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氏名 菅野 修一
所属 家政学部 家政学科
職名 教授
学位 工学博士
専門分野 高分子合成、イオン液体物性
主な担当教科 有機化学Ⅰ・Ⅱ、化学Ⅰ・Ⅱ、被服繊維学、被服材料学、課題研究(ポリマーケミストリー)

研究題目

  • 新規なラジカル重合開始剤としてのイオン液体に関する研究
  • 新規なリビングラジカル重合開始剤としてのホウ素化合物に関する研究
  • 遷移金属系常温レドックスラジカル重合開始剤の開発
  • 古典的ラジカル重合開始剤を用いた空気雰囲気下における重合の応用に関する研究

最近の主な業績

Ⅰ.研究活動

著書・論文等の名称 単著・共著 発行又は発表の年月(西暦) 発行所、発表雑誌(及び巻、号数)等の名称 共著者名 掲載頁
Specific Radical Polymerization Initiated with Imidazolium Ionic Liquids under Various Polymerization Conditions-2 2016年 東北生活文化大学紀要, 47 須田 篤 83-92
Specific Radical Polymerization Initiated with Imidazolium Ionic Liquids under Various Polymerization Conditions-2 2016年 東北生活文化大学紀要, 47   51-60
Unique Radical Polymerization Initiated with Borane-Lewis Base Complexes such as Borane-trimethylamine Complex and Borane-triethylamine Complex 2015年 東北生活文化大学紀要, 46 須田 篤 75-95
Manifestation of the Unique Initiating Ability about Radical Polymerization by the Combination of Cations and Anions of Imidazolium Ionic Liquids 2015年 東北生活文化大学紀要, 46   45-74
Unique Radical Polymerization Initiated with Borane-Lewis Base Complexes such as Borane-N,N-diethylaniline Complex and Borane-ammonia Complex 2014年 東北生活文化大学紀要, 45   41-59
Influences about the Cationic Structure of Bis(trifluoromethylsulfonyl)imide Anion Based Ionic Liquids as a Radical Initiator of Butyl Acrylate Polymerization 2014年 東北生活文化大学紀要, 45 須田 篤 25-40
Challenges for Unique Application of Ionic Liquids as a Novel Initiator of Radical Polymerization 2014年 Molecular Crystals & Liquid Crystals, Volume 603, Issue 1   3-19
Studies on the Polymerization of Styrene Initiated with Borane-diethylaniline Complex under Air 2013年 東北生活文化大学紀要, 44 須田 篤 55-74
Ionic Liquid as an Radical Initiator: A Powerful Approach to Polymerize Vinyl Acetate by Using Imidazolium Based Ionic Liquids 2013年 東北生活文化大学紀要, 44   31-54
New Aspects of Ionic Liquids as a Novel Initiator of Radical Polymerization 2012年 Molecular Crystals & Liquid Crystals, Volume 556, Issue 1   61-73

*ここに示した業績は、著者の業績の一部として当大学の紀要を中心に記載した。尚、本紀要は国立国会図書館に収蔵されているので、著者の業績の概要は各紀要のReferenceを御参照下さい。そこにこれよりは広範に記載されているとおり、著者の業績は英文ジャーナル誌・日本国特許・国内専門誌・国際会議プロシーディング・国内各種学会予稿集など数百にわたる。

