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

jisanrhee@hanmail.net

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