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Utilization of CO and CO2 as C1 Sources: Synthesis of Carboxylic Acids, Organic Carbonates and Polyketones

Utilization of CO and CO2 as C1 Sources: Synthesis of Carboxylic Acids, Organic Carbonates and Polyketones

초록/요약

Greenhouse gas (GHG) generated in the use of fossil fuels that is not consumed naturally in the atmosphere and caused by the human race has resulted in global warming. GHGs generally include carbon dioxide (CO2), methane (CH4), carbon monoxide (CO), nitrogen dioxide (NO2), hydrofluorocarbons (HFCS), and perfluorocarbons (PFC), etc. The utilization of C1 gas like carbon monoxide, carbon dioxide, and, methane as chemical feedstock can be the solution to global warming. I have presented the chemical conversion of CO and CO2 as a C1 source in this thesis. In Chapter 1, the metal-catalyzed carbonyl/carboxylation of alkene and alkynes reaction have been reviewed overall. Typically, catalysts such as Pd, Ru, and Ni are known as an active catalyst for carbonylation. In particular, Pd catalysts have been successfully used for the synthesis of carboxylic acid and carboxylic acid esters from alkene and alkynes. Thus, in the first section of Chapter 1, I reviewed Pd-catalyzed carbonylation of alkenes and alkynes from CO. On the other hand, in the second section of Chapter 1, I reviewed the metal-catalyzed carboxylation of alkene and alkyne from CO2. The carbonation of CO2 was different from the carbonylation of CO, with the reaction acting according to the metal catalysts acting on the reaction different from each other. The Ni catalyst mainly induces hydrocarbonylation and the Cu or Ag catalyst induces a direct coupling reaction. In Chapter 2, a Pd catalyst was used to polymerize CO and ethylene. The co-polymers of CO and ethylene, called polyketone, can be used for the same industrial materials used in automotive and electronics as polymers with high impact strength, chemical resistance, flame retardancy, and so on. However, polyketones had the problem of having a "reactor fouling" (disturbed formation of some of the polymer particles attached to the reactor wall and the agitator) and a high melting point (over 250 oC). In this study, we have developed polyketones without reactor fouling by using sulfonated HMON, silica, and polystyrene as heterogonous catalysts. Terpolymerization was performed to add a phenyl acetylene derivative to reduce meting point. In Chapter 3, the synthesis of the transition metal-free organic carbonates and carboxylic acid was carried out using a CO2 and CO2 derivative (Cs2CO3). The CO2 required vigorous reaction condition using an organometallic catalyst for activating CO2 due to its high thermo-dynamic and kinetic safety. In this research, we developed an environmentally-friendly CO2 activation process with a mild condition that uses a transition metal free method and uses CO2 as low pressure. We used TBD and DBU for CO2 activation and synthesized various organic carbonates by advancing CO2 direct coupling to alcohol. Also, carboxylic acid was synthesized through direct CO2 coupling to acetylene derivatives using TBD.

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목차

Part 1. Utilization of CO and CO2 as C1 Sources: Synthesis of Carboxylic Acids, Organic carbonates and Polyketones 1
Chapter 1. Background of metal-catalyzed carbonylation / carboxylation of alkenes and alkynes. 2
1.1. Palladium-catalyzed carbonylation of alkenes and alkynes. 2
1.1.1. Introduction 2
1.1.2. Hydroxycarbonylation/hydroesterification of alkenes and alkynes. 2
A. Hydroxycarbonylation of alkenes 2
B. Hydroesterification of alkenes 7
C. Hydroesterification of alkynes 11
1.1.3. Oxidative carbonylation of alkenes and alkynes 15
A. Oxidative carbonylation of alkenes 15
B. Oxidative carbonylation of alkynes 19
1.1.4. Summary 22
1.2. Metal-catalyzed carboxylation of alkenes and alkynes 23
1.2.1. Introduction 23
1.2.2. Hydrocarboxylation of alkenes/alkynes 23
A. Hydrocarboxylation of alkenes. 23
B. Hydrocarboxylation of alkynes 25
1.2.3. Direct carboxylation of alkynes 27
A. Carboxylative coupling of alkynes and alkyl halide. 27
B. Direct carboxylation of terminal alkynes. 29
1.2.4. Summary 32
1.3. References 33
Chapter 2. Pd-catalyzed polymerization of CO and olefins. 36
2.1. Introduction 36
2.2. Development of process for synthesizing antifouling polyketones. 39
2.2.1. Result and discussion. 39
A. Synthesis of polyketones using HMON-SO3H, 1.8μm-SiO2-SO3H and PS-SO3H as co-catalyst 39
B. Plausible mechanism. 45
2.2.2. Conclusions. 46
2.3. Thermal property controlled polyketones: terpolymerization of ethylene, alkynes and CO. 47
2.3.1. Result and discussion 47
2.3.2. Conclusions 52
2.4. References 53
Chapter 3. Synthesis of various organic carbonates and carboxylic acids using CO2 54
3.1. Introduction 54
3.2. Synthesis of acyclic and cyclic carbonate using alcohols. 57
3.2.1. Result and discussion 57
3.2.2. Conclusions 63
3.3. Synthesis of Acyclic carbonate with CO2 derivative (Cs2CO3). 64
3.3.1. Result and discussion 64
3.3.2. Conclusions 68
3.4. Metal-free direct carboxylation of acetylene derivatives 69
3.4.1. Result and discussion 69
3.4.2. Conclusions. 73
3.5. References 74
Part 2. Experimental Section 76
Chapter 2. Pd-catalyzed polymerization of CO and olefins. 77
2.2. Development of process for synthesizing antifouling polyketones. 77
2.3. Thermal property controlled polyketones: terpolymerization of ethylene, alkynes and CO. 81
Chapter 3. Synthesis of various organic carbonates and carboxylic acids using CO2. 90
3.2. Synthesis of acyclic and cyclic carbonate using alcohols. 90
A. Synthesis of 14a 90
B. Synthesis of 18O-labeled 12a 91
3.3. Synthesis of Acyclic carbonate with CO2 derivative (Cs2CO3). 102
3.4. Metal-free direct carboxylation of acetylene derivatives 106

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