Presentations -

Enzymatic ring-opening polymerization behavior of cyclic thioester

Makoto Kato, Kazunobu Toshima, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Oral presentation (general), 高分子学会

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The enzymatic ring-opening polymerization (ROP) behavior of cyclic thioester was studied and compared with that of cyclic oxyester. It was found that the cyclic oxyester polymerized significantly faster than the cyclic thioester by the lipase. A living nature of the polymerization was observed for the ROP of cyclic thioester, and the rate-determining step was determined to be the deacylation of the enzyme-activated monomer by the propagating thiol chain.

Enzymatic synthesis of green poly(ester-urethane)

Yoshio YANAGISHITA, Makoto KATO, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Oral presentation (general), 高分子学会

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Poly(diester-urethane) (PDEU) was prepared by the lipase-catalyzed polymerization of diethyl adipate and urethanediol which was prepared by the reaction of ethylene carbonate and amino alcohol. Also, poly(ester-urethane) (PEU) was prepared by the polymerization of hydroxyl carboxylic acid containing urethane linkage. Their polymerization behavior, mechanical properties,
chemical recyclabilities and biodegradabilities were studied and compared with respect to the molecular structure.

Novel synthesis and properties of polythionoester

Keiko HASHIMOTO, Makoto KATO, Kazunobu TOSHIMA、MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Poster presentation, 高分子学会

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Aliphatic polythionoesters were prepared by the one-pot thionoesterification of polycaprolactone,
polypentadecanolactone, poly (butylene succinate) and poly (butylene adipate) using diphosphorus pentasulfide and hexamethyldisiloxane. And their physico-chemical properties as well as enzymatic degradabilities and
chemical recyclabilities were evaluated.

Chemical recycling of lactic acid based polymer blend using solid acid

Yota TSUNEIZUMI, Kazunobu TOSHIMA, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Poster presentation, 高分子学会

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The poly(L-lactic acid) (PLLA)-based polymer blend, PLLA/polyethylene (PE), into
repolymerizable oligomer was carried out using montmorillonite K5 (MK5) with the objective of
developing a selective chemical recycling process. The PLLA in the PLLA/PE polymer blend was
selectively degraded by MK5 in a toluene solution at 100 °C for 1 h to produce the LA oligomer
(OLLA) having a molecular weight of a few hundreds. The PE remained unchanged by MK5 and
was quantitatively separated by the reprecipitation method. The OLLA was repolymerized using a
conventional chemical catalyst to produce a high-molecular weight PLLA.

Chemical recycling of poly (butylene succinate) using a lipase

Maiko Kuwahara, Kazunobu TOSHIMA, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Poster presentation, 高分子学会

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Chemical recycling of poly (butylene succinate) (PBS) was studied using a lipase with respect to the
ring-size of the oligomer. It was found that PBS was degraded in a dilute toluene solution using a lipase
(Novozym 435) to produce cyclic oligomers mainly consisting of dimer and trimer. The cyclic dimer produced a
higher molecular weight polyester than cyclic trimer by the ring-opening polymerization. And differences
between cyclic dimer and trimer on the ring-opening polymerization were analyzed. The cyclic dimer was
exclusively obtained by sublimation under reduced pressure.

Chemical recycling of poly (butylene succinate) using a lipase

Yoshio YAMAMOTO, Sachiko KAIHARA, Kazunobu TOSHIMA, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Poster presentation, 高分子学会

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Cyclic oligo(tetramethylene carbonate) was synthesized by the condensation of butane-1,4-diol and diphenyl carbonate in a toluene solution using immobilized lipase from Candida antarctica (lipase CA) as an environmentally benign catalyst. The cyclic oligo(tetramethylene carbonate) was readily polymerized by lipase
CA in bulk to produce poly(tetramethylene carbonate) (PTeMC) with a molecular weight of 119,000. When the
conversion was exceeded about 90 %, the degradation reaction was more pronounced than the propagation
reaction, and the molecular weight of the polymer was gradually decreased. It was also found that PTeMC was
amorphous as determined by DSC, and the contact angle of the PTeMC film was 83ｏ(±1.3ｏ). Sufficient cell
viability and cell attachment of the PTeMC film were demonstrated

Degradability and cell viability of a novel biomaterial containing cyclic acetal

Sachiko KAIHARA, John P. Fisher, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子討論会 (名古屋工業大学) , 

2007.09

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Poster presentation, 高分子学会

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Poly[poly(ethylene glycol-co-cyclic acetal)] (PECA) hydrogel consisting of degradable cyclic acetal segments and hydrophilic poly(ethylene glycol) segments was synthesized. A toxicity study of PECA and degradation products upon BMSC viability showed that there was little effect of PECA molecular weight on cell viability. Bulk PECA hydrogels were incubated in PBS buffer at 37°C during long term in vitro degradation, with results indicating that approximately 40% of the hydrogel dry mass was lost after 5 months. Results further confirmed that there was minimal change in pH during degradation. BMSCs were encapsulated in PECA hydrogel and were observed by fluorescence microscopy. Cells were viable inside PECA hydrogels after 14 days incubation. This work demonstrates that PECA hydrogels may be a viable biomaterial for cell transplantation as well as other biomedical applications.

