PVK-b-PVP 블록 공중합체의 존재 하에서 안정한 비 수계 그래핀 분산액을 위한 용매-고분자 상호작용에 관한 연구 Solvent-Polymer Interactions for Stable Non-Aqueous Graphene Dispersions in the Presence of PVK-b-PVP Block Copolymer원문보기
본 연구에서는 poly(N-vinyl carbazole) (PVK), poly(4-vinylpyridine) (PVP), PVK-b-PVP 블록 공중합체를 RAFT 중합법으로 합성하였으며, 이를 이용하여 ethanol, N-methyl-2-pyrrolidone (NMP), dichloromethane (DCM), tetrahydrofuran (THF)와 같은 비 수계 용매에서 그래핀 분산액을 제조하였다. 합성된 고분자의 화학적 구조는 양성자 및 탄소 핵자기 공명 분광기($^1H-$, $^{13}C-NMR$), 크기 배제 크로마토그래피 (size exclusive chromatography, SEC), 시차 주사 열량계 (differential scanningcalorimetry, DSC)를 이용하여 분석하였으며, 그래핀 분산액의 분산 안정성은 Turbiscan을 이용하여 시간에 따른 터비스캔 안정성 지수(Turbiscan stability index, TSI)를 측정, 정량적으로 평가하였다. 용매, 고분자, 그래핀의 표면장력(${\sigma}$), 용해도 상수(${\delta}$)를 이용하여 물질간의 상호작용에 대하여 설명하였으며, 이를 바탕으로 용매와 그래핀간의 용해도와 표면장력의 차이가 분산안정성에 큰 영향을 미침을 확인하였다. 그래핀의 분산 안정성이 좋지 못한 ethanol 및 THF 용매 하에서 PVK-b-PVP를 사용하여 그래핀을 분산시킬 경우 낮은 TSI값을 효과적으로 유지할 수 있었으며, 그래핀을 잘 분산시킨다고 알려진 NMP에 비하여 DCM이 더 좋은 그래핀 분산안정성을 보임을 확인하였다.
본 연구에서는 poly(N-vinyl carbazole) (PVK), poly(4-vinylpyridine) (PVP), PVK-b-PVP 블록 공중합체를 RAFT 중합법으로 합성하였으며, 이를 이용하여 ethanol, N-methyl-2-pyrrolidone (NMP), dichloromethane (DCM), tetrahydrofuran (THF)와 같은 비 수계 용매에서 그래핀 분산액을 제조하였다. 합성된 고분자의 화학적 구조는 양성자 및 탄소 핵자기 공명 분광기($^1H-$, $^{13}C-NMR$), 크기 배제 크로마토그래피 (size exclusive chromatography, SEC), 시차 주사 열량계 (differential scanning calorimetry, DSC)를 이용하여 분석하였으며, 그래핀 분산액의 분산 안정성은 Turbiscan을 이용하여 시간에 따른 터비스캔 안정성 지수(Turbiscan stability index, TSI)를 측정, 정량적으로 평가하였다. 용매, 고분자, 그래핀의 표면장력(${\sigma}$), 용해도 상수(${\delta}$)를 이용하여 물질간의 상호작용에 대하여 설명하였으며, 이를 바탕으로 용매와 그래핀간의 용해도와 표면장력의 차이가 분산안정성에 큰 영향을 미침을 확인하였다. 그래핀의 분산 안정성이 좋지 못한 ethanol 및 THF 용매 하에서 PVK-b-PVP를 사용하여 그래핀을 분산시킬 경우 낮은 TSI값을 효과적으로 유지할 수 있었으며, 그래핀을 잘 분산시킨다고 알려진 NMP에 비하여 DCM이 더 좋은 그래핀 분산안정성을 보임을 확인하였다.
Poly(N-vinyl carbazole) (PVK) homopolymer, poly(4-vinylpyridine) (PVP) homopolymer, and PVK-b-PVP block copolymer were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and the polymers were used to prepare non-aqueous graphene dispersions with four different solv...