Ⅱ.教育活動

教育実践上の主な業績 年月日 概要
Impact Behavior of Phosphonium-Based Ionic Liquids as a Novel Initiator of
Radical Polymerization
BOOK OF ABSTRACTS The 11th International Chemistry Conference and Exhibition in
Africa, (2010) 337./ (pyramisa isis hotel Luxor/ Luxor, Egypt)
The author recognized that there may be no research on the radical polymerization initiated with ionic liquid except for the author’s investidations.In this study, the author discussed fundamental features of the radical polymerization initiated with some phosphonium-based ionic liquids. For example, until then, the author reported an radical initiating ability of trihexyl(tetradecyl)phosphonium tetrafluoroborate ([P(h3)t]BF4), but the initiating mechanism was not clear. Consequently, a further study about the detailed mechanism of [P(h3)t]BF4-initiated polymerization was needed. Needless to say, the kinetic aspects of the radical polymerization process are very important for the better understanding of the polymerization mechanism. As typical examples, from the data for the effect of initiator concentration and monomer concentration on the polymerization of methyl methacrylate (MMA) initiated with [P(h3)t]BF4 under air at 70 oC in dioxane, it was easily understood that the initiator concentration does not affect the rate of polymerization. In addition, surprisingly, the rate of polymerization decreased with increase of the monomer concentration. In the typical case of conventional radical polymerization, the rate of polymerization is proportional to the square root of the initiator concentration, and that is first order with respect to monomer concentration. Consequently, this polymerization seemed to be significantly different from the usual radical polymerization at this point.
The Novel Conception of Ionic Liquids as an Initiator of Radical Polymerization
of Vinyl Monomers
BOOK OF ABSTRACTS The 11th International Chemistry Conference and Exhibition in
Africa, (2010) 265./ (pyramisa isis hotel Luxor/ Luxor, Egypt)
The author targeted ionic liquids as an specific initiator of radical polymerization so far, while there were no reports about the application of ionic liquids as an initiator of radical polymerization except for the author’s investigations. Generally, since ionic liquids are characterized by good thermal and chemical stability, nobody focuses on them as an initiator of radical polymerization. Hence, in this study, the author discusses the simple approach to prove the initiating ability of radical polymerization on some kinds of ionic liquids. One can observe the typical example as follows. From the data about the effect of temperature on the polymerization of ethyl acrylate (EA) initiated with 2,2′-azobisisobutyronitrile (AIBN) as a conventional radical initiator and 1-butyl-3-methylimidazolium thiocyanate ([bmim]SCN) as an ionic liquid under air in tetrahydrofuran, it was obviously that the polymerization proceeds via radical pathway, because the inhibitory effects of 1-dodecanethiol as a radical chain transfer agent and hydroquinone or 2,6-di-tert-butyl-p-cresol as a radical inhibitor were observed. One should pay attention to the fact that a 15.6 % conversion of EA was observed in [bmim]SCN-initiated polymerization at 40 oC after 120 minutes, but AIBN did not initiate the EA-polymerization under the same reaction conditions. Needless to say, thermal polymerization of EA under same reaction conditions did not proceed. The obtained results indicate that [bmim]SCN has the initiating ability of radical polymerization. Additionally, with regard to the temperature range on the initiating activity the results show an advantage of [bmim]SCN, which is more wide than that of AIBN.
Recent Achievements in Radical Polymerization of Vinyl Monomers Initiated with Ionic
Liquids
Macro2010 – 43rd IUPAC World Polymer Congress Polymer Science in the Service of Society – Abstract book and programme, (2010) C11_O23. /
(Scottish Exhibition and Conference Centre / Glasgow, UK)
In recent years, ionic liquids have been extensively investigated for use as replacement solvents for a variety of radical polymerizations. It is found from some of these investigations that the large increases in both the polymerization rate and the molecular weight of the resulting polymer compared to polymerizations in conventional organic solvents are observed. In addition, to date it is well known that ionic liquids have great potential as media for radical polymerizations because of their outstanding solution properties, vanishing vapor pressure, high thermal stability, and recycling capability. In this manner, in the polymer chemistry community, research and development relating to ionic liquids concentrated mainly on the use of replacement media for radical polymerizations. Nevertheless, the author targeted for the first time ionic liquids as an specific initiator of radical polymerization. In this investigation, the author discusses recent achievements in radical polymerization of vinyl monomers initiated with ionic liquids. For instance, the data about the solution polymerization of butyl acrylate (BA) initiated with 1-ethyl-2,3-dimethylimidazolium bromide ([edmim]Br) in diglyme under air at 70 oC suggest that the polymerization proceeds via a radical pathway, because the inhibitory effects of hydroquinone or 2,6-di-tert-butyl-p-cresol as a radical inhibitor and 1-dodecanethiol as a radical chain transfer agent were observed. In addition, as contrasted with the polymerization at 70 ℃, the polymerization at 60 ℃ under the same reaction conditions was perfectly inhibited. These results about the effects of additives and temperature suggest that [edmim]Br is a thermally decomposing radical initiator. On the other hand, the bulk polymerization and the solution polymerizations in the other conventional organic solvents under air at 70 oC were perfectly inhibited. The solvent effect of the BA-polymerization initiated with [edmim]Br is completely different from that of traditional radical polymerization. Anyhow, the author believes that the author’s investidations in the radical polymerization initiated with ionic liquids have significantly improved the general understanding of ionic liquids.
The New Type Radical Polymerization Initiated with Imidazolium Ionic Liquids BOOK OF ABSTRACTS EUCHEM 2010 Conference on Molten Salts and Ionic Liquids,
(2010) 105./ (Bamberg, Germany)
