Name: designed for molecular recycling: a lignin-derived semi-aromatic biobased polymer
Uploaded: 2020-11-30T14:00:00
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著者らは、オランダ科学研究機構(NWO)(ジャック・ファン・シンデルに授与された助成金023.007.020)からの財政的支援に感謝しています。

1. 5 mol%重炭酸アンモニウムを用いたシリンアルデヒドのシリンアルデヒドの結露
<ol><li>マロン酸(20.81 g、200.0 mmol)とシリンアルデヒド(36.4 g、200.0 mmol)を250 mLラウンドボトムフラスコに加えます。酢酸エチルの20.0 mLに両方の成分を溶解し、フラスコに重炭酸アンモニウム(790mg、10.0 mmol)を加えます。 注:結露反応を完全に完了するために、ロータリーエバポレーターを使用して酢酸エチルを蒸...

<ol>
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ジヒドロシナピアン酸を反応容器内で加熱すると、出発物質の昇華が発生し、真空を加えた場合にこの効果が高まりました。昇華を避けるためにジヒドロシナピアン酸に対してアセチル化が行われている。Kricheldorfら12,27は、アセチル化だけでなく、同様に二及びオリゴマー化が起こったことを認識した。しかしながら、これらのエステル化モノマ?...

高分子廃棄物の焼却とは対照的に、化学リサイクルはモノマーを回収する可能性を提供します。化学リサイクルは、これらの高分子材料が化学的に製造されるので、ポリマー材料の技術的寿命の終わりに論理的な選択である1.高分子材料を化学的にリサイクルする方法は2つありますが、熱分解と分子リサイクル2.熱分解により、ポリマー材料は、極限条件3、4を用いてより高い価値の製品に変換される。分子リサイクルは、脱重合を用いて出発物質を回収する効率的な方法です。脱重合後、単量体単位をバージンポリマー材料5に再重合することができる。より大きなスケールで分子リサイクルを適用するのに適したモノマーの利用可能性が望んでいる。現在のプラスチック問題は、社会が頑丈で堅牢なポリマー材料を要求することを指示します。同時に、同じポリマー材料が容易にリサイクル可能であり、環境中で耐えられないことも好ましい。良好な熱および機械的特性を有する現在のポリマー材料は、容易に6を脱重しない。
血管植物に一般的に見られるリグニンは、世界の天然炭素含有量の30%を占めており、セルロースに次いで2番目に豊富な生体高分子です。リグニンは複雑なアモルファス構造を有し、化石材料から抽出された芳香族を置き換えるのに適した代替手段であるように見える。リグニンの立体構造は、木材に強さと剛性だけでなく、劣化に対する耐性を提供します。化学的に言えば、リグニンは非常に複雑なポリフェノール熱硬化性である。それは3つの異なるメトキシル化フェニルプロパン構造の様々な組成から成る。シリンギル、グアヤシル、およびp-ヒドロキシフェニル(それぞれS、G、Hと略される)は、モノリニョールシナピルアルコール、針葉ニルアルコール、およびp-コマリルアルコール7に由来する。これらの単位の分布はバイオマスの種類ごとに異なり、例えば、グアイアシル単位とグアイアシル単位とシリンギル単位8,9の広葉樹からなる針葉樹とが異なる。樹木や植物などの再生可能な自然源は、革新的な高分子材料10のための再設計されたモノマーの生産に望ましい。これらのモノマーは、天然源から単離および合成され、いわゆるバイオベースポリマー11に重合される。
芳香族カルボン酸は、電子的な理由12のために同等の脂肪族カルボン酸よりも数桁少ない電子親水性である。様々な市販のポリエステルは、脂肪族カルボン酸の代わりに芳香族カルボン酸を使用しています。その結果、ポリ(エチレンテレフタレート)(PET)繊維から作られたポリエステル繊維の繊維は、洗浄中の加水分解に対してほとんど無感症、または例えば雨13である。ポリエステルの分子リサイクルが望まれる場合、ポリマーの蓄積に脂肪族エステルを使用することをお勧めします。
前述の理由から、我々は4-ヒドロキシ-3,5-ジメトキシジヒドロシンアミン酸からポリエステルを作る可能性を検討した。Kricheldorf15、マイヤー16、ミラー17、18による以前の研究は、4-ヒドロキシ-3,5-ジヒドロシン酸を使用してポリマーを構築することが困難であることを示しています。脱炭酸および架橋は重合を妨げ、したがってこれらの合成の成功を制限した。また、重縮合のメカニズムは不明のままでした。本論文では、ポリエステルポリ(ジヒドロシナピエン酸)を、規則的かつ高収率で合成し、分子的にリサイクル可能な半芳香族ポリエステルを使用する道を開く条件を説明しています。
シリンアルデヒドとマロン酸19,20の縮合反応を用いて、シナピエン酸を合成するグリーンかつ効率的な方法を開発しました。このグリーンクノエナゲルの後、水素化はジヒドロシナピアン酸を生成し、可逆的な重縮合に適しています。本論文は、ポリ-Sと呼ばれるリグニンの塩基単位を参照して、分子リサイクル性ポリマーポリ(ジヒドロシナピエン酸)への合成ステップを可視化する。高分子材料を分析した後、ポリ-Sは比較的良好な条件下でモノマージヒドロシナピ酸に脱重化され、何度も何度も再重合される。

