Inorganic Material Lab. SKKU Formation of Polymer-Inorganic Hybrid Materials by in situ Polymerization of Muconates in the Interlayer Space of [LiAl 2 (OH) 6 ] + Layers 이석우  정덕영 * 성균관대학교 화학과

Inorganic Material Lab. SKKU Abstract Polymer-inorganic hybrid materials were synthesized by in situ radical polymerization of muconates in the interlayer space of LDHs. When [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ]  zH 2 O and [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ]  zH 2 O were treated 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 properties of hybrids, which were characterized using elemental analysis, TGA, XRPD, FT-IR, 1 H NMR and 13 C 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 space ref) Q. Wu et al. Polymer, 2000, 41, 2029.

Inorganic Material Lab. SKKU Schematic diagrams for the in situ polymerization of muconates in the intercalates S 2 O 8 2- (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[LiAl 2 (OH) 6 ]Cl + (Z,Z)-C 6 H 4 O synthesis of LDHs intercalated with (Z,Z)- and (E,E)-muconates [LiAl 2 (OH) 6 ] 2 [(Z,Z)-C 6 H 4 O 4 ] + 2Cl - 2[LiAl 2 (OH) 6 ]Cl + (E,E)-C 6 H 4 O 4 2- [LiAl 2 (OH) 6 ] 2 [(E,E)-C 6 H 4 O 4 ] + 2Cl - 2. polymerization of muconates in the interlayer of LDHs [LiAl 2 (OH) 6 ] 2 [C 6 H 4 O 4 ] NH 4 S 2 O 8 (aq) 340 K, N 2 Polymer-inorganic hybrids 3. a free radical initiator of polymerization

Inorganic Material Lab. SKKU Layered organic-inorganic hybrid materials XRPD Spectra 13 C CP-MAS NMR Spectra (a), (c): LDH-ZZ-MU; (b),(d): LDH-EE-MU

Inorganic Material Lab. SKKU XRPD Spectra of Layered polymer-inorganic hybrid materials (a) from LDH-ZZ-MU, (b) from LDH-EE-MU * LDH-SO 4 2-

Inorganic Material Lab. SKKU Stereochemistry of polymuconate in the hybrids 13 C CP-MAS NMR Spectra cis-trans- Exp. a C=O b C=C c C-C , 56.0 s: spinning side bands (a) from LDH-ZZ-MU, (b) from LDH-EE-MU (a) (b)

Inorganic Material Lab. SKKU Stereochemistry of polymuconate deintercalated s HCl(aq) H 2 NCH 2 C 6 H 5 1 H NMR Spectra (a) from LDH-ZZ-MU, (b) from LDH-EE-MU

Inorganic Material Lab. SKKU 13 C NMR Spectra Stereochemistry of polymuconate deintercalated cis-trans- Exp. a C=O b C=C c C-C (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, 11122A. Matsumoto et al. JPC B, 2001, 105, 4155

Inorganic Material Lab. SKKU Thermal analyses of layered hybrids

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 ). Dr. Rhee also acknowledges KRF for BK-21 fellowship