[보고서]이산화탄소-해양바이오매스 기반 플랫폼 화합물 제조 및 EcoPolymer의 기능화 연구

김용진

이산화탄소-해양바이오매스 기반 플랫폼 화합물 제조 및 EcoPolymer의 기능화 연구
Synthesis of CO₂-Marine Biomass based Platform Chemical and Functionalization of Eco-polymer 원문보기

보고서 정보
주관연구기관	한국생산기술연구원 Korea Institute of Industrial Technology
연구책임자	김용진
참여연구자	조진구 , 신승한 , 이홍식 , 박인 , 김상범 , 이도훈 , 김백진 , 이성구 , 이혜진 , 트엉 꽁지엔 , 느윙 뒤손 , 느윙 딴 뚱 , 흰윙 트위 뜨람 , 트란 안 비 , 느오 황 롱 , 보테이 황 안 , 느윙 딴 팟 , 마이 뜨완 , 흐위탄티엔냔
보고서유형	최종보고서
발행국가	대한민국
언어	한국어
발행년월	2014-07
과제시작연도	2015
주관부처	미래창조과학부 Ministry of Science, ICT and Future Planning
등록번호	TRKO201700011957
과제고유번호	1711026291
사업명	첨단융합기술개발
DB 구축일자	2017-11-04
키워드	이산화탄소.바이오매스.이소시아네이트.카바메이트.우레아.폴리우레탄.퓨란.폴리올.CO₂.Biomass.Isocyanate.Carbamate.Urea.Polyurethane.Furan.Polyol.
DOI	https://doi.org/10.23000/TRKO201700011957

초록 ▼

- 방향족 아민의 수소화 반응을 통해 지환족아민 전환용 고활성 촉매시스템 개발
- 3성분계 아민의 카르복실화 반응용 신촉매 개발 및 반응 메카니즘 규명
- 아민/CO₂ 기반 치환우레아 및 카바메이트 제조용 신촉매 개발
- 아민/CO₂/MeOH 기반 카바메이트 직접 제조용 신촉매 개발
- 방향족아민/H₂ 기반 지방족 카바메이트 직접 제조용 신촉매 시스템 개발
- HMF의 산화반응을 통한 FDCA/DFF/FDM 제조용 신촉매 개발
- 해양바이오매스 유래 퓨란계 전구체 제조를 통해 CMF 제조 가능성 파악

Abstract ▼

Ⅳ. Research Results
○ CO₂-based platform compouds
- 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.
○ Marine biomass based platform Compounds
- 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.
○ Polymerization & their potential application to bio-medicals
- 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)
(출처:SUMMARY 8~9p)

목차 Contents

표지 ... 1제 출 문 ... 2보고서 요약서 ... 3요 약 문 ... 4SUMMARY ... 7CONTENTS ... 10목차 ... 11제 1 장 연구개발과제의 개요 ... 13 1. 연구개발의 목적 ... 13 2. 연구개발의 필요성 ... 13 가. 경제적·산업적 중요성 ... 13 나. 연구개발의 필요성 및 범위 ... 15제 2 장 국내외 기술개발 현황 ... 20 1. CO2 기반 플랫폼 화합물 제조연구 ... 20 2. 해양 바이오매스 기반 플랫폼 화합물 제조연구 ... 24 3. 에코폴리우레탄의 중합 및 의료용 폴리머 적용연구 ... 27제 3 장 연구개발수행 내용 및 결과 ... 30 제 1절 CO2 기반 플랫폼 화합물 제조연구 ... 30 1. 방향족 화합물의 수소화 반응을 통한 지환족 아민 제조용 촉매 연구 ... 30 2. CO2 기반 플랫폼 화합물 제조용 신촉매 시스템 연구 ... 36 3. 방향족 아민으로부터 Ring Hydrogenated Carbamates 제조용 촉매연구 (1단계 반응촉매 시스템) ... 91 제 2절 해양 바이오매스 기반 플랫폼 화합물 제조연구 ... 99 1. 바이오매스 유래 폴리올 전구체 제조용 단위반응 연구 ... 99 2. 바이오매스 유래 폴리올 제조를 위한 반응경로 탐색 ... 125 제 3절 에코폴리우레탄의 중합 및 의료용 폴리머 적용연구 ... 136 1. 바이오매스 유래 퓨란기반 에스터계 폴리올 합성 및 에코폴리우리텐 중합 ... 136 2. Sugar diol을 이용한 친환경 폴리우레탄 합성 기술 ... 141제 4 장 목표달성도 및 관련분야에의 기여도 ... 154 1. 최종 목표 달성도 ... 154 2. 정량적 목표 달성도 ... 156 3. 세부기관과의 협업내용 ... 164제 5 장 연구개발결과의 활용계획 ... 165 1. 활용계획 ... 165제 6 장 연구개발과정에서 수집한 해외과학기술정보 ... 166제 7 장 연구시설·장비 현황 ... 168제 8 장 참고문헌 ... 171끝페이지 ... 175