<table>
	<tbody>
		<tr>
			<td>Reaction 1: Green Knoevenagel condensation</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Ammonium bicarbonate</td>
			<td>Sigma Aldrich</td>
			<td>&#62;99%</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethanol</td>
			<td>Boom</td>
			<td>Technical grade</td>
			<td></td>
		</tr>
		<tr>
			<td>Ethyl acetate</td>
			<td>Macron</td>
			<td>99.8%</td>
			<td></td>
		</tr>
		<tr>
			<td>Hydrochloric acid</td>
			<td>Boom</td>
			<td>37%</td>
			<td></td>
		</tr>
		<tr>
			<td>Malonic acid</td>
			<td>Sigma Aldrich</td>
			<td>99%</td>
			<td>used as received</td>
		</tr>
		<tr>
			<td>Sodium bicarbonate</td>
			<td>Sigma Aldrich</td>
			<td>&#62;99.7%</td>
			<td></td>
		</tr>
		<tr>
			<td>Syringaldehyde</td>
			<td>Sigma Aldrich</td>
			<td>98%</td>
			<td>used as received</td>
		</tr>
		<tr>
			<td>Reaction 2: Hydrogenation</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Magnesium sulfate</td>
			<td>Macron</td>
			<td>99%</td>
			<td>dried</td>
		</tr>
		<tr>
			<td>Raney&#8482; nickel</td>
			<td>Sigma Aldrich</td>
			<td>&#62;89%</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium hydroxide</td>
			<td>Boom</td>
			<td>Technical grade</td>
			<td>dissolved</td>
		</tr>
		<tr>
			<td>Reaction 3: Acetylation</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Acetic anhydride</td>
			<td>Macron</td>
			<td>&#62;98%</td>
			<td></td>
		</tr>
		<tr>
			<td>Acetone</td>
			<td>Macron</td>
			<td>&#62;99.5%</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium acetate</td>
			<td>Sigma Aldrich</td>
			<td>&#62;99%</td>
			<td></td>
		</tr>
		<tr>
			<td>Reaction 4A: Polymerisation</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>1,2-xylene</td>
			<td>Macron</td>
			<td>&#62;98%</td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium hydroxide</td>
			<td>Boom</td>
			<td>Technical grade</td>
			<td>finely powdered</td>
		</tr>
		<tr>
			<td>Zinc(II)acetate</td>
			<td>Sigma Aldrich</td>
			<td>99.99%</td>
			<td></td>
		</tr>
		<tr>
			<td>Reaction 4B: Depolymerisation</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>Sodium hydroxide</td>
			<td>Boom</td>
			<td>Technical grade</td>
			<td>dissolved</td>
		</tr>
		<tr>
			<td>Sulfuric acid</td>
			<td>Macron</td>
			<td>100%</td>
			<td></td>
		</tr>
		<tr>
			<td>Analysis</td>
			<td></td>
			<td></td>
			<td></td>
		</tr>
		<tr>
			<td>CDCl3</td>
			<td>Cambride Isotope Laboratories, Inc.</td>
			<td>99.5%</td>
			<td></td>
		</tr>
		<tr>
			<td>CF3COOD</td>
			<td>Cambride Isotope Laboratories, Inc.</td>
			<td>98%</td>
			<td></td>
		</tr>
		<tr>
			<td>Dimethylformamide</td>
			<td>Macron</td>
			<td>&#62;99.9%</td>
			<td></td>
		</tr>
		<tr>
			<td>Hexafluoro-2-propanol</td>
			<td>TCI Chemicals</td>
			<td>&#62;99%</td>
			<td></td>
		</tr>
		<tr>
			<td>Methanol</td>
			<td>Macron</td>
			<td>&#62;99.8%</td>
			<td></td>
		</tr>
		<tr>
			<td>Tetrahydrofuran</td>
			<td>Macron</td>
			<td>&#62;99.9%</td>
			<td></td>
		</tr>
	</tbody>
</table>