Poly(N-vinyl carbazole) (PVK) homopolymer, poly(4-vinylpyridine) (PVP) homopolymer, and PVK-b-PVP block copolymer were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and the polymers were used to prepare non-aqueous graphene dispersions with four different solvents, ethanol, N-methyl-2-pyrrolidone (NMP), dichloromethane (DCM), and tetrahydrofuran (THF). $^1H-$ and $^{13}C-NMR$ spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) were carried out to confirm the chemical structure of the polymers. Stability of graphene dispersions was measured by on-line turbidity measurement. Time-dependent Turbiscan Stability Index (TSI) values were interpreted in terms of surface tension (${\sigma}$) and solubility parameter (${\delta}$) among solvents, polymers, and graphene. It was confirmed that the solubilities of polymer and surface tension between solvent and graphene affected the dispersion stability of graphene. PVK-b-PVP block copolymer could effectively maintain the low TSI values of graphene dispersions in ethanol and THF, which have been known as poor solvents for graphene dispersions. It can also be noted that DCM shows good dispersion stability comparable to NMP, which has been known as the best solvent for graphene dispersion.
Poly(N-vinyl carbazole) (PVK) homopolymer, poly(4-vinylpyridine) (PVP) homopolymer, and PVK-b-PVP block copolymer were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization and the polymers were used to prepare non-aqueous graphene dispersions with four different solvents, ethanol, N-methyl-2-pyrrolidone (NMP), dichloromethane (DCM), and tetrahydrofuran (THF). $^1H-$ and $^{13}C-NMR$ spectroscopy, size exclusion chromatography (SEC), and differential scanning calorimetry (DSC) were carried out to confirm the chemical structure of the polymers. Stability of graphene dispersions was measured by on-line turbidity measurement. Time-dependent Turbiscan Stability Index (TSI) values were interpreted in terms of surface tension (${\sigma}$) and solubility parameter (${\delta}$) among solvents, polymers, and graphene. It was confirmed that the solubilities of polymer and surface tension between solvent and graphene affected the dispersion stability of graphene. PVK-b-PVP block copolymer could effectively maintain the low TSI values of graphene dispersions in ethanol and THF, which have been known as poor solvents for graphene dispersions. It can also be noted that DCM shows good dispersion stability comparable to NMP, which has been known as the best solvent for graphene dispersion.
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제안 방법
In order to study the effect of homopolymer on the dispersion stability of graphene, PVK and PVP were also used and compared. Four different solvents, ethanol, NMP, DCM, and THF were used as dispersion media and the dispersion stability of graphene in different solvent was analyzed and compared. For the graphene dispersion, 20 mg of M-25, and 10 mg of homopolymer or block copolymer in 4 mL of solvent were added into a vial.
For a study on dispersion stability of graphene platelets, non-oxidative graphene was dispersed with or without PVK-b-PVP diblock copolymer. In order to study the effect of homopolymer on the dispersion stability of graphene, PVK and PVP were also used and compared. Four different solvents, ethanol, NMP, DCM, and THF were used as dispersion media and the dispersion stability of graphene in different solvent was analyzed and compared.
Solvent-polymer interaction was studied by solubility tests in four different solvents, such as ethanol, NMP, DCM, and THF. The prepared homopolymers and block copolymer were used as dispersants for non-aqueous dispersion of graphene platelets, and their dispersion stability was investigated and compared by using on-line turbidity. Surface tension and solubility parameters between solvent-polymer and solvent-graphene were considered to explain the dispersion stability of graphene in different solvent-polymer pairs.
성능/효과
VK monomer (98%, TCI, Japan) was used as received without further purification. 2-(Dodecylthiocarbonothioylthio)-2-methylpropionic acid (TTC, 98%, Aldrich, USA), 1,4-dioxane (99.5%, Acros, USA), N,N-dimethyl formamide (DMF, 99.5%, Duksan, Korea), hexanes (95%, Duksan, Korea), THF (99.5%, Duksan, Korea), DCM (99.5%, Duksan, Korea), NMP (99.5%, Samchun, Korea), and ethanol (99.8%, Duksan, Korea) were used as received without further purification. 2,2’-Azobisisobutyronitrile (AIBN, 98%, Junsei, Japan) was used after recrystallization in methanol.
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