표/그림 (188)

표 바이오매스 기반 바이오 폴리에스테르
표 Kolbe 반응
표 Urea 제조법
표 에폭사이드 이용 방법
표 Phosphorous 이용 방법
표 플랫폼 화합물로서 이산화탄소
표 아이소시아네이트 제조 방법
표 바이오매스기반 탄수화물
표 해양계 바이오매스 자원
표 포스겐 공정관련 특허 현황
표 Non-포스젠 공정 관련 특허 현황
표 CO2 이용공정 특허 현황
표 포스겐 법을 이용한 국내 TDI/MDI 생산업체 생산현황과 제조기술
표 의료용 폴리우레탄 응용분야 및 의료용 카테터 시장 (국내) 2011년 의료기기 산업분석 보고서
표 Reaction scheme for conversion of aromatic nitro compounds into alicyclic amines.
표 DSU and carbamates from 3-component reaction
표 Products and pathways from 3-component system.
표 Effect of promoter on the DCU yield using [Bmim][InCl4] as catalyst
표 [Bmim][InCl4] 제조 공정
표 Perparation of [Bmim][InI4]
표 NMR Spectra of [Bmim][InCl4] and [Bmim][InI4]
표 Catalytic activities comparison with various iodide-containing compounds
표 Effect of ratio on CHA with PO on the product composition.
표 Formation of DCU from reaction of HPC and CHA
표 Plausible mechanism for DCU from HPC catalysed by [Bmim][InI4].
표 FI-IR spectra
표 In situ FR-IR spectral change
표 DFT Calculation Results using [Bmim][InI4] vs without cat.
표 Direct synthesis of DSUs from carbon dioxide and amines
표 Effect of Ionic liquid on the formation of DCU.
표 Effect of alkaline salts on the formation of DCU
표 Effect of solvent on the formation of DCU
표 Effect of ratio reaction time on the formation of DCU
표 Effect of ratio(substrate/catalyst) on the formation of DCU
표 Effect of temperature on the formation of DCU
표 Effect of pressure on the formation of DCU
표 Effect of acetate salt on the formation of DCU
표 이온성 액체계 촉매를 구성하는 유기계 음이온
표 Catalytic activity of ILs on the formation of DCU.
표 Effect of reaction time and molar ratio on the yield of DCU
표 Effect of reaction temperature and pressure of CO2 on the yield of DCU
표 용매 DMF에서 BA의 반응의 부산물
표 Effect of solvents on the yield of DCU.
표 Catalyst Reuse Test using [Bmim][Triazolide]
표 Synthesis of 1,3-disubtituted urea from various amines
표 Synthesis of polyureas from diamines
표 IR spectra of polyuria from HMDA
표 IR spectra of polyuria from MBC
표 Synthesis of cesium azolide derivatives
표 Synthesis cesium benzotiazolide
표 FT-IR spectrum of Cs[BTd]
표 Elemental Analysis data of Cs[BTd]
표 Single-Crystal Structure of Cs[BTd]
표 Transformation of Cs[BTd] into [BTA]-Cs[BTd]
표 13C NMR spectra of Cs[BTd] in [d6]DMSO (a); after adding equiv of water into the NMR tube, followed by introduction of 13CO2 at room temperature (b).
표 Transformation of BTA into Cs[BTd] in the presence of CsHCO3.
표 Activities of various alkali metal benzotriazolides for carboxylation of n-hexylamine
표 comparing Cs-azolide catalyst with previously noted catalysts.
표 Effect of cation metal
표 Effect of different of anion
표 Effect of different of anion
표 Effect of added water on the DHU yield.
표 Effect of reaction time on the DHU yield
표 Effect of temperature on the DHU yield
표 Effect of pressure on the DHU yield
표 Effect of ratio(substrate/catalyst) on the formation of DHU