Synthesis and properties of green surfactant builder containing fumarate oligomer

Yu Okada, Taisuke Banno, Kazunobu Toshima, MATSUMURA SHUICHI

[Domestic presentation]  第46回日本油化学学会年会 (京都工芸繊維大学、京都) , 

2007.09

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Poster presentation, 日本油化学学会

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アニオン性界面活性剤は優れた機能を発揮することから現在最も広く使用されている。しかし、多価金属イオンと不溶性の塩を形成し、洗浄力が著しく低下することが知られている。さらに、環境問題から界面活性剤は優れた生分解性とバイオベース由来原料の使用が求められる。これまでに著者らは、フマル酸オリゴマーが良好な金属イオン封鎖能と生分解性を有することを報告した。そこで、本報ではフマル酸オリゴマーを親水基に用い、長鎖アルキル基を導入することにより、金属イオン封鎖能と生分解性を併せ持つ界面活性剤を、グリーンなプロセスにより得た。さらに、得られた界面活性剤の界面活性能や金属イオン封鎖能といった機能及び生分解性について評価を行った。

Enzymatic synthesis and characterization of 12-hydroxystearate based copolymer directed towards biodegradable elastomer

Hiroki Ebata, Kazunobu Toshima, MATSUMURA SHUICHI

[Domestic presentation]  第46回日本油化学学会年会 (京都工芸繊維大学、京都) , 

2007.09

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Oral presentation (general), 日本油化学学会

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プラスチックは優れた利便性から急速な発展を遂げ、金属材料やセラミックスとともに欠くことの出来ない材料となっている。その反面、廃プラスチックの処理、石油資源の枯渇やCO2濃度増大などの問題が顕在化し、生分解性プラスチックの開発や植物資源を利用した素材開発が強く求められるようになっている。本報では生分解性を併せ持つエラストマー素材を指向し、種子油より得られる12-ヒドロキシステアリン酸(12HS)および12-ヒドロキシドデカン酸(12HD)を原料に共重合ポリエステルを合成し、その特性について検討を行った。

Synthesis and properties of gemini cationic surfactants having biodegradability and chemical recyclability

Taisuke Banno, Kazunobu Toshima, Kazuo Kawada, MATSUMURA SHUICHI

[Domestic presentation]  第46回日本油化学学会年会 (京都工芸繊維大学、京都) , 

2007.09

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Oral presentation (general), 日本油化学学会

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優れた抗菌性と界面活性を有する第四級アンモニウム塩型カチオン性界面活性剤は多くの分野で使用されているが、循環型社会構築の観点から、環境調和性、高機能性、生分解性、さらにはリサイクル性が求められる。本報では、第四級アンモニウム塩に生分解性とリサイクル性を付与する目的で、分子内にカーボネート結合を有するジェミニ型カチオン性界面活性剤を設計し、それらのグリーンプロセスによる合成と機能について検討を行った。

Synthesis and chemical recycling of polythioester using an enzyme

Makoto Kato, Kazunobu Toshima and MATSUMURA SHUICHI

[International presentation]  3rd International Conference on Green and Sustainable Chemistry (Delft University of Technology, Delft, The Netherlands) , 

2007.07

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Poster presentation

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The nivel synthesis of a high molecular weight polythioester using an enzyme was studied. The enzyme-catalyzed polymerization may become one of the environmentally benign methods that meet the green chemistry requirements since no hazadous substance is used or generated. It is also an attractive method since polythioesters with a variety of molecular structures can be synthesized.

Synthesis and chemical recycling of green polyesters using environmentally benign catalyst

MATSUMURA SHUICHI

[International presentation]  3rd International Conference on Green and Sustainable Chemistry (Delft University of Technology, The Netherlands) , 

2007.07

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Oral presentation (general)

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Chemically recyclable and biodegradable polyesters were prepared using biobased and potentially biobased compounds, and their sustainable recyclabilities were studied using an environmentally benign catalyst, such as an enzyme or clay catalyst. Diol-diacid type green polyesters were prepared by the lipase-catalyzed polymerization of succinic, adipic, fumaric, maleic and itaconic acid with their reduction products of butane-1,4-diol, hexane-1,6-diol and 2-butene-1,4-diol. A high-molecular weight polyester was produced via the lipase-catalyzed ring-opening polymerization of the cyclic oligomer/monomer which was prepared by the condensation of the diol and diacid/diester in a dilute organic solution. The produced polyester was equally degraded into the repolymerizable cyclic oligomers by lipase (Figure 1). Furthermore, it was confirmed that no cis/trans isomerization of the fumarate, maleate and itaconate units occurred during the polymerization and recycling processes using a lipase. Also, the unsaturated polyesters were readily crosslinked by the conventional organic peroxides.

