Title Page
Contents
ABSTRACT 12
Ⅰ. INTRODUCTION 14
1. CO₂-based poly(ether carbonate) 14
2. Catalysts for ring-opening copolymerization of CO₂ and epoxide 17
2.1. Double metal cyanide catalyst 17
2.2. Others 19
3. Purpose of thesis 21
Ⅱ. Synthesis of CO₂-derived poly (glycidol carbonate) polyol for rigid polyurethane foam under double metal cyanide catalyst 22
1. Materials and experiments 22
1.1. Materials 22
1.2. Preparation of catalysts 22
1.3. Copolymerization of glycidol and CO₂ in batch system 23
1.4. Column chromatography 23
1.5. Preparation of rigid polyurethane foam 24
1.6. Characterization 24
2. Results and discussions 26
2.1. Catalyst characterization 26
2.2. Results of glycidol-CO₂ copolymerization 31
2.3. Properties of poly (glycidol carbonate) polyol 35
2.4. Synthesis of rigid polyurethane using PGC polyol 44
Ⅲ. Synthesis of poly(propylene carbonate) over DMC catalysts 50
1. Materials and experiments 50
1.1. Materials 50
1.2. Preparation of catalysts 50
1.3. Copolymerization of epoxide and CO₂ in batch system 51
1.4. Characterization 51
2. Results and discussion 53
2.1. Catalyst characterization 53
2.2. Optimization of copolymerization conditions 66
2.3. Structure analysis of PPC 77
2.4. Terpolymerization of CO₂, PO and CHO and the properties of terpolymers 79
Ⅳ. Conclusion 84
Ⅴ. References 86
국문초록 96
Table 1. Characterization of DMC-THFA catalysts with various THFA contents 28
Table 2. Results of reaction using various DMC-THFA catalysts 33
Table 3. Yields and productivities of glycidol-CO₂ copolymerization 34
Table 4. The properties of PGC(0.1) and PG(0.1)_N₂ from spot 3 43
Table 5. The properties of spot 2 from PGC(0.1) and PG(0.1)_N₂ 45
Table 6. The recipe for synthesizing various rigid polyurethane foam using PGC(0.1) and PG(0.1)_N₂ 46
Table 7. Apparent density and compressive strength of PU samples 48
Table 8. The recipe of Zn-Co DMC catalysts including DAA and PPG as CA and co-CA 54
Table 9. Crystal sizes and elemental compositions of DMC-DAA(0.15) catalysts with various molecular weights of PPG as co-CA 62
Table 10. The surface area of DMC-DAA(0.15) catalysts with various molecular weight of PPG as co-CA 63
Table 11. The pore volumes and average pore diameters of DMC-DAA(0.15) catalysts with various molecular weight of PPG as co-CA 64
Table 12. PPC productivities under various reaction condition 68
Table 13. The amounts of byproduct and the properties of resulting PPCs 69
Table 14. The results of copolymerization with different injection mode of PO 72
Table 15. The results of copolymerization along different molecular weight of co-CA in catalysts 73
Table 16. The results of terpolymerization at various weight ratios of PO and CHO, and the properties of terpolymers 81
Figure 1. Polymers synthesizable from CO₂ in direct pathway 16
Figure 2. The structure of (a) Zn-Co double metal cyanide, (b) zinc glutarate, (c) Co-Salen catalysts. 20
Figure 3. FT-IR spectra of DMC catalysts with different amount of THFA. Amount ofTHFA added=0, 0.05, 0.1 mol. 29
Figure 4. XRD patterns of DMC catalysts with different amount of THFA. Amount ofTHFA added=0, 0.05, 0.1 mol. 30
Figure 5. The copolymerization of glycidol and CO₂ over DMC catalysts resulting poly(glycidol carbonate) polyol. 36
Figure 6. The SEC analysis of spot 1, 2, and 3 of PGC(0.1). 37
Figure 7. The chemical structures of repeating units in PGC and PG polyols. 40
Figure 8. ¹³C Inverse-gated NMR spectra of spot 1,2, and 3 from PGC(0.1) in methanol-d₄. The samples were numbered in order of eluting.[원문불량;p.28] 41
Figure 9. ¹³C Inverse-gated NMR spectra of spot 3 from PGC(0.1) and PG(0.1)_N₂ in methanol-d₄. 42
Figure 10. Load-deformation curve of PUCO₂.[이미지참조] 49
Figure 11. The FT-IR spectra of Zn-Co DMC catalysts with various contents of DAA. (a=0,b=0.1, c=0.15 mole) 58
Figure 12. The XRD patterns of Zn-Co DMC catalysts with various contents of DAA.(a=0, b=0.1, c=0.15 mole) 59
Figure 13. The FT-IR spectra of DMC-DAA(0.15) catalysts with various molecular weights of PPG as co-CA. (a=no co-CA, b=PPG446, c=PPG725, d=PPG2000, c=PPG4000) 60
Figure 14. The XRD patterns of DMC-DAA(0.15) catalysts with various molecularweights of PPG as co-CA. (a=PPG446, b=PPG725, c=PPG2000, d=PPG4000) 61
Figure 15. N₂ adsorption-desorption isotherms of DMC-DAA(0.15) with (a) PPG446, (b) PPG725, (c) PPG2000, and (d) PPG4000. 65
Figure 16. The values of FCO₂, Wpc, and productivity under different pressure conditions.[이미지참조] 70
Figure 17. The change in FCO₂ and Wpc depending on the volume and diameter ofmicropore at DMC-DAA(0.15) with PPG446, 725, 2000, and 4000 as a co-CA.[이미지참조] 75
Figure 18. The change in productivity depending on the BET surface area and crystal size of DMC-DAA(0.15) with PPG446, 725, 2000, and 4000 as a co-CA. 76
Figure 19. NMR spectra of PPC produced by DMC-DAA(0.15)w/PPG446 before and after washing. The solvent is CDCl₃. 78
Figure 20. ¹H NMR spectra of terpolymers with various PO:CHO weight ratios. 82
Figure 21. DSC curves of terpolymers with various PO:CHO weight ratios. 83