표 Effect of solvent on the activity
표 screening of different metal oxides.
표 The effect of catalysts on the reaction
표 A comparison of various supported catalysts
표 The effect of Cs2CO3 amount on Ceria on the yield of DCU
표 FT-IR for various loaded amount of Cs2CO3 on Ceria
표 Effect of reaction time on the DCU yield
표 The effect of temperature on the DCU yield
표 The effect of catalyst loading on the DCU yield.
표 The effect of solvents on the DCU yield.
표 Recycling studies using Cs2CO3/CeO2
표 FT-IR spectra of the reused catalyst
표 SEM images of a) Non-modified Merrifield’s resin, b) Poly-3.
표 XPS spectrum of (a) Merrifield’s resin, (b) Poly-3 (c) magnifying N 1s of poly-3 in (b).
표 FT-IR spectra of poly-3 and its precursors
표 The effect of anionic species on the formation of DCU.
표 Various properties of the synthesized polymer catalysts.
표 Effect of reaction time on the formation of DCU
표 Effect of temperature on the formation of DCU.
표 Effect of solvents on the formation of DCU
표 direct synthesis for producing carbamates from carbon dioxide
표 Preparation of defective ceria
표 XPS analysis on defective ceria and ceria
표 Raman analysis on defective ceria and ceria (argon ion laser of 514 nm)
표 atalyst screening
표 Effect of hydrogen reduction condition.
표 Effect of reaction time on the carbamate yield
표 Effect of temperature on the carbamate yield
표 Effect of catalyst amount on carbamate yield
표 Screening on the metal/treated ceria
표 Process diagram for producing HPC from aniline
표 TEM images of catalysts
표 TEM-EDX chromatogram images of catalysts
표 Specific surface area correlation with respect to catalytic reactivity for HPC formation.
표 Effect of molar ratio of CatNARO on the product composition
표 Effect of temperature on the product composition
표 Catalytic reusability tests
표 Plausible mechanism for the formation of HPC through RH and NARO reaction
표 Dehydration of biomass-derived furanose into HMF.
표 Polymer-supported NHC metal catalysts for dehydration of furanose into HMF.
표 (a) XPS spectra of polystyrene-bound imidazolium (PS-IM) and Fe(III) coordinated by polystyrene-attached NHC (PS-NHC-Fe(III)) (widescan), (b) peaks of Fe(III) 2p from PS-NHC-Fe(III), N 1s speaks from (c) PS-IM and (d) PS-NHC-Fe(III).
표 Dehydration of fructose into HMF using metal coordinated by polystyrene-attached NHC
표 (a) Intermediates during the dehydration of fructose into HMF and (b) proposed intermediates by mechanistic study.
표 Dehydration of fructose into HMF using EG-based solvents
표 Effect of (a) reaction temperature, (b) initial concentration of fructose, (c) catalyst dosage, (d) water content on dehydration of HFCS into HMF in 1,4-dioxane. Filled circles and reverse triangles indicate reaction rates and maximum yield of HMF, respectively.
표 Dehydration of fructose into HMF using rare metal triflates in 1,4-dioxane.
