (2) Suggestion of Structure of Complexes
[0252] It can be said that complex 8 has a structure of a general
Salen ligand-containing cobalt complex in which all of the four
ligands of Salen are coordinated to cobalt, when observed by the
.sup.1H, .sup.13C, and .sup.15N NMR spectra. After carrying out
ICP-AES, elemental analysis and .sup.19F NMR spectrometry, it is
found that one equivalent of NaBF.sub.4 is inserted into the
complex. In the .sup.1H NMR spectrum, a broad DNP signal is
observed, which suggests that the DNP ligand undergoes continuous
conversion/reversion between the coordinated state and the
de-coordinated state. As a part of the conversion/reversion, a
square-pyramidal cobalt compound may be present transiently and the
square-pyrimidal compound is known to be a paramagnetic compound
[(a) Konig, E.; Kremer, S.; Schnakig, R.; Kanellakopulos, B. Chem.
Phys. 1978, 34, 79. (b) Kemper,S.; Hrobarik, P.; Kaupp, M.;
Schlorer, N. E. J. Am. Chem. Soc. 2009, 131, 4172.]. Therefore, an
abnormal signal is always observed at -2 to 0 ppm in the .sup.1H
NMR spectrum of complex 8.
[0253] When complex 7 has the above-mentioned non-imine coordinated
structure, the analytic data may be understood. In addition, the
structure is demonstrated through the following DFT calculation and
electrochemical experiments. The structure is characterized in that
four DNP ions, which are conjugate anions of quaternary ammonium
salt, are coordinated instead of imine. The last operation of the
catalyst preparation includes reaction with 5 equivalents of NaDNP
suspended in CH.sub.2Cl.sub.2 to perform a change of [BF4].sup.-
into DNP anion. [DNP]/[Salen-unit] integration ratio is 4.0 and
this is not significantly changed even when using a more excessive
amount of NaDNP (10 equivalents) or when increasing the reaction
time. In other words, one among the four BF.sub.4 remains
unsubstituted. Since BF.sub.4 signals are observed in .sup.19F NMR
but Na.sup.+ ion is not observed from ICP-AES analysis unlike
complex 8, it can be seen that BF.sub.4 anion is present as a
conjugate anion of quaternary ammonium salt. Even when preparing a
catalyst with ligands having more quaternary ammonium salt units
like complex 9, only the compound having four DNP ligands are
observed even in the presence of a significantly excessive amount
of NaDNP and even after a longer time. It is thought that an
octahedral coordination compound having two Salen-phenoxy ligands
and four DNP ligands is obtained in methylene chloride as a
solvent, and formation of the octahedral compound causes the anion
exchange. Cobalt (III) metal is classified into hard acid, and the
hard acid prefers DNP to imine-base, resulting in the compound with
such a different structure. In the case of complex 8, steric
hindrance of t-butyl hinders formation of such a compound. The
octahedral cobalt (III) compound in which cobalt has a charge of -3
is previously known [(a) Yagi, T.; Hanai, H.; Komorita, T.; Suzuki
T.; Kaizaki S. J. Chem. Soc., Dalton Trans. 2002, 1126. (b) Fujita,
M.; Gillards, R. D. i Polyhedron 1988, 7, 2731.]
[0254] Complexes 5, 9 and 10 provide .sup.1H and .sup.13C NMR
spectrum and IR spectrum behaviors similar to complex 7, and thus
may be regarded as a complex with a different coordination system
having no imine coordination. Particularly, complex 5 has been
regarded as a general Salen-compound structure having imine
coordination like complex 8 in the previously known publication of
the present inventors (Angew. Chem. Int. Ed., 2008, 47, 7306-7309)
and patent applications [Korean Patent Application No.
10-2008-0015454 (2008. 02. 20, titled with "METHOD FOR RECOVERING
CATALYST FROM COPOLYMER PREPARATION PROCESS", Bun Yeoul Lee, Sujith
S, Eun Kyung Noh, Jae Ki Min, "A PROCESS PRODUCING POLYCARBONATE
AND A COORDINATION COMPLEXES USED THEREFOR" PCT/KR2008/002453 (Apr.
