臺灣博碩士論文加值系統

此研究透過開環共聚合反應(Ring-opening copolymerization, ROCOP)，將環己氧化物(CHO)、Carbon dioxide (CO2)和聚乙二醇(Polyethylene glycol, PEO)成功合成了PEO-b-PCHC，並通過傅立葉變換紅外光譜儀(FTIR)、核磁共振(NMR)和凝膠滲透色譜法(GPC)驗證了合成成功。利用蒸發誘導自組裝(EISA)方法，製備不同比例的PEO-b-PCHC/酚醛樹脂二元混合物，最通過高溫鍛燒去除模板，以獲得中孔碳材料，並進行了詳細的孔徑分析。這是首次使用CO2聚合物作為模板來製備中孔材料的研究，且發現碳材料具有高比表面積(509 m2 g-1)，並在0 °C時表現出非常高的二氧化碳吸附能力(4.51 mmol g -1)。

In this study, successfully synthesized PEO-b-PCHC via ring-opening copolymerization (ROCOP) of cyclohexane oxide (CHO), carbon dioxide (CO2), and polyethylene glycol (PEO). This was confirmed by Nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), and Fourier transform infrared spectroscopy (FTIR) were used to confirm the successful synthesis of PEO-b-PCHC. Afterwards, the phenolic resin-like mesoporous materials were prepared using the evaporation-induced self-assembly (EISA) method. The interaction changes in differential scanning calorimetry (DSC) were observed through binary blends by phenolic resin in different ratios. After curing, elimination of the templates through high-temperature forging to obtain mesoporous carbon materials and detailed pore analysis was carried out.
Finally, the carbon material was found to have a high specific surface area (509.7 m2 g-1) and exhibited a very high CO2 adsorption capacity (4.51 mmol g-1) at 0 °C. This is the first study to use CO2 polymer as a template for the preparation of mesoporous materials.

Content
論文審定書 ii
誌謝 ii
摘要 iii
Abstract iv
Content v
Figure Captions vii
Scheme Captions ix
Table Captions x
Chapter 1. Introduction and Literature Review 1
1.1 Ring-opening copolymerization (ROCOP) 1
1.2 Phenol-Formaldehyde Resin 3
1.3 Self-Assembly of block Polymer 4
1.3.1 Block copolymer 4
1.3.2 Hydrogen Bonding 6
1.3.3 Evaporation-induced self-assembly (EISA) 8
1.4 Diffusion-Ordered Spectroscopy (DOSY) 9
1.5 Adsorption Theory 10
1.5.1 Porous materials 10
1.5.2 Adsorption Principle and Type 11
1.5.3 CO2 Adsorption 15
Chapter 2. Motivation and Objectives 16
Chapter 3. Experimental Section 17
3.1 Synthesis of LH and LZn2OAc2 17
3.2 Synthesis of PEO-b-PCHC 18
3.3 Synthesis of phenolic resin (Resol type). 19
3.4 Self-Assembled Resol/ PEO-b-PCHC Blends 19
3.5 Synthesis of Mesoporous Phenolic Resins and Carbon. 19
3.6 Characterization 20
Chapter 4 Results and Discussion 21
4.1 Structure Identification of PEO-b-PCHC 21
4.2 Analyses of PEO-b-PCHC /Resol binary blends. 30
4.2.1 DSC of PEO-b-PCHC /Resol binary blends. 30
4.2.2 FTIR of Resol/PEO-b-PCHC binary blends. 31
4.3 Analysis of Small-angle X-ray scattering (SAXS) 34
4.4 Analysis of TEM 37
4.5 Analysis of BET 40
4.5.1 Surface area analyses 40
4.5.2 CO2 capture analysis 42
4.6 Raman spectroscopy analyses 43
Chapter 5 Conclusions 45
References 46

 
Figure Captions
Figure 1- 1 Ring opening copolymerizations (ROCOP) 2
Figure 1- 2 Ring opening polymerizations (ROP) 2
Figure 1-3 Initiation of ROCOP 2
Figure 1-4 Reactions of Novolac and Resol 3
Figure 1-5 Four main types of copolymer 4
Figure 1-6 Theoretical phase diagram and corresponding morphologies for diblock copolymers 5
Figure 1-7 Hydrogen bond 7
Figure 1-8 The IUPAC classification of adsorption isotherm ] 12
Figure 1-9 The IUPAC classification of hysteresis 14
Figure 4-1 FTIR spectrum of PEO114-b-PCHC178 22
Figure 4-2 FTIR spectrum of PEO114-b-PCHC268 22
Figure 4-3 GPC spectrum of PEO114-b-PCHC178 23
Figure 4-4 GPC spectrum of PEO114-b-PCHC268 23
Figure 4-5 1H NMR spectrum of PEO114-b-PCHC178 24
Figure 4-6 1H NMR spectrum of PEO114-b-PCHC268 24
Figure 4-7 13C NMR spectrum of PEO114-b-PCHC178 25
Figure 4-8 13C NMR spectrum of PEO114-b-PCHC268 25
Figure 4-9 TGA analyses of PEO-b-PCHC 27
Figure 4-10 DSC thermal analyses of PEO-b-PCHC 27
Figure 4- 11 DOSY of PEO114-b-PCHC178 29
Figure 4- 12 DOSY of PEO114-b-PCHC268 29
Figure 4-13 DSC thermai analyses of Resol/PEO114-b-PCHC268 30
Figure 4-14 FTIR spectra recorded at 120 °C displaying the (a) hydroxyl stretching, (b) carbonyl stretching 32
Figure 4-15 Curve fitting the C=O absorptions of selected Resol/PEO114-b-PCHC178 binary blends. 33
Figure 4-16 SAXS patterns of (a) Resol/PEO114-b-PCHC268 (b) Resol/PEO114-b-PCHC268 = 60/40, recorded at various temperatures 35
Figure 4-17 SAXS patterns of Resol/PEO114-b-PCHC178 (a) 60/40 (b)50/50 recorded at various temperatures 35
Figure 4-18 SAXS patterns of Resol/PEO114-b-PCHC268 (a) 40/60 (b)50/50 recorded at various temperatures 36
Figure 4- 19 TEM images and SAXS of mesoporous templated by PEO114-b-PCHC178 at weight fraction of Resol/template = (a,d) 60/40 (b,e) 50/50 (c,f) 40/60 37
Figure 4-20 TEM images and SAXS of mesoporous templated by PEO114-b-PCHC268 at weight fraction of Resol/template = (a,d) 30/70, (b,e) 40/60, (c,f) 50/50, (g,j) 60/40 (h,k) 70/30, and (i.l) 80/20 38
Figure 4-21 TEM images and SAXS of mesoporous templated by PEO114-b-PCHC178 at weight fraction of Resol/template = (a,d) 60/40, (b,e) 50/50, and (c,f) 40/60 39
Figure 4-22 The N2 adsorption-desorption isotherms of mesoporous carbon 41
Figure 4-23 CO2 capture property of mesoporous carbon 42
Figure 4-24 Raman spectra of mesoporous carbon 44
 
Scheme Captions
Scheme 3-1 Synthesis of LH and LZn2OAc2 17
Scheme 3-2 Synthesis of PEO-b-PCHC 18
Scheme 3-3 Synthesis of phenolic resin (resol type). 19
 

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