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Inorganic Material Lab. SKKU Polymerization in the gallery space of layered materials Advantage Molecular weight Molecular weight distribution Stereochemistry LDH 2-D layered material Nanometer sized layer Relative inactive gallery space ref) Q. Wu et al. Polymer, 2000, 41, 2029.
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Inorganic Material Lab. SKKU
Formation of Polymer-Inorganic Hybrid Materials by in situ Polymerization of Muconates
in the Interlayer Space of [LiAl2(OH)6]+ Layers
이석우 정덕영 *
성균관대학교 화학과
Inorganic Material Lab. SKKU
Abstract
Polymer-inorganic hybrid materials were synthesized by in situ radical poly
merization of muconates in the interlayer space of LDHs. When [LiAl2(OH)
6]2[(Z,Z)-C6H4O4]zH2O and [LiAl2(OH)6]2[(E,E)-C6H4O4]zH2O were treate
d by disulfate anion in the aqueous suspension at 340 K, the (Z,Z)- and (E,
E)-muconates underwent polymerization in the interlayer space, resulting in
the formation of polymer-inorganic hybrids. The chemical and structural pro
perties of hybrids, which were characterized using elemental analysis, TGA,
XRPD, FT-IR, 1H NMR and 13C CP-MAS NMR will be presented.
Inorganic Material Lab. SKKU
Polymerization in the gallery space of layered materials
Advantage
Molecular weight
Molecular weight distribution
Stereochemistry
LDH
2-D layered material
Nanometer sized layer
Relative inactive gallery spaceref) Q. Wu et al. Polymer, 2000, 41, 2029.
Inorganic Material Lab. SKKU
Schematic diagrams for the in situ polymerization of muconates in the intercalates
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
OO
O O O O O O
O O O O O O
O O O O O O
O O O O O O
S2O82-(aq)
340 K, 24 h
LDH-ZZ-MU
LDH-EE-MU
LDH-poly-MU
Inorganic Material Lab. SKKU
Synthesis of organic-inorganic hybrid materials
2[LiAl2(OH)6]Cl + (Z,Z)-C6H4O42-
1. synthesis of LDHs intercalated with (Z,Z)- and (E,E)-muconates
[LiAl2(OH)6]2[(Z,Z)-C6H4O4] + 2Cl-
2[LiAl2(OH)6]Cl + (E,E)-C6H4O42- [LiAl2(OH)6]2[(E,E)-C6H4O4] + 2Cl-
2. polymerization of muconates in the interlayer of LDHs
[LiAl2(OH)6]2[C6H4O4]NH4S2O8(aq)
340 K, N2
Polymer-inorganic hybrids
3. a free radical initiator of polymerization
O
SO-
O
S-O OO O
O
O
S-O OO
2
Inorganic Material Lab. SKKU
Layered organic-inorganic hybrid materials
XRPD Spectra 13C CP-MAS NMR Spectra
10 20 30 40 50 60 70 80
I
2, degrees
(a)
(b)
13.07
6.57
14.06
7.09
-50050100150200250300
ppm
(c)
(d)
a
abc
bc
s ss s ss
ssss
sssss s s
s ss
CO2--O2C
bca
-O2C
CO2-
abc
(a), (c): LDH-ZZ-MU; (b),(d): LDH-EE-MU
Inorganic Material Lab. SKKU
XRPD Spectra of Layered polymer-inorganic hybrid materials
10 20 30 40 50 60 70 80
2, degrees
(a)
(b)
11.91
12.27
5.97
6.12
*
*
(a) from LDH-ZZ-MU, (b) from LDH-EE-MU
* LDH-SO42-
Inorganic Material Lab. SKKU
Stereochemistry of polymuconate in the hybrids
050100150200250
zz
ppm
ss
s
s
ss
s
s
ab
a
c
bc
13C CP-MAS NMR Spectra
cis- trans- Exp.
a C=O 172 172 181
b C=C 132 132 131
c C-C 45-47 50-52 55.7, 56.0
COO-
COO-n
cis- or trans-1,4-polymuconate
s: spinning side bands
(a) from LDH-ZZ-MU, (b) from LDH-EE-MU
(a)
(b)
Inorganic Material Lab. SKKU
Stereochemistry of polymuconate deintercalated
123456789
(a)
(b)
ppm
a
c
d
b
a
c
db
55.56 2.533.5
s
CH-CH=CH-CH
CO2- +H3NCH2C6H5
CO2- +H3NCH2C6H5
ab
cd
O O O O O O
O O O O O O
O O O O O O
O O O O O O
HCl(aq)
H2NCH2C6H5
1H NMR Spectra
CH-CH=CH-CH
CO2- +H3NCH2C6H5
CO2- +H3NCH2C6H5
(a) from LDH-ZZ-MU, (b) from LDH-EE-MU
Inorganic Material Lab. SKKU
050100150200250
ppm
(a)
(b)
a c
db
e
f
a
db
e
f
c
175180185 125130135 505560
CH-CH=CH-CH
CO2- +H3NCH2C6H5
CO2- +H3NCH2C6H5
a
bc
d,ef
13C NMR Spectra
Stereochemistry of polymuconate deintercalated
COO-+NH3CH2C6H5
COO-+NH3CH2C6H5n
cis- or trans-1,4-polymuconate diammonium salt
cis- trans- Exp.
a C=O 172 172 181
b C=C 132 132 131
c C-C 45-47 50-52 57.5
(a) from LDH-ZZ-MU, (b) from LDH-EE-MU
Inorganic Material Lab. SKKU
Proper orientation of muconates in the gallery space
A. Matsumoto et al. JACS, 1999, 121, 11122 A. Matsumoto et al. JPC B, 2001, 105, 4155
Inorganic Material Lab. SKKU
Thermal analyses of layered hybrids
40
60
80
100
-0.4
-0.3
-0.2
-0.1
0.0
0.1
0 200 400 600 800
Wei
ght,
%
Temperature, oC
Derivative of TG
(Z,Z)-monomer
40
60
80
100
-0.4
-0.3
-0.2
-0.1
0.0
0.1
0 200 400 600 800
Wei
ght,
%
Temperature, oC
Derivative of TG
(E,E)-monomer
40
60
80
100
-0.4
-0.3
-0.2
-0.1
0.0
0.1
0 200 400 600 800
Wei
ght,
%
Temperature, oC
Derivative of TG
(Z,Z)-polymer
40
60
80
100
-0.4
-0.3
-0.2
-0.1
0.0
0.1
0 200 400 600 800
Wei
ght,
%
Derivative of TG
Temperature, oC
(E,E)-polymer
Inorganic Material Lab. SKKU
Conclusion
Layered polymer-inorganic hybrid materials were synthesized by in situ radical polymerization of muconates in the interlayer space of LDHs.
Disulfate anion plays a role in the polymerization as an initiator in the aqueous suspension.
A trans-1,4-polymuconate was a major product of radical polymerization.
Acknowledgements. This work was supported by Korea Research Foundation Grant (KRF-2000-031-000). Dr. Rhee also acknowledges KRF for BK-21 fellowship