30, 2008.); Sujith S, Jae Ki Min, Jong Eon Seong, Sung Jea Na, and
Bun Yeoul Lee* "A HIGHLY ACTIVE AND RECYCLABLE CATALYTIC SYSTEM FOR
CO.sub.2/(PROPYLENE OXIDE)"]. However, it is found herein that
complex 5 has such a different structure.
[0255] Complexes 6 and 11 provide .sup.1H and .sup.13C NMR spectrum
and IR spectrum behaviors similar to complex 8, and thus may be
regarded as a general Salen-compound structure having imine
coordination.
[0256] (3) DFT Calculation
[0257] DFT calculation is carried out to determine the structures
and energy levels of complex 7 with a different coordination
structure having no imine coordination, and another complex that
are an isomer of complex 7 and have a general imine coordination
structure, wherein two DNP ligands are coordinated at the axial
site and the remaining two are present in a free state. FIG. 6
shows the most stable conformation of complex 7 obtained from the
calculation. As can be seen from FIG. 6, complex 7 with a different
structure having no imine coordination as disclosed herein has a
more stable energy level than the general imine-coordinated
structure by 132 kcal/mol. Such a difference in energy levels is
significant.
[0258] (4) Movability of DNP Ligand
[0259] When observed from .sup.1H NMR in methylene chloride used in
the last anion exchange reaction during the preparation of a
catalyst, complexes 7, 9 and 10 show DNP signals at 8.4, 8.1 and
7.9 ppm with a [DNP]/[Salen-unit] integration ratio of 2.0 (FIG.
4). In other words, only two DNP ligands are observed among the
four DNP ligands with the remaining two non-observed. This is
because two DNP ligands undergo continuous conversion/reversion
between the coordinated state and the non-coordinated state at a
level of NMR time.
[0260] On the other hand, in the case of complex 5, four DNP
signals are observed at the same range. The DNP signals observed
herein has a chemical shift greatly different from the chemical
shift of [Bu.sub.4N]+[DNP].sup.-. Thus, it is though that the
observed signals result from DNP coordinated in the complex. In
other words, in the case of complexes 7, 9 and 10, two DNP ligands
are coordinated and the remaining two undergo continuous
conversion/reversion between the coordinated state and
de-coordinated state in methylene chloride solvent at room
temperature. In the case of complex 5, four DNP ligands are
coordinated. FIG. 7 is a reaction scheme illustrating a change in
the state of DNP at room temperature depending on the solvent, in
the case of a compound with a different coordination system having
no coordination with imine. As demonstrate by FIG. 7, the above
statement that the complex obtained from the last anion exchange
reaction has an octahedral coordination structure having two
Salen-phenoxy ligands and four DNP ligands conforms to the
structure adopted from the DFT calculation.
[0261] In addition, as observed from .sup.1H NMR spectrum of
complex 7 measured in THF-d.sub.8 at room temperature, signals
corresponding to the two coordinated DNP ligands are observed at
8.6, 8.1 and 7.9 ppm (FIG. 4). When the temperature is reduced to
0.degree. C., the signals become sharper and a signal coupling
behavior is observed. The coordinated DNP signals may be more
clearly understood by determining .sup.1H-.sup.1H COSY NMR spectrum
(FIG. 8). When the temperature is further reduced to -25.degree.
C., a new DNP signal is observed (marked with `*` in FIG. 8). The
new signal has a similar chemical shift to [Bu.sub.4N]+DNP.sup.-.
