아크릴산 그라프트 폴리프로필렌 부직포로부터 아민형 음이온 교환체의 합성 및 PO₄-P의 제거특성

나춘기,박현주,정일현 7개 국립대학교 환경연구 논문집 공동발행 위원회 2003 공업기술연구 Vol.3 No.-

Aminated PP-g-AA that possess anionic exchangeable function was prepared by photoinduce grafting of acrylic acid onto polypropylene nonwoven fabric and followed chemical treatments using diethylene triamine coupled with aluminum chloride catalyst. Amination of grafted acrylic acid increased with increasing the reaction time and temperature of the aluminum catalysed amination procedure. Increasing the degree of amination, resulting in increasing the PO_(4)-P exchange capacity of aminated PP-g-AA and therefore, it reaches maximum value at the degree of amination as about 50-60%. Its value was much higher than those of conventional anion resins and activated carbon. Futhermore, aminated PP-g-AA nonwoven fabric could be regenerated in more than ten times by acid washing without any degradation of ion exchange capacity and physical properties.

Synthesis of substituted amines: Catalytic reductive amination of carbonyl compounds using Lewis acid Zn–Co-double metal cyanide/polymethylhydrosiloxane

Jadhav, Amol R.,Bandal, Harshad A.,Kim, Hern Elsevier 2016 Chemical Engineering Journal Vol. No.

<P><B>Abstract</B></P> <P>Zn–Co double metal cyanide (DMC) is found to be an effective heterogeneous catalyst for reductive amination reaction of carbonyl compounds with aromatic amines using inexpensive polymethylhydrosiloxane (PMHS) as a reducing agent. The asprepared catalyst was characterized by scanning electron microscopy (SEM), fourier transform infrared spectroscopy, X-ray diffraction, energy dispersive X-ray spectrometer (EDX), N<SUB>2</SUB> adsorption–desorption, and thermogravimetric analysis. Substituted amines were efficiently synthesized by a convenient, simple and environment friendly procedure in excellent yields. In order to optimize the reaction condition, it was carried out by varying reaction parameter such as temperature and using different solvent. Notably, the highest yield of the desired amine product was achieved in methanol at 60°C. The main advantages of this methodology is easy catalyst preparation and separation, high thermal catalytic stability, mild reaction condition, recyclable catalyst and high yield.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Selective reductive amination of carbonyl compounds using Zn–Co-DMC/PMHS. </LI> <LI> The Zn–Co-DMC catalyst showed higher activity than Zn–Co-PEG-DMC. </LI> <LI> The highest yield of the desired amine product was achieved in methanol at 60°C. </LI> <LI> Stability of the Zn–Co-DMC catalyst system tested by recycling. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Tertiary Amination/Hydroxypropylsulfonation of Cornstarch to Improve the Adhesion-to-Fibers and Film Properties for Warp Sizing

Wei Li,Zhenzhen Xu,Zongqian Wang,Changlong Li,Quan Feng,Yanan Zhu 한국섬유공학회 2018 Fibers and polymers Vol.19 No.7

To investigate the effects of tertiary amination/hydroxypropylsulfonation on the adhesion-to-fibers and film properties of corn starch for warp sizing, a series of tertiary aminated and hydroxypropylsulfonated corn starch (TAHPSS) samples were prepared by the tertiary amination and hydroxypropylsulfonation of acid-hydrolyzed corn starch (AHS) with 2- dimethylaminoethyl chloride hydrochloride (DMC-HCl) and 3-chloro-2-hydroxy-1-propanesulfonic acid sodium salt (CHPS-Na) simultaneously. The adhesion was evaluated by measuring the bonding force of starch to the fibers. The film properties were investigated in terms of tensile strength, breaking elongation, degree of crystallinity, and moisture regain. The results showed that tertiary amination/hydroxypropylsulfonation was able to increase bonding forces of starch to cotton and polyester fibers, enhance breaking elongation and moisture regain of the starch film and to decrease the tensile strength and degree of crystallinity of the film, thereby improving the adhesion and reducing film brittleness. Increasing the level of tertiary amination/hydroxypropylsulfonation was favorable for gradually improving the adhesion and decreasing the brittleness. The TAHPSS showed potential for use in cotton warp sizing.