バイオリサイクル：酵素によるケミカルリサイクルを中心に

MATSUMURA SHUICHI

[Domestic presentation]  第2回グリーンケミストリー研究会講座　精密ケミカルリサイクルのための基礎講座（第2回） (東京都　日大理工学部駿河台校舎) , 

2007.06

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Oral presentation (general), 高分子学会　グリーンケミストリー研究会

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酵素及び微生物を用いたグリーンプラスチックのケミカルリサイクルについてまとめた

Preparation and enzymatic degradation of environmentally benign poly(carbonate/ester-urethane) based on lactide oligomer

MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子学会年次大会 (京都国際会館) , 

2007.05

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Poster presentation, 高分子学会

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Environmentally benign poly(carbonate/ester-urethane) (PC/LU) was synthesized by the reaction of enzymatically prepared oligocarbonate diol and lactide oligomer end-capped by trimethylene glycol with hexamethylene diisocianate. Thermal and physical properties of PC/LUs were measured. And the enzymatic degradation of PC/LU was also evaluated.

Chemical recycling of poly (butylene succinate) using a lipase

MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子学会年次大会 (京都国際会館) , 

2007.05

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Poster presentation, 高分子学会

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Chemical recycling of poly (butylene succinate) (PBS) was studied using a lipase with respect to the ring-size of the oligomer. It was found that PBS was degraded in a dilute toluene solution using lipase CA to produce cyclic oligomers mainly consisting of dimer and trimer. By the ring-opening polymerization of isolated cyclic BS dimer by lipase, PBS with an Mw of 170,000 was produced. On the other hand, PBS with an Mw of 130,000 was produced from isolated cyclic trimer. That is, cyclic dimer produced a higher molecular weight polyester than from cyclic trimer by the ring-opening polymerization. By degradation of PBS using lipase CA, cyclic dimer was obtained in a maximum yield of 70%.

Enzymatic synthesis and polymerization of seven-membered cyclic carbonate

Yoshio YAMAMOTO, Sachiko KAIHARA, Kazunobu TOSHIMA, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子学会年次大会 (京都国際会館) , 

2007.05

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Poster presentation, 高分子学会

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Seven-membered cyclic tetramethylene carbonate was synthesized by the condensation of butane-1,4-diol and diphenyl carbonate in a toluene solution using immobilized lipase from Candida antarctica(lipase CA) as an environmentally benign process. The cyclic tetramethylene carbonate was readily polymerized by lipase CA in bulk to produce poly(tetramethylene carbonate) (PTeMC) with a molecular weight of 103,000. The molecular weight of PTeMC prepared by the ring-opening polymerization of cyclic carbonate was significantly higher than that produced by the direct polycondensation of butane-1,4-diol and diethyl carbonate using lipase CA. It was also found that PTeMC was amorphous as determined by DSC, and the contact angle of the surface of PTeMC was 83ｏ(±1.3ｏ).

Synthesis of Poly(thio-oxyester) Using an Enzyme

Makoto KATO, Kazunobu TOSHIMA, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子学会年次大会 (京都国際会議場) , 

2007.05

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Poster presentation, 高分子学会

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Recently, polythioester has attracted attention due to their interesting properties, such as high melting point
and heat stability. Synthesis of high molecular weight poly(thio-oxyester) using an enzyme was studied. First,
6-mercapto-1-hexanol and dimethyl sebacate were reacted in n-nonane using lipase CA to produce cyclic(thio-oxyester). A poly(thio-oxyester) having an Mw of about 120,000 was prepared by the ring-opening polymerization of cyclic(thio-oxyester)using lipase CA. A higher melting point was observed compared with the corresponding poly(oxyester). The rate-determining step of the polymerization was determined to be the nucleophilic attack by the thiol, which differs from the corresponding enzymatic polymerization reactions.

Enzymatic synthesis and properties of poly(ester-urethane) from bio-based amino acid

Yoshio YANAGISHITA, Makoto KATO, Kazunobu TOSHIMA, MATSUMURA SHUICHI

[Domestic presentation]  第56回高分子学会年次大会 (京都国際会館) , 

2007.05

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Poster presentation, 高分子学会

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Poly(ester-urethane) was synthesized from bio-based amino acid using an enzyme. Thermal and physical properties as well as chemical recyclability and biodegradability of
poly(ester-urethane) were evaluated.

標的糖鎖を選択的に光分解する人工分子の開発

Ishii Maiko, MATSUMURA SHUICHI, Toshima Kazunobu

[Domestic presentation]  日本ケミカルバイオロジー研究会第２回年会 (京都大学) , 

2007.05

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Oral presentation (general), 日本ケミカルバイオロジー研究会

Synthesis and characterization of novel biomaterials based on cyclic acetal and PEG hydrogels

MATSUMURA SHUICHISachiko KAIHARA, John P. Fisher, Shuichi Matsumura

[International presentation]  Annual Meeting of American Chemical Society (PMSE/Poly Division) (Chicago, USA) , 

2007.03

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Poster presentation, American Chemical Society