Thus, the new signal may be regarded as DNP remaining in the
de-coordinated state for a long time. At 70.degree.0 C., four DNP
ligands are observed as one set of broad signals at 9.3, 9.0 and
7.8 ppm. This is similar to the chemical shift of the coordinated
DNP signal, and it is thought that all of the four DNP ligands
remain in the coordinated state for a long time. In other words, as
the temperature increases, DNP ligands may be more adjacent to the
cobalt center. The de-coordinated DNP ligands are surrounded with
solvent molecules, resulting in a decrease in entropy. Such
de-coordination accompanied with a decrease in entropy is preferred
at low temperature. Thus, de-coordinated signals are observed at
reduced temperature, while a shift into the coordinated state is
observed at high temperature. Similarly, a transition from a
contact ion pair to a solvent separated ion pair at reduced
temperature is well known [(a) Streitwieser Jr., A.; Chang, C. J.;
Hollyhead, W. B.; Murdoch, J. R. J. Am. Chem. Soc. 1972, 94, 5288.
(b) Hogen-Esch, T. E.; Smid, J. J. Am. Chem. Soc. 1966, 88,
307.(c)Lu, J.-M.; Rosokha, S. V.; Lindeman, S. V.; Neretin, I. S.;
Kochi, J. K. J. Am. Chem. Soc. 2005, 127, 1797]. FIG. 8 shows VT
.sup.1H NMR spectrum of compound 7 in THF-d.sub.8.
[0262] Salen Complex 8 coordinated with imine shows highly
different .sup.1H NMR spectrum in THF-d.sub.8, as compared to
complex 7. This demonstrates that complexes 7 and 8 have different
structures. When reducing the temperature to 0.degree. C., all DNP
signals become broadened so that any signals may not be observed.
At -25.degree. C., a relatively sharp DNP signal set is observed at
8.1, 7.6 and 6.8 ppm with a [DNP]/[Salen-unit] integration ratio of
2.0. In addition, a significantly broad set of signals is observed
at 8.9, 8.0 and 6.8 ppm, and these chemical shift values are
similar to the chemical shift values (8.7, 8.0 and 6.8 ppm) of DNP
remaining in the de-coordinated state for a long time as observed
in complex 7. At -50.degree. C., the two sets of signals become
sharper so that two sets of DNP signals may be seen clearly. The
DNP signals observed at 8.1, 7.6 and 6.8 ppm may correspond to two
DNP ligands coordinated at the axial site of the conventional Salen
coordination complex. Another set of signals observed at 8.9, 8.0
and 6.8 ppm may correspond to the de-coordinated state.
[0263] The state of DNP in THF at room temperature depending on the
structure of ligand is demonstrated via .sup.1H NMR. In the case of
complex 7, a set of signals of two coordinated DNP ligands is
observed and the remaining two DNP ligands are not observed. This
suggests that the two DNP ligands that are not observed herein
undergo continuous conversion/reversion between the coordinated
state and the de-coordinated state. On the other hand, in the cases
of complexes 5, 9 and 10, two sets of signals, i.e., one set of two
coordinated DNP signals and another set of signals of two DNP
ligands remaining mainly in the de-coordinated state are observed.
The signals of two DNP ligands remaining mainly in the
de-coordinated state as observed in complexes 9 and 10 are broader
than the corresponding signals in complex 5. This suggests that the
two DNP ligands in complexes 9 and 10 remain in the de-coordinated
state for a shorter time as compared to complex 5. As a result, the
degree of retention (binding affinity to cobalt) of the two DNP
ligands remaining mainly in the de-coordinated state is in order of
7>9 and 10>5.
[0264] As determined from .sup.1H NMR spectrum of complexes 5, 7, 9
and 10 in DMSO-d.sub.6 at 40.degree. C., four DNP ligands are
observed as a set of broad signals (FIG. 1). The chemical shift
values of the signals (8.6, 7.8 and 6.4 ppm) are similar to the
chemical shift values of [Bu.sub.4N].sup.+DNP.sup.- (8.58, 7.80 and
6.35 ppm). Therefore, it can be said that the four DNP ligands
remain mainly in the de-coordinated state at 40.degree. C. However,
such broad signals also suggest that the ligands undergo continuous
conversion/reversion between the coordinated state and the
de-coordinated state. At room temperature, another set of DNP
signals are observed at 8.5, 8.1 and 7.8 ppm along with a set of
signals of DNP ligands remaining mainly in the de-coordinated state
with an integration ratio of 1:3. The less observed DNP signals
have similar chemical shift values as compared to the chemical
shift values of the coordinated DNP ligands observed in THF and
methylene chloride. Thus, the signals may correspond to coordinated
DNP ligands. In other words, in DMSO at room temperature, one DMP
remains mainly in the coordinated state and the other three DMP
ligands remain in the de-coordinated state. It is thought that DMSO
is coordinated at the vacant site generated by de-coordination of
DNP. DMSO is coordinated well to hard acid such as cobalt (III)
metal.
