초록 ▼

○ CO₂ 기반 플랫폼 화합물 제조용 신촉매 개발 (신촉매 11종 개발)
- CO₂기반 플랫폼(지환족아민, 치환우레아, 카바메이트) 제조용 신촉매 개발(5종)
- CO₂를 이용한 아민의 카르복실화 반응 촉매 개발(1종) 및 반응 메카니즘 규명
- 디아민과 CO₂ 유도체간의 반응을 통한 디우레탄 합성 공정 및 촉매 개발(2종)
- 이소시아네이트 제조용 촉매열분해 시스템 구축
- 촉매열분해 시스템 구축 및 ZnO 기반의 고활성 촉매 개발(3종)
○ 바이오매스 기반 플랫폼 화합물 제조용 신공정 개발 (신촉

○ CO₂ 기반 플랫폼 화합물 제조용 신촉매 개발 (신촉매 11종 개발)
- CO₂기반 플랫폼(지환족아민, 치환우레아, 카바메이트) 제조용 신촉매 개발(5종)
- CO₂를 이용한 아민의 카르복실화 반응 촉매 개발(1종) 및 반응 메카니즘 규명
- 디아민과 CO₂ 유도체간의 반응을 통한 디우레탄 합성 공정 및 촉매 개발(2종)
- 이소시아네이트 제조용 촉매열분해 시스템 구축
- 촉매열분해 시스템 구축 및 ZnO 기반의 고활성 촉매 개발(3종)
○ 바이오매스 기반 플랫폼 화합물 제조용 신공정 개발 (신촉매 5종 개발)
- 해양바이오매스 유래 플랫폼 합물 제조용 촉매 5종 개발
- EVO에 이산화탄소를 고정화시켜 고리형 카보네이트를 제조하는 기술
- 에폭시화 반응의 다양한 촉매공정 개발 및 활용기술 개발
- EVO를 개시제로 활용, DMC 촉매로 분자량이 2000~6000인 다기능성 폴리올 제조
○ EcoPolymer 구조제어 및 기능화
- 퓨란계 폴리올에 무황변 타입의 이소시아네이트를 도입하여 에코폴리우레탄을 제조
- 기능성 및 구조가 제어된 식물유 폴리올을 이용한 eco-TPU의 합성
- 식물유 폴리올을 이용하여 분자량 105,000 g/mol 이상, 바이오매스 개질도 7 wt% 이상 의 TPU를 성공적으로 합성함
- 도출된 thiol-ene 반응 조건을 바탕으로, ethylene oxide 기능화 식물유 폴리올, TPU와 수분산 폴리우레탄을 성공적으로 합성함.
(출처:요약서 3p)

Abstract ▼

Ⅳ. Research Results
1. CO₂ Conversion Catalyst System for the Synthesis of Platform Chemicals
- 96.3% yields of aliphatic amines were obtained from aromatic amines by using a catalyst system comprising Ru/C and NaNO₂.
- A 3-component cascade reaction system consisting of amines, carbon diox

Ⅳ. Research Results
1. CO₂ Conversion Catalyst System for the Synthesis of Platform Chemicals
- 96.3% yields of aliphatic amines were obtained from aromatic amines by using a catalyst system comprising Ru/C and NaNO₂.
- A 3-component cascade reaction system consisting of amines, carbon dioxide, and epoxide for producing disubstituted urea has been developed using a catalyst system comprising [Bmim][InCl₄] and NaI or their active species of [Bmim][InI4] that delivered more than 64% yield of urea product.
- A direct synthesis of disubstituted urea by reacting of amines and carbon dioxide by using a homogeneous catalyst (Cs[benzotriazolide]) that afforded 95.1% yield of disubstituted urea with a high TOF of 344 h^-1 .
- A direct synthesis of disubstituted urea by reacting of amines and carbon dioxide by using a highly recyclable heterogeneous catalyst system (PAIL) that afforded 65.5% yield of product.
- 88% yields of aliphatic carbamates were obtained from reacting aromatic amines and organic carbonates by using a catalyst system comprising Ru/C and Na₂CO₃.
- Dialkyl ureas were synthesized in yields over 90% in the presence of a catalyst, K3PO4 or K2CO₃ using absorption phenomenon.
- Cyclic ureas and polyureas were obtained almost quantitatively from the reactions of CO₂ with C2 - C3 diamines and C4 - C6 diamines, respectively in the presence of K₃PO₄, K₂CO₃, or KHCO₃.
- Monourethanes were produced in yield about 80% carbamate from the direct carboxylation of amines using CO₂ absorption phenomenon in the co-presence of alcohol and NMP.
- C4 - C6 dicarbamates were produced in yield over 99% from the one-step urealysis of diamines in the presence of an alcohol by continuous removal of NH₃.
- C4 - C6 dicarbamates were obtained in yield over 99% from the methoxycarbonylation of C2 - C6 diamines with DMC.
- The reactions of C4 - C6 diamines with EC afforded corresponding dicarbamates quantitatively even at 50 oC.
- Cost-effective preparation method was developed for the carboxylation of epoxides with CO₂ to produce alkylene carbonates.
- Dbutylcarbonate was produced in high yields from the reaction of butanol and butyl iodide in the presence of K₂CO₃, andbutyl iodide was regenerated by the reaction of KI and butanol in the presence of an acid.
- Calculation of kinetic parameters for catalytic decomposition of carbamate
- Catalyst screening in a batch reactor
- Confirmation of carbamate reaction mechanism using quasi in-situ FT-IR
- Set-up of catalytic decomposition system and optimization of reaction variables
- Development of two highly active catalysts
> ZnO/CuO-SP method: HDI yield = 91.5%
> ZnO/CuO-CP method: HDI yield = 91.7%