왕겨를 이용한 생체흡착제 제조: GMA공중합과 아민화를 통한 음이온 흡착관능기 도입

나춘기 한국폐기물자원순환학회 2014 한국폐기물자원순환학회지 Vol.31 No.7

This research investigated the feasibility of rice husk (RH) as a biosorbent for the removal of anions from aqueoussolution. RH-g-GMA-Am biosorbent, which possesses anionic exchangeable function, was prepared through graftpolymerization of glycidyl methacrylate (GMA) in the presence of N,N'-methylene-bis-acrylamide as a cross-linker usingpotassium peroxydisulphate as a redox initiator and subsequent amination reaction using ethylenediamine (EDA),diethylenetriamine (DETA), dimethylamine (DMA) and trimethylamine (TMA) as a amine source. Fourier transforminfrared (FTIR) and scanning electron microscopy (SEM) analysis as well as the sorption capacity for anions verifiedthe presence of grafted GMA polymers and amine groups on the RH surface. The zero point of surface potential ofaminated RH-g-GMA-Am sorbent was 6.4, which facilitated the sorption of anions on the positively charged sorbent atpH<6.4. The sorption capacity of RH-g-GMA-Am depending on the amination chemicals increased in the order:DETA≥EDA>DMA>TMA, i.e., primary amine>secondary amine>tertiary amine. The sorption selectivity of RH-g-GMA-Am sorbent aminated with DETA and EDA in the presence of equimolar anions and at pH 4.7 increased in theorder: SO4>PO4>NO3>F. Furthermore, their sorption capacities for PO4 were much higher than those of commercialanion-exchange resins. The results obtained suggest that the RH-g-GMA-Am biosorbent prepared by the GMA graftcopolymerization and subsequent amination can be used as an effective anion-exchanger comparable to commercial anion-exchange resins.

Fundamental reaction kinetics of high-pressure reductive amination of polyalkylene glycol

Kyungjun Kim,Dong Woo Kang,Chan Yeong Yun,Youngheon Choi,Jae W. Lee 한국공업화학회 2022 Journal of Industrial and Engineering Chemistry Vol.106 No.-

This study investigates reaction kinetics of high-pressure amination of polyalkylene glycol (PAG) to polyetheramine(PEA). The reductive amination of PAG was carried out depending on the NH3 amount, reactiontemperature, reaction pressure, and H2O content in a batch reactor to understand the effect of thesefactors on activity and selectivity toward the primary amine. Contrary to the fact that the amination stepis a zero-order reaction and dehydrogenation of alcohol to ketone is the rate-limiting step in the reductiveamination of alcohol, the amount of NH3 significantly affected the reaction rate. The increasedamount of NH3 enhanced the activity and selectivity for PEA, in contrast with the results reported in priorstudies. A Langmuir-Hinshelwood kinetic model was established to reflect the effect of the NH3 amount,and kinetic parameters such as the rate constant and activation energy were obtained at a high pressurearound 150 bar. It was also found that the absence of NH3 caused the reverse reaction of PEA to the secondaryamine in the presence of H2. The fundamental kinetic analysis provides a competitive synthesisroute for improving the activity and selectivity toward the primary amine.

Cobalt based catalysts for reductive amination of polypropylene glycol

김경준,최영헌 한국공업화학회 2019 한국공업화학회 연구논문 초록집 Vol.2019 No.0

Cobalt based catalysts were used for the facile one-pot synthesis of polyetheramine (PEA) from polypropylene glycol (PPG) through reductive amination. It was shown that high hydrogen partial pressures inhibit theformation of cobalt nitride and lead to a high PEA yield although it has been known that dehydrogenation from alcohol to ketone is the rate-determining step. Cobalt based catalysts developed also showed high yield toward PEA even under low hydrogen partial pressures, not only preventing the formation of cobalt nitride but alsopromoting hydrogenation of imine to amine. Thus cobalt based catalysts we developed provides unique performance toward increasing the PEA yield while suppressing the catalyst deactivation caused by the cobalt nitride formation.

Y₂O₃-Inserted Co-Pd/zeolite catalysts for reductive amination of polypropylene glycol

Kim, Kyungjun,Choi, Youngheon,Lee, Hyunjoo,Lee, Jae W. Elsevier 2018 Applied Catalysis A Vol.568 No.-

<P><B>Abstract</B></P> <P>Cobalt-based catalysts having different base strengths were prepared by controlling the amount of yttrium oxide (Y<SUB>2</SUB>O<SUB>3</SUB>). These catalysts were used for the facile one-pot synthesis of polyetheramine (PEA) from polypropylene glycol (PPG) through reductive amination. It is noticed that high hydrogen partial pressures up to 40 bar inhibit the formation of cobalt nitride and lead to a high PEA yield although it has been known that dehydrogenation from alcohol to ketone is the rate-determining step. The Y<SUB>2</SUB>O<SUB>3</SUB>-inserted Co-Pd/Molecular sieve13X catalyst also showed high activity toward PEA even at low hydrogen partial pressure. Y<SUB>2</SUB>O<SUB>3</SUB> played a crucial role in giving basicity to the catalyst, which not only prevents the formation of cobalt nitride but also promotes hydrogenation of imine to amine at a wide range of H<SUB>2</SUB> pressure. Thus Y<SUB>2</SUB>O<SUB>3</SUB> inserted Co-Pd/Molecular sieve 13X provides unique performance toward enhancing the PEA yield while suppressing the catalyst deactivation caused by the cobalt nitride formation.</P> <P><B>Highlights</B></P> <P> <UL> <LI> Y<SUB>2</SUB>O<SUB>3</SUB>–Inserted Co-Pd catalysts were prepared for reductive amination. </LI> <LI> The catalysts led to 99% PEA yield from PPG via a facile one-pot synthesis. </LI> <LI> The Y<SUB>2</SUB>O<SUB>3</SUB>-inserted catalysts inhibit Co<SUB>3</SUB>N but promote hydrogenation of imine. </LI> <LI> Basicity of Y<SUB>2</SUB>O<SUB>3</SUB> hinders NH<SUB>3</SUB> access into the cobalt surface of the catalysts. </LI> </UL> </P> <P><B>Graphical abstract</B></P> <P>[DISPLAY OMISSION]</P>