[0265] (5) Complicated NMR Spectrometric Analysis Observed in
DMSO-d.sub.6
[0266] The complicated .sup.1H, .sup.13C and .sup.15N NMR spectra
of complex 7 observed in DMSO-d.sub.6 may be understood through the
above-described non-imine coordinated structure and the state of
DNP. In the structure and state of complex 7 in DMSO at room
temperature as shown in FIG. 7, two phenoxy ligands contained in
one Salen-unit are subjected to different situations. One phenoxy
ligand is at trans-position to DMSO, and the other is at
trans-position to DNP. Therefore, two signals are observed in
.sup.15N NMR spectrum (FIG. 3), and a part of aromatic signals is
divided at a ratio of 1:1 in .sup.1H and 13C NMR (FIGS. 1 and 2).
Especially, NCH.sub.2CH.sub.2N signal is divided into three signals
at 4.3, 4.15 and 4.1 ppm with a ratio of 1:1:2. After the analysis
through .sup.1H-.sup.1H COSY NMR spectrometry, it can be seen that
three signals are derived from one NCH.sub.2CH.sub.2N-unit (FIG.
1). In the structure obtained by the DFT calculation, complex 7
shows a conformation of .dbd.NCH.sub.2CH.sub.2N.dbd. unit and is
similar to the structure as illustrated in FIG. 6. In the above
structure, complex 7 may not be converted into a structural isomer
of the cobalt octahedral structure. Thus, the structure having
three DMSO coordinations and one DNP coordination is chiral. Due to
such chirality, two hydrogen atoms of N--CH.sub.2 show NMR shift
values at different positions. In the case of a complex with a
chiral center, such as complex 5 or 10, .sup.1H and 13C NMR spectra
are more complicated. As the temperature increases to 40.degree.
C., two coordinated DNP signals disappear and one broad signal
appears. In this case, the asymmetric coordination environment is
broken and a simple Salen-ligand signal appears. Since the
coordination environment around cobalt is symmetric in THF and
CH.sub.2Cl.sub.2 at room temperature as shown in FIG. 7, a sharp
Salen-ligand signal appears in .sup.1H, .sup.13C and .sup.15N
NMR.
(6) Cyclic Voltammetry (CV) Test
[0267] CV test also indirectly demonstrates that complexes 5 and 6
have different structures. If complexes 5 and 6 have the same
structure, complex 5 having a methyl substituent is expected to
cause reduction more easily. This is because methyl has lower
electron donating property than t-butyl, and thus the cobalt center
has less abundant electrons so that the electrons go into the
cobalt center more easily. However, the opposite results are
observed. Complex 5 with a methyl substituent causes reduction at a
more negative potential than complex 6. It is observed that
complexes 5 and 6 have a E.sub.1/2 value of Co(III/II) of -0.076V
and -0.013V, respectively, versus SCE. The difference, 63 mV, in
reduction potentials between the two complexes is significant. A
reduction potential difference of 59 mV from the Nernst equation
[E=E.degree.-(0.0592)log {[Ox]/[Red]}] means a difference in
[Co(II)]/[Co(III)] ratios of 10 times at the same potential.