표 Procedure for preparation of biomass-derived acid catalyst (sulfonated amorphous carbon).
표 Characteristics (BET surface area and acid capacity) of prepared AC-SO3H
표 (a) FT-IR and (b) XPS spectra of sulfonated amorphous carbonaceous materials.
표 Dehydration of fructose into HMF using homogeneous and heterogeneous acid catalysts containing -SO3H in an EG-based solvent
표 (a) Conversion and (b) selectivity in oxidation of HMF by Ru/γ-Al2O3 according to solvents. Reaction conditions: HMF (2 mmol), Ru/γ-Al2O3 (200 mg), solvent (15 ml), O2 (40 psi), 120 ℃, 4 h, 650 rpm).
표 Influence of substrate concentration on HMF conversion (Reaction conditions: HMF (designated amount), Ru/γ-Al2O3 (200 mg), toluene (15 mL), O2 (40 psi), 120 ℃, 4 h, 650 rpm)
표 (a) Influence of temperature on HMF conversion to DFF (Reaction conditions: HMF (2 mmol), Ru/γ-Al2O3 (200 mg), toluene (15 mL), O2 (40 psi), 4 h, 650 rpm); (b) Reusability of the catalyst (Reaction conditions: HMF (2 mmol), Ru/γ-Al2O3 (200 mg), solvent (15 mL), O2 (40 psi), 120 ℃, 4 h, 650 rpm).
표 Process for production of DFF by selective oxidation of HMF using oxygen and heterogeneous metal catalyst in MIBK, the extracting solvent of HMF.
표 (a) Comparison of XPS spectra of V/AC prepared from VCl3 (red) and NH4VO3 (green); (b) TEM image of V/AC prepared from VCl3.
표 (a) Influence of O2 pressure (Reaction conditions: HMF: 200 mg, V@HMF: 5 mol%, temperature: 100 ℃, time: 4 h) and (b) temperature (Reaction conditions: HMF: 200 mg, V to HMF: 5 mol%, O2 pressure: 40 psi, time: 4 h) on oxidation of HMF in MIBK.
표 Influence of molar ratio of catalyst to substrate in oxidation of HMF (Reaction conditions: HMF; 200 mg, catalyst; V/AC, solvent; MIBK, temperature; 100 ℃, O2 pressure; 40 psi, time; 4 h)
표 (a) Time-course investigation and (b) recyclability of V/AC of HMF oxidation (Reaction conditions: HMF: 200 mg, V/HMF: 10 mol%, O2pressure:40 psi, temperature: 100 ℃).
표 Powders of MnCo2CO3 (left), MnCo2O4(middle) and of Ru/MnCo2O4 after drying (right).
표 XRD patterns of synthesized MnCo2CO3 and MnCo2O4(left) and SEM image of MnCo2O4 (right)
표 XPS spectra of the Ru/MnCo2O4 microspheres: Survey spectrum-(a), Co 2p-(b), Mn 2p-(c), O 1s-(d), Ru 3d-(e), and Ru 3p-(f).
표 TEM image of Ru/MnCo2O4 (a), and elementals mapping layered image (b), Mn (c), Co (d), O (e), and Ru (f).
표 Texural properties of MnCo2O4 and Ru(4%)/MnCo2O4
표 Reaction of DFF from HMF
표 Effect of amount of catalysts.
표 Reaction of DFF from HMF
표 Catalyst screening in oxidation of HMF
표 Product compositional changes as a function of time
표 Possible reaction pathway for the formation of FDCA from HMF
표 Catalyst recycling test (Catalyst=Ru(4.0%)/MnCo2O4, HMF/Ru=33.6, solvent (H2O)= 20 mL, T=100 oC, P(air)= 2.4 MPa)
표 Switchable production of FDCA or DFF depending on the solvent.
표 Reduction of DFF to produce FDM