designed for molecular recycling: a lignin-derived semi-aromatic biobased polymer

化学的にリサイクル可能なバイオポリマーの開発は、循環経済の追求の中で機会を提供します。化学的にリサイクル可能なバイオポリマーは、使用段階後の処分段階におけるポリマー材料の問題を解決するために積極的に努力する。本論文では、リグニンなどのバイオマスから完全に抽出できるバイオベースの半芳香族ポリエステルの製造について説明し、可視化する。本論文に記載されているポリマーポリ-Sは、PETのような一般的に使用されるプラスチックと同様の熱特性を有する。芳香族アルデヒドとマロン酸からモノマーを効率的に生成できるグリーンクノエナゲル反応を開発しました。この反応はスケーラブルであることが証明されており、計算されたEファクターは著しく低くなっています。リノフィトケミカルを出発点としたこれらのポリエステルは、最小限の損失で効率的な分子リサイクルを示しています。ポリエステルポリ(ジヒドロシナピアン酸)(ポリ-S)は、これらの半芳香族ポリエステルの一例として提示され、重合、脱重合、および再重合について説明する。

シリンアルデヒドから高純度かつ高収率(>95%)で合成されたシナピエン酸は、グリーンクノエネナゲル縮合を用いた。(サポート情報:図 S1)Eファクターは、より高い数がより多くの廃棄物を示す廃棄物生産の指標です。E係数は、材料総入力を取り、目的の最終製品の量を差し引き、最終製品の量で全体を除算することによって計算されます。このグリーンクノエナゲル凝縮はEファ?...

Watch this Scientific Journal Video about Designed for Molecular Recycling: A Lignin-Derived Semi-aromatic Biobased Polymer at JoVE.com

Designed for Molecular Recycling: A Lignin-Derived Semi-aromatic Biobased Polymer

循環材料経済に向けた閉ループアプローチの例をここに説明します。生物ベースの半芳香族ポリエステルが重合、脱重合によって設計され、その後、その収率または最終的な特性のわずかな変化だけで再重合される、全体の持続可能なサイクルが提示されます。

分子リサイクル向けに設計:リグニン由来の半芳香族バイオベースポリマー

The development of chemically recyclable biopolymers offers opportunities within the pursuit of a circular economy. Chemically recyclable biopolymers make ...