[0268] On the other hand, it is expected that complexes 12 and 13
having no DNP ligands have the same general imine-coordinated
structure regardless of methyl or t-butyl substitution in a
non-coordinatable solvent such as methylene chloride. After
carrying out CV study with complexes 12 and 13 in methylene
chloride, the two complexes show the same reduction potential (0.63
V vs. SCE). In other words, there is no difference in reduction
potentials between methyl substitution and t-butyl substitution
under the same structure. Thus, the above difference in reduction
potentials suggests that the two complexes have different
coordination systems. When the solvent is changed from
CH.sub.2Cl.sub.2 to DMSO, the reduction potential difference
appears again. The reduction potentials of complexes 12 and 13
observed in DMSO (-0.074 and -0.011 V vs. SCE) are similar to the
reduction potentials of complexes 5 and 6 observed in DMSO (-0.076
and -0.013 V vs. SCE). Since DMSO is coordinated well to cobalt
(III) metal, in DMSO as a solvent, complex 12 is converted into a
complex with a different coordination system, such as complex 5
having no imine coordination, while four DMSO ligands are
coordinated to complex 12 having a methyl substituent.
[0269] (7) Initiation Reaction
[0270] Complex 10 reacts with propylene oxide. FIG. 9 is .sup.1H
NMR spectrum illustrating the reaction between complex 10 or 8 and
propylene oxide. The signal marked with `*` is a newly generated
signal that corresponds to the anion of Meisenheimer salt shown in
complex 14. The oxygen atom of alkoxide obtained by the attack to
propylene oxide coordinated with DNP further attacks ipso-position
of the benzene ring, so that the anion of Meisenheimer salt is
formed. Complicated aromatic signals of Salen are observed at
7.0-7.4 ppm. However, this is not caused by the breakage of the
Salen-unit. When an excessive amount of acetic acid is added to the
compound prepared after the reaction with propylene oxide, simple
three Salen aromatic signals are observed. This suggests that the
Salen-unit is not broken. The anion of Meisenheimer salt is stopped
at a [Meisenheimer anion]/[DNP] integration ratio of 1:1. During
the first one hour, DNP is converted rapidly into the anion of
Meisenheimer salt so that the [Meisenheimer anion]/[DNP]
integration ratio reaches 1:1. However, the conversion does not
proceed any longer, and thus the integration ratio is unchanged
even after 2 hours. The anion of Meisenheimer salt is a previously
known compound [(a)Fendler, E. J.; Fendler, J. H.; Byrne, W. E.;
Griff, C. E. J. Org. Chem. 1968, 33, 4141. (b) Bernasconi, C. F.;
Cross, H. S. J. Org. Chem. 1974, 39, 1054)]. Conversion of DNP into
the anion of Meisenheimer salt is significantly lowered in the
presence of a certain amount of water. When 5 equivalents of water
are present per equivalent of cobalt, the conversion rate is not
significantly changed. However, introduction of 50 equivalents of
water causes a rapid drop in the conversion rate, so that the
[Meisenheimer anion]/[DNP] integration ratio becomes 0.47 after 1
hour, becomes 0.53 after 2 hours, and remains at 0.63 even after 4
hours while not providing complex 14 (FIG. 8).
[0271] The reactivity of the general imine-coordinated complex 8
with propylene oxide is different from that of the non-imine
coordinated complex 10. Although the same anion of Meisenheimer
salt is observed, the [Meisenheimer anion]/[DNP] integration ratio
is not stopped at 1.0 but gradually increases over time (0.96 after
1 hour; 1.4 after 2 hours; 1.8 after 7 hours; and 2.0 after 20
hours). Further, unlike the behavior of complex 10, complex 8 shows
a relatively large amount of broad signals between -1 ppm and 0.5
ppm. This suggests that reduction into a paramagnetic cobalt (II)
compound occurs. The broad signal gradually increases over time.
The cobalt (II) compound has no catalytic activity.