표 Reduction of DFF to produce FDM
표 Schematic view of direct conversion of biomass-derived carbohydrates into CMF under biphasic system using conc. hydrochloric acid and 1,1,2-trichloroethane.
표 Conversion of agarose into CMF using diluted HCl (6 N) and 1,1,2-TCE
표 Conversion of CMF into AMF with alkylammonium acetate.
표 Reactivity of alkylammonium acetates in the conversion of CMF into AMF.
표 Heterogeneous conversion of CMF into AMF by using polymer-supported alkylammonium acetate.
표 Reusability of acetate-exchanged Amberlite IRA-900.
표 Dehydration of galactaric acid into FDCA alkyl esters.
표 (a) Experimental view of dehydration of galactaric acid into FDCA dialkyl esters using a Dean-Stark apparatus and photos of reaction mixture (b) at initial stage and (c) at the end of reaction.
표 Yields of FDCA butyl esters according to acid catalyst
표 (a) Yields of FDCA butyl esters according to the amount of PTA and (b) selectivity of FDCA butyl ester isomers.
표 Scheme for FDCA synthesis from galactaric acid via esterification and solventless dehydration.
표 Change of reaction mixture during esterification of galactaric acid into dibutyl galactarate.
표 Appearance of precipitate after reaction (right) and 1H-NMR spectra of the precipitate.
표 Comparison of yields of ester products according to alcohols.
표 (a) HPLC profile of solventless dehydration of dibutyl galactarate into FDCA and (b) FDCA yields according to reaction time.
표 Synthesis of PDoF and PDoFPU.
표 GPC of polyesterpolyol and polyurethane.
표 DSC data of polyesterpolyol and polyurethane.
표 FT-IR data of polyesterpolyol and polyurethane.
표 GPC data ofpolyurethane using various mol ratio of H12MDI.
표 FT-IR data of polyurethane using various mol ratio of H12MDI.
표 GPC data of polyurethane.
표 FT-IR data of polyurethane.
표 Sugar-diol을 이용한 폴리우레탄 합성 방법
표 다양한 diol을 이용한 폴리우레탄 프리폴리머의 인장특성
표 정제법에 따른 furan-diol의 1H-NMR과 성상 사진
표 Furan-diol을 이용한 폴리우레탄 합성 schem
표 폴리우레탄 프리폴리머 제조 조건 및 그에 따른 분자량
표 PTMG 와 Furan-diol로 제조한 폴리우레탄에서 발생한 dark particles
표 온도에 따른 dark particle 생성 결과
표 반응 조건 변경에 따른 dark particle 발생 변화
표 PTMG 와 Furan-diol의 비율 차이에 따른 합성 조건과 결과
표 PTMG와 Furan-diol을 이용한 폴리우레탄의 재현성 결과
표 Furan-diol의 안정성 변화
표 온도 상승에 따른 Furan-diol의 1H-NMR 변화
표 신규 furan-diol을 이용한 폴리우레탄 프리폴리머 합성
표 신규 Furan-diol을 이용한 폴리우레탄 프리폴리머 합성
표 신규 furan-diol을 이용한 프리폴리머 합성
표 Chain extending을 이용한 폴리우레탄 합성
표 Chain extending 온도 및 시간에 따른 폴리우레탄 합성 결과
표 PU-3의 Strain-Stress curve
표 폴리우레탄의 기계적 특성 비교
표 다양한 다이올을 이용한 퓨란계 매크로머 합성
표 적정법에 의한 매크로머의 OH 값 측정
표 퓨란계 매크로머를 이용한 폴리우레탄 합성 스킴
표 매크로머 비율 변화에 따른 폴리우레탄 합성 결과
표 HD-매크로머를 이용한 폴리우레탄의 S-S 커브
표 폴리우레탄의 기계적 특성 비교
표 Synthesis of carbamate or isocyanate from amine and CO2 Using organotin derivatives

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연합인증

이산화탄소-해양바이오매스 기반 플랫폼 화합물 제조 및 EcoPolymer의 기능화 연구
Synthesis of CO₂-Marine Biomass based Platform Chemical and Functionalization of Eco-polymer 원문보기