Biofouling 방지를 위한 항균성 멤브레인 필터의 제조 : GMA의 그라프트 중합과 아민화/술폰화에 의한 표면개질

나춘기 ( Choon-ki Na ),송재준 ( Jee-june Song ) 한국환경기술학회 2021 한국환경기술학회지 Vol.22 No.3

Biofouling is a major problem of membrane processes in water and wastewater treatment. One of the anti-biofouling strategies is to construct an antimicrobial membrane surface. In this study, polypropylene(PP) microfiltration membranes with antimicrobial property were fabricated by grafting glycidyl methacrylate(GMA), followed by amination or sulfonation with ethylenediamine or sodium sulfite solution. GMA was facilely grafted onto PP membrane by UV-induced graft polymerization, and the graft chains were easily aminated or sulfonated by a simple chemical reaction. The modified PP membranes were characterized by FT-IR, SEM, water permeability and antimicrobial tests. The PP membranes modified by grafting GMA improved the water permeability due to the hydrophilization of the surface, but the antimicrobial activity was too low. In contrast, aminated or sulfonated PP membranes exhibited high antimicrobial activity against both E. coli and S. aureus without a significant reduction in the water permeability.

선택적 1차 아민 합성을 위한 Alcohol의 Amination

강지선,기현준,최란주,이경진,윤석일 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.0

아민기는 양성자와 결합하여 양전하를 띠는 양이온이 될 수 있고, 질소 원자가 가지고 있는 비공유 전자쌍으로 인하여 친핵체로 작용하는 등 반응성이 매우 커 상업적으로 주요한 작용기이다. 또한 아민기의 함유량에 따라 친수성이 증가하고 acetylation등의 반응을 일으킬 수 있는 특징이 있다. 본 연구에서는 1차 알콜인cinnamyl alcohol의 말단기 -OH를 -NH2로 치환하는 amination을 진행하였다. Pt를 기반으로 한 [Pt(cod)Cl2] 촉매와 DPEphos 리간드를 사용하여 cinnamyl alcohol의 선택적 1차 아민 합성을 진행하였다. 반응 온도와 반응 시간등을 변수로 하여 반응을 진행하였을 때, 생성물의 전환율과 전환된 물질의 아민 선택도를 분석하여 요구조건에 가장 적합한 반응조건을 찾아보았다. NMR과 GC/MS를 통해 합성된 물질을 분석하고 부가적으로 적정법을 이용하였다. 분석결과를 비교하여 간략화된 분석방법과 기존의 기기분석방법과의 차이를 알아보았다.

Ammonia를 이용한 Polyol의 아민화 반응 연구

홍샘,이경진,강지선,윤석일 한국공업화학회 2016 한국공업화학회 연구논문 초록집 Vol.2016 No.1

Amine은 공업적으로 중요한 중간체이며, 특히 1차 아민은 유도체화 반응의 중간체로서 유용하다. 현재 공업적으로 가장 많이 이용되는 지방족 아민을 합성법은 탄화수소 화합물의 환원성 아민화 반응으로 수소 공급이 필요한 방법이다. 최근 주목 받고 있는 합성법은 “borrowing hydrogen” 또는 “hydrogen auto-trasfer”으로 알데하이드나 케톤을 사용하지 않고 암모니아를 이용해 알콜을 1차 아민으로 직접 합성하는 것을 말한다. 이 방법은 Amination의 마지막 단계인 hydrogenation에 필요한 수소를 알콜의 dehydrogenation 반응에서 제거된 수소로 공급함으로서 추가적으로 수소 가스를 공급할 필요가 없을 뿐 아니라 높은 온도와 압력도 필요하지 않다. 또한 반응성이 좋은 carbonyl 화합물이 낮은 농도에서 생성되어 원치 않는 부반응을 최소화할 수 있다. 본 연구에서는 borrowing hydrogen 방법에 적합하다고 알려진 Ru 촉매를 이용해 Polyol을 Polyetheramine으로 합성하는 실험을 진행하였다. 촉매의 양과 암모니아의 양을 조절해 다양한 조건에서 실험을 진행해 각 변수가 전환율, 선택도에 미치는 영향을 조사하였다.