EXAMPLE 15
Preparation of carbon dioxide/propylene oxide copolymer
[0272] (a) Copolymerization Using Complexes of Examples 3-10 as
Catalyst
[0273] To a 50 mL bomb reactor, any one complex obtained from
Examples 3-10 (used in an amount calculated according to a ratio of
monomer/catalyst of 7.58) and propylene oxide (10.0 g, 172 mmol)
are introduced in a dry box and the reactor is assembled. As soon
as the reactor is removed from the dry box, carbon dioxide is
introduced under a pressure of 18 bar, the reactor is introduced
into an oil bath controlled previously to a temperature of
80.degree. C. and agitation is initiated. The time at which carbon
dioxide pressure starts to be decreased is measured and recorded.
After that, the reaction is carried out for 1 hour, and then carbon
dioxide gas is depressurized to terminate the reaction. To the
resultant viscous solution, monomers (10 g) are further introduced
to reduce the viscosity. Then, the resultant solution is passed
through a silica gel column [400 mg, Merck, 0.040-0.063 mm particle
diameter (230-400 mesh)] to obtain a colorless solution. The
monomers are removed by depressurization under reduced pressure to
obtain a white solid. The weight of the resultant polymer is
measured to calculate turnover number (TON). The polymer is
subjected to .sup.1H NMR spectrometry to calculate selectivity. The
molecular weight of the resultant polymer is measured by GPC with
calibration using polystyrene standards.
[0274] (b) Copolymerization Using Complex of Example 13 as
Catalyst
[0275] To a 50 mL bomb reactor, complex 40a (6.85 mg, 0.0030 mmol,
monomer/catalyst ratio=50,000) obtained from Example 13 and
propylene oxide (9.00 g, 155 mmol) are introduced and the reactor
is assembled. The reactor is introduced into an oil bath controlled
previously to a temperature of 80.degree. C. and is agitated for
about 15 minutes so that the reactor temperature is in equilibrium
with the bath temperature. Next, carbon dioxide is added under 20
bars. After 30 minutes, it is observed that carbon dioxide is
depressurized while the reaction proceeds. Carbon dioxide is
further injected continuously for 1 hour under 20 bars. To the
resultant viscous solution, monomers (10 g) are further introduced
to reduce the viscosity. Then, the resultant solution is passed
through a silica gel column [400 mg, Merck, 0.040-0.063 mm particle
diameter (230-400 mesh)] to obtain a colorless solution. The
monomers are removed by depressurization under reduced pressure to
obtain 2.15 g of a white solid. The catalytic activity of the
complex used in this Example corresponds to a TON of 6100 and a
turnover frequency (TOF) of 9200 h.sup.-1. The resultant polymer
has a molecular weight (M.sub.n) of 89000 and a polydispersity
(Mw/Mn) of 1.21 as measured by GPC. The polymer formation
selectivity is 96% as determined by .sup.1H NMR.
EXAMPLE 16
Recovery of copolymer and catalyst
[0276] In the cases of complexes 5, 7 and 10, the following process
is used to recover catalysts. The colored portion containing a
cobalt catalyst component at the top of the silica column in
Example 12 is collected, and dispersed into methanol solution
saturated with NaBF.sub.4 to obtain a red colored solution. The red
solution is filtered, washed twice with methanol solution saturated
with NaBF.sub.4 until the silica becomes colorless, the resultant
solution is collected, and the solvent is removed by
depressurization under reduced pressure. To the resultant solid,
methylene chloride is added. In this manner, the brown colored
cobalt compound is dissolved into methylene chloride, while the
unsoluble white NaBF.sub.4 solid may be separated. To the methylene
chloride solution, 2 equivalents of solid 2,4-dinitrophenol and 4
equivalents of sodium 2,4-dinitrophenolate are introduced per mole
of the catalyst, followed by agitation overnight. The resultant
mixture is filtered to remove methylene chloride solution and to
obtain brown colored powder. After .sup.1H NMR analysis, the
resultant compound is shown to be the same as the catalyst compound
and to have similar activity in the copolymerization.
[0277] Table 1 shows the polymerization reactivity of each
catalyst.