Although ionic liquids may be the most versatile material among the recently developed materials, the author recognizes that there may be no research on the radical polymerization initiated with ionic liquid except for the author’s investidations. In other words, the author targeted ionic liquids as a specific initiator of radical polymerization for the first time. Without doubt, an answer to the essential question relating to the apparent effectiveness of ionic liquids as a radical initiator is clearly important to systematically understand and evaluate the performance of individual ionic liquids and design new type ionic liquids. In this study, the author discusses fundamental features of the polymerizations initiated with imidazolium ionic liquids. For instance, the data about the effect of temperature on the polymerization of ethyl acrylate initiated with 2,2′-azobisisobutyronitrile (AIBN) as a conventional radical initiator and 1-ethyl-3-methylimidazolium thiocyanate ([emim]SCN) as an ionic liquid under air were tried. This polymerization run can b done in two ways. In one way, the polymerization is initiated with AIBN. Needless to say, all AIBN molecules undergo homolytic bond breakage in a short time at the suitable temperature to produce the initiating radical moiety. In the other way, [emim]SCN initiates the polymerization. In addition, it was clear that the polymerization proceeds via radical mechanism, because the inhibitory effects of 1-dodecanethiol (1-DT) as a radical chain transfer agent and hydroquinone (HQ) or 2,6-di-tert-butyl-p-cresol (BHT) as a radical inhibitor were observed. With regard to the relationship about the initiating ability between AIBN and [emim]SCN, the temperature range on the initiating activity of [emim]SCN is more wide than that of AIBN. For example, only a 15.7 % conversion of EA was observed in AIBN-initiated polymerization at 50 oC after 120 minutes, but a 45.8 % conversion of EA was observed in [emim]SCN-initiated polymerization under same reaction conditions. Moreover, as contrasted with the polymerization at 50 oC, only a 22.9 % conversion of EA was observed in [emim]SCN-initiated polymerization at 40 50 oC after 120 minutes, but AIBN did not initiate the EA-polymerization under same reaction conditions. Such experimental
results strongly indicate that [emim]SCN has the initiating ability of radical polymerization. In this manner, there is an ongoing investigation in the author’s laboratory to develop the new type radical polymerization initiated with imidazolium ionic liquids. Much of the driving force for the investigation derives from the belief that the determination of the active ionic liquid structure as the initiator of radical polymerization will offer substantial advantages to understand and exploit ionic liquids. Conversely, without improved understanding of ionic liquids as an initiator of radical polymerization, the real comprehension of ionic liquids will be limited.
New Possibility of Ionic Liquids as a Novel Initiator of Radical Polymerization BOOK OF ABSTRACTS 10th INTERNATIONAL CONFERENCE ON FRONTTIERS OF
POLYMERS AND ADVANCED MATERIALS, (2009) 89./ (Santiago de Chile)
The author has recently reported the property of one or another ionic liquid as a novel initiator of radical polymerization. In this investigation, the author studied the radical polymerization initiated with some kinds of ionic liquids. For example, it has been shown for the first time that 1-ethyl-2,3-dimethylimidazolium bromide ([edmim]Br) exhibited the initiating ability of radical polymerization. The polymerization of methyl methacrylate (MMA) initiated with [edmim]Br proceeded under air at 70 oC in N,N-dimethylformamide, however, an addition of radical inhihibitors such as hydroquinone or 2,6-di-tert-butyl-p-cresol completely inhibited the polymerization. In addition, the rate of the MMA-polymerization in the presence of radical chain transfer agent such as 1-dodecanethiol was strongly depressed, and the molecular weight of obtained polymer was reduced. Needless to say, thermal polymerization of MMA under same reaction conditions did not proceed. In the meanwhile, the polymerization behavior of ethyl acrylate initiated with [edmim]Br under argon at 70 oC in toluene was almost same as that of MMA initiated with [edmim]Br as described above.
Application of Guanidinium Ionic Liquids as a Specific Initiator of Radical Polymerization Preprints of EUCHEM 2008 Conference on Molten Salts and Ionic Liquids,
(2008) 148./Admiral Hotel (Copenhagen, Denmark)
The author initially recognized the suitability of ionic liquids as an initiator for radical polymerization. In order to find the new possibility of ionic liquids as an initiator for radical polymerization, in this study, the author studied the vinyl polymerization initiated with guanidinium-based ionic liquids. The kinetic order of the guanidinium tris(pentafluoroethyl)trifluorophosphate-initiated polymerization of styrene(St) in bulk was completely different from that of conventional radical polymerization. Moreover, the remarkable feature of the St-polymerization is that the molecular weights of obtained polymers are very small in spite of their relatively high percentages of conversion.
Monomer Selective Radical Polymerization Initiated with 1-Hexyl-3-methylimidazolium
Bromide
Preprints of 3rd International Conference on Green and Sustainable Chemistry,
(2007) 104./Department of Biotechnology of the Delft University of Technology
(Delft, The Netherlands)
Until then the author reported the application of ionic liquids as an initiator of vinyl polymerization. The object of this investigation is to explore the possibility for imidazolium ionic liquids as a novel initiator of vinyl polymerization. The author has shown for the first time that imidazolium ionic liquid such as 1-hexyl-3-methylimidazolium bromide ([hmim]Br) has the ability to initiate the radical polymerization. For example, the polymerizations of styrene and methyl methacrylate (MMA) initiated with [hmim]Br under air and argon at 70 ℃ in bulk were completely inhibited or scarcely proceeded. Furthermore, these polymerizations in benzene, toluene, carbon tetrachloride and dimethyl sulfoxide exhibited the same tendency. However, it was proved that the MMA-polymerization initiated with [hmim]Br in tetrahydrofuran at 60 ℃ under air and under argon proceeded smoothly via a radical pathway as a result of careful consideration. Alternatively the careful consideration indicated strongly that [hmim]Br possesses the ability to initiate the radical polymerization of a limited number of vinyl monomers in a limited number of solvents. After all, the author believes that [hmim]Br is very attractive for the novel initiator of unique radical polymerization, because [hmim]Br selectively initiates a limited number of vinyl monomers.

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