Preparation of Double-Metal Cyanide Catalysts containing Zn-OAc moiety for Propylene Oxide/CO2 Copolymerization
- 주제(키워드) Double metal cyanide complex , CO2 copolymerization , CCU technology , polyol , polyurethane
- 주제(DDC) 547
- 발행기관 아주대학교 일반대학원
- 지도교수 이분열
- 발행년도 2024
- 학위수여년월 2024. 2
- 학위명 석사
- 학과 및 전공 일반대학원 분자과학기술학과
- 실제URI http://www.dcollection.net/handler/ajou/000000033401
- 본문언어 영어
- 저작권 아주대학교 논문은 저작권에 의해 보호받습니다.
초록/요약
Zn and Co-based double metal cyanide (DMC) catalysts are frequently employed in polyether polyol production utilizing the ring opening polymerization for epoxide. When pressurized with CO2 during the reaction, these catalysts have the ability to incorporate CO2 into polyol chains, presenting DMC as a potential frontrunner in Carbon Capture and Utilization (CCU) technology. However, it has been challenging to find catalysts that maintain high activity under high pressure of CO2 gas, produce minimal cyclic carbonate byproducts, and have a significant CO2 incorporation ability. In this study, our team innovated a synthesis method for Zn-OAc containing catalysts, capable of fulfilling all these criteria. This technique also permits the inclusion of Zn-Cl and Zn-OtBu units, which vary with the stoichiometry of the reactants. These catalysts were analyzed using NMR, SEM-EDS, XRD, ATR-FTIR, and ICP-OES instruments. It was observed that in Propylene Oxide/CO2 copolymerization, the higher the Zn-OAc portion ratio, the greater the CO2 content in the polymer. Notably, the Zn-OAc/OtBu(0.95/0.08) catalyst, which contains a slight amount of Zn-OtBu moiety which is effective in suppressing byproduct formation yet producing high molecular weight impurities, demonstrated a performance, the turnover frequency (TOF) of 64,000 PO-consumption/Co/h and 20,000 CO2-consumption/Co/h with cyclic carbonate at a level of 3.4 wt%, making it a viable candidate for commercial application.
more목차
1. Introduction 1
2. Results and Discussion 2
2.1 Preparation of DMC catalyst containing acetate groups 2
2.2 PO/CO2 copolymerization 8
3. Experimental Section 15
3.1 General remarks 15
3.1.1 Materials 15
3.1.2 Characterization method 16
3.2 Preparation of DMC catalysts 16
3.2.1 Preparation of [DMC-Cl][MeOC3H6OH] 16
3.2.2 Preparation of [DMC-Cl][tBuOH] 17
3.2.3 Preparation of DMC-OC3H6OMe, DMC-(OC3H6OMe/Cl)(p/(1-p)), DMC-OtBu and DMC-(OtBu/Cl)(0.5/0.5) 17
3.2.4 Preparation of DMC-OAc, DMC-(OAc/OtBu)(p/q), DMC-(OAc/OtBu/Cl)(p/q/r) 19
3.3 PO polymerization 20
3.4 PO/CO2 copolymerization 21
4. Conclusions 21
5. Acknowledgements 22
6. References 22
7. Supporting information 25