2. Process Development for Biomass Conversion for Platform Chemicals
- Biomass-derived furanose could be successfully dehydrated into aromatic platform chemical, HMF in 70-80% yields using heterogeneous iron catalyst coordinated by polymer-supported NHC ligand (PS-NHC-Fe(III)) and bio-based solid acid catalyst (AC-SO₃H).
- The method for the production of HMF by the dehydration of biomass-derived furanose was developed. Using polymer-supported heterogeneous iron catalyst coordinated by NHC ligand (PS-NHC-Fe(III)), bio-based solid acid catalyst (AC-SO₃H) and bio-EG based solvents, 80% yield of HMF in maximum was achieved.
- Highly active and recyclable catalyst, Ru/MnCO₂O₄ were developed that afforded 99.1% yield of FDCA (furan dicarboxylic acid) from HMF using base-free and water solvent via air-oxidation process.
- By using same catalyst, it was found to be also active for producing FDM (diformyl furan) from DFF under H2 pressure and by switching the solvent from toluene to methanol that afforded 97.0% yield of FDM.
- By using same catalyst, it was found to be also active for producing FDM (furan dimethanol) from DFF just by switching the solvent from toluene to methanol that afforded 98.7% yield of DFF.
- By using same catalyst, it was found to be also active for producing FDM (Furan dimethanol)
- Ru/γ-Al₂O₃ and V/AC were prepared as catalysts for selective oxidation of HMF and analyzed by IR, XRD, XPS, BET, TEM, and EDX for physical and chemical characterization. Following optimization of reaction parameters, HMF could be successfully oxidized with the prepared catalyst in max. 96% yield of DFF.
- Direct conversion of galactaric acid and agarose from marine-based biomass could afford FDCA esters, CMF and AMF as alternatives to petroleum-based aromatics in ca. 60% yields.
- Direct conversion of galactaric acid and agarose from marine-based biomass could afford FDCA esters and CMF as as alternatives to petroleum-based aromatics in around 60% yields.
- Organize a variety of catalytic processes for epoxidation reaction.
- Formic acid is economical and simple process using the process and at the same time epoxidation reaction proceeds in high yield can be seen.
- Developed an unsaturated bond in the vegetable oil prepared by epoxidation of an epoxidized vegetable oil is a vegetable oil can be readily chemically modified.

3. Structure Controlling and their Functionalization of EcoPolymer
- Terminal group modification of furanic diol was performed in advance to PU polymerization due to the unstability of furanic diol. Molecular weights (Mw) of PUs prepared with modified furanic diol were 40,000-180,000 g/mol depending on the reaction conditions.
- Furan-based oligomeric diols were synthesized using furan dicarboxylic acid and aliphatic diols with titanium based catalyst.
- A model ecopolyurethanes synthesized from aliphatic diisocyanates and furan-base oligomeric diols showed 56,000 of molecular weight (108,400 g/mol of Mw)
- Since synthesizing a polyurethane with furan-diol was not successful because of unstability of furan-diol, new furan-diol and macro-diol having furan core were synthesized and used as comonomer.
- Polyurethanes prepared with new furan-diol showed good tensile strength (16.4 MPa) and elongation at break (1400%).
- A quantitative and complete conversion (~ 100%) of C=C of vegetable oils to OH functionalities was achieved through the optimization on the thiol-ene reaction conditions.
- The quantitative transformation of the carbon􍾢 carbon double bonds to hydroxyl groups allowed for the preparation of polyols with predetermined hydroxyl functionalities (2~ 4 OH per polyol).
- The polyols were successfully incorporated into TPUs, affording elastomers with hyperbranched chain architectures and improved mechanical properties (elongation at break > 600%, tension set < 8.3%, transparency > 88%). The TPUs also exhibited excellent shape memory characteristics (Rf & Rr ~ 100%).
- TPU with molecular weight of 105,000 g/mol and biomass content (content of bio-carbon) of 7 wt% was successfully prepared. TPU with molecular weight of 107,000 g/mol and biomass content (content of bio-carbon) of 16 wt% was also achieved through the incorporation of biomass based diisocyanate and chain extender.
- Through the thiol-ene synthetic procedures, ethylene oxide functionalized polyols, TPUs and waterborne PUs were successfully prepared.
- A wound healing patch was demonstrated as an application of the ethylene oxide functionalized PUs. A PU coating and multi-functionalized polyols were also demonstrated as examples of the application of the vegetable oil based polyols and PUs.
(출처:SUMMARY 12~15p)