TABLE-US-00002 TABLE 1 Polymerization reactivity of each
catalyst.sup.a ##STR00038## Induction M.sub.n.sup.d No. Catalyst
Time (min) TOF.sup.b Selectivity.sup.c (10.sup.-3) M.sub.w/M.sub.n
1 5 60.sup.e 13,000 92 210 1.26 2 6 0 1,300 84 38 2.34 3 7
120.sup.e 8,300 97 113 1.23 4 8 0 5,000 85 120 1.41 5 9 0 6 10
260.sup.e 11,000 96 140 1.17 7 11 0 8 14 30 13,000 99 170 1.21 9 15
0 15,000 99 270 1.26 10.sup.f 15 0 16,000 99 300 1.31
.sup.aPolymerization condition: PO (10 g, 170 mmol), [PO]/[Cat] =
100,000, CO.sub.2 (2.0-1.7 MPa), temperature 70-75.degree. C.,
reaction time 60 minutes. .sup.bcalculated based on the weight of
the polymer containing cyclic carbonate. .sup.ccalculated by
.sup.1H NMR. .sup.dmeasured by GPC using polystyrene standards.
.sup.einduction time of 1-10 hours depending on batch.
.sup.fpolymerization using 220 g of PO.
[0278] As can be seen from Table 1, the general compounds having
imine coordination, i.e. complexes 6, 8 and 11 has little or no
polymerization activity. On the other hand, the complexes with a
different structure having no imine coordination according to the
present invention have high polymerization activity. However,
complex 9 with a different structure having no imine coordination
but containing six ammonium units has no activity.
[0279] Complexes 5, 7 and 10 have higher activity in order of
5>10>7, which is the converse of order of Co-binding affinity
of weak bound DNP undergoing continuous conversion/reversion
between the Co-coordinated state and the de-coordinated state.
[0280] Complex 10 is used to perform many experiments. Under a
high-temperature high-humidity condition in the summer season, a
great change is observed in induction time (1-12 hours). After the
induction time, polymerization rate are observed to be nearly
constant (TOF, 9,000-11,000 h.sup.-1). In the summer season, the
amount of water infiltrating into the dry box for a polymerization
reactor is not negligible. In this case, the polymerization system
absorbs water and the induction time varies with the amount of
water. In fact, under a dry low-temperature condition in the winter
season, induction time decreases to 1 hour. In this case, when an
additional amount of water is added thereto (50 equivalents vs.
cobalt), induction time increases to 3 hours (entry 10).
Introduction of a significant amount of water (250 equivalents)
does not allow polymerization.
[0281] When a certain amount of water is present, the rate of
polymerization initiation caused by an attack of DNP to propylene
oxide is decreased significantly, as determined by NMR (FIG. 9).
When using compound 15 obtained from the reaction with propylene
oxide as a catalyst, it is possible to solve the problem of such a
great change in induction time depending on the amount of water
(entry 13). When using compound 15 as a catalyst, water sensitivity
decreases to allow polymerization even under a [propylene
oxide]/[catalyst] ratio of 150000:1, resulting in further
improvement in TON (entry 14). Under such a condition, complex 10
has no polymerization activity even when using thoroughly purified
propylene oxide. Compound 15 is obtained by dissolving a high
concentration of complex 10 into propylene oxide and by performing
a reaction for 1 hour. In this case, it is possible to neglect the
ratio of [water remaining in propylene oxide]/[compound 10].
[0282] The present application contains subject matter related to
Korean Patent Application Nos. 10-2008-0074435, 10-2008-0126170,
10-2009-0054481 and 10-2009-0054569 filed in the Korean
Intellectual Property Office on Jul. 30, 2008, Dec. 11, 2008, Jun.
18, 2009, and Jun. 18, 2009, the entire contents of which are
incorporated herein by reference.
[0283] While the present invention has been described with respect
to the specific embodiments, it will be apparent to those skilled
in the art that various changes and modifications may be made
without departing from the spirit and scope of the invention as
defined in the following claims.
* * * * *