목차 Contents

• 표지 ... 1제 출 문 ... 2보고서 요약서 ... 3요 약 문 ... 4SUMMARY ... 10CONTENTS ... 18목차 ... 19제 1 장 연구개발과제의 개요 ... 21 1. 연구개발의 목적 ... 21 2. 연구개발의 필요성 ... 21 가. 경제적·산업적 중요성 ... 21 나. 연구개발의 필요성 및 범위 ... 23제 2 장 국내외 기술개발 현황 ... 27 제 1절 CO2 기반 플랫폼 화합물 제조용 신촉매 시스템 개발 ... 27 1. 국외 연구개발 현황 ... 27 2. 국내 연구기관의 연구개발 현황 ... 29 3. 국외 연구기관의 연구개발 내용 및 결과 ... 30 4. 국내 연구기관의 연구개발 내용 및 결과 ... 30 5. 당해 연구개발기술의 국내외 기술개발현황에서 차지하는 위치 ... 31 제 2절 바이오매스 기반 플랫폼 화합물 제조용 신공정 개발 ... 32 1. 퓨란계 탈수화반응 촉매 기술개발 현황 ... 32 2. 탈수화반응용 용매 기술개발 현황 ... 32 3. HMF의 전환기술 현황 ... 33 4. 바이오매스 유래 폴리올 제조를 위한 반응경로 탐색 ... 33 5. 식물유 기반 폴리올/폴리머 제조기술 ... 33 제 3절 EcoPolymer 구조제어 및 기능화 ... 35 1. 국외 연구개발 현황 ... 35 2. 국내 수준 ... 36 3. 연구개발대상 기술의 세계적 현황 ... 39 4. 연구개발대상 기술의 국내 현황 ... 40제 3 장 연구개발수행 내용 및 결과 ... 41 제 1절 CO2 기반 플랫폼 화합물 제조용 신촉매 시스템 개발 ... 41 1. 방향족 화합물의 수소화 반응을 통한 지환족 아민 제조용 촉매 연구 ... 41 2. 방향족 아민으로부터 Ring Hydrogenated Carbamates 제조용 촉매연구 ... 41 3. CO2 기반 플랫폼 화합물 제조용 신촉매 시스템 연구 ... 43 4. CO2 흡수현상을 이용한 치환우레아 및 카바메이트 제조 ... 56 5. 카바메이트의 열분해 ... 66 제 2절 바이오매스 기반 플랫폼 화합물 제조용 신공정 개발 ... 74 1. 해양 바이오매스 기반 플랫폼 화합물 제조연구 ... 74 2. 유지계 바이오매스 유래 폴리올 제조 ... 82 제 3절 EcoPolymer 구조제어 및 기능화 ... 85 1. 파자마유를 기반으로 활용한 우레탄 젓합 특성 및 공정개발 ... 85 2. Furan계 diol을 이용한 친환경 폴리우레탄 합성 기술 ... 86 3. 유지계 바이오매스 유래 고분자 제조 ... 88 제 4절 바이오매스도 및 이산화탄소 저감율 ... 100 1. 바이오매스도 ... 100 2. 이산화탄소 저감율 ... 102제 4 장 목표달성도 및 관련분야에의 기여도 ... 103 1. 평가 착안점 별 달성도 (최종평가) ... 103 2. 정량적 목표 달성도 (최종) ... 104 3. 기타 실적 ... 105제 5 장 연구개발결과의 활용계획 ... 107 제 1절 CO2 기반 플랫폼 화합물 제조용 신촉매 시스템 개발 ... 107 제 2절 바이오매스 기반 플랫폼 화합물 제조용 신공정 개발 ... 108 제 3절 EcoPolymer 구조제어 및 기능화 ... 109 제 4절 허브-스포크간 협업내용 ... 111제 6 장 연구시설·장비 현황 ... 114끝페이지 ... 118