Throughout the synthesis described in this paper provides a way to produce a new polymeric material specifically designed for molecular recycling, which is a way of chemical recycling. The depolarization and repolarization of the foreign material poly-S creates a fully sustainable cycle, which is a proof of concept for the future of polymers. The polymer waste of the world accumulates.For instance in the ocean, as the plastic soup, which could be prevented by introducing molecularly recyclable polymers. The polymer presented is an example of a polymeric material designed for molecular recycling. This in our opinion, should be implemented in other materials to prevent accumulation in nature.Green Knoevenagel reaction and subsequent steps have been designed for and by our undergraduated students. So certain robustness is already implemented in these reaction steps. The COVID-19 pandemic creates a situation where online learning becomes more important than ever.Visualization of these experiments helps us and others to deepen practical chemical education. Begin by adding 20.81 grams of malonic acid and 36.4 grams of syringaldehyde to a 215 milliliter round bottom flask. Dissolve both constituents in 20 milliliters of ethyl acetate and add 719 milligrams of ammonia bicarbonate to the flask.Mix and distill the solvent with a water bath. Keep the reaction mixture at 90 degrees Celsius for two hours in the open flask without stirring for complete conversion to sinapinic acid. In the work-up of the sinapinic acid product, dissolve the residue in 100 milliliters of a saturated aqueous sodium bicarbonate solution, then transfer the solution to a beaker, and acidify it to a pH two.Using six molar hydrogen chloride, separate the resulting residue by vacuum filtration and wash it with demineralized water. Charge a 450 milliliters flask with 33.6 grams sinapinic acid. Dissolve the sinapinic acid in 300 milliliters of two molar sodium hydroxide solution, and add 1.5 grams of nickel slurry before fitting the flask to the operators.Pressurize the reactor with three bar of hydrogen gas and mechanically shake the reaction at 80 degrees Celsius for three hours. Cool the reactor to room temperature and depressurize slowly. Recover most of the nickel catalyst with a magnet, then filter the solution.Acidify the solution with four molar hydrogen chloride solution to a pH of two, then perform an extraction with ethyl acetate. Remove the solvent under reduced pressure after drying over magnesium sulfate and dry the dihydrosinapinic acid at 60 degrees Celsius in a vacuum oven. Add 22.6 grams dihydrosinapinic acid to a 250 milliliter round bottom flask.Followed by 14.2 milliliters of acetic anhydride and 0.82 grams of sodium acetate. Heat the solution to 90 degrees Celsius while stirring for one hour for complete conversion of dihydrosinapinic acid to 4-Acetoxy-dihydrosinapinic acid, and it's acetylated oligomers. Dissolve the solid in 25 milliliters of acetone precipitated into 250 milliliters of 0.1 molar hydrogen chloride, then filtered on the vacuum.Add the monomers 20.8 grams of 4-Acetoxy-dihydrosinapinic acid and prepolymer to a 100 milliliter round bottom flask. Then add 400 milligrams of finely powdered sodium hydroxide, heat the reaction mixture for three hours at a set temperature of 140 degrees Celsius in the open flask while staring at 100 RPM. Set up a solvent assisted polymerization by adding 180 milligrams of zinc two acetate and 25.0 milliliters of 1, 2-xylene to the flask, then raise the set temperature to 160 degrees Celsius.Reflux the mixture at 144 degrees Celsius for three hours with constant water and acetic acid removal using Dean-Stark head. Cool the reaction mixture down and remove the 1, 2-xylene by applying a vacuum. Raise the temperature to 240 degrees Celsius during the final stage of the polymerization and apply a high vacuum for 30 minutes.Cool the polymer poly-S to room temperature and wash it with methanol to eliminate dihydrogen sinapinic acid and prepolymers. The obtained product should be a light brown solid. Finally grind and serve the poly-S into particles smaller than 180 micrometres to measure hydrolytic degradation.Load several test tubes with 20 milligrams of poly-S and add one milliliter of one molar sodium hydroxide solution. Incubate the tubes at three different temperatures with an agitation of 500 RPM. Neutralize the test tubes at regular time intervals with one milliliter of 0.5 molar sulfuric acid, and add two milliliters of methanol after cooling.Filter all samples using 0.45 micro meter PTFE syringe filters and inject 20 microliters into HPLC using an auto sampler. Monitor the absorbance at 254 nanometers and calculate the concentrations from a calibration curve of known dihydrosinapinic acid standard solutions. Sinapinic acid was synthesized in high purity and a greater than 95%yield from syringaldehyde using the Green Knoevenagel Condensation, the proposed mechanism of the step growth polymerization of 4-Acetoxy-dihydrosinapinic acid is shown here.Hydrogen one and MR measurements were taken during the polymerization process. When poly-S was hydrolyzed in sodium hydroxide, the molecularly recyclable polyester yielded the starting material dihydrosinapinic acid in less than 10 minutes. As confirmed by HBLC melting point analysis and hydrogen one and MR.Extended reaction times did not increase the yield.The thermal grams and GPC analysis of poly-S 1.0 and their successive generations poly-S 2.0 and polyester 3.0 after forced amorphicity with a tactic polystyrene are shown here. DSC analysis of poly-S shows a glass transition signal at 113 degrees Celsius and endothermic melting signal at 281 degrees Celsius. The polymers from re-polymerized sinapinic acid three eight poly-S 2.0 up and poly-H 3.0 exhibit similar thermal properties.Poly-S is a semi crystalline polymeric material because glass transition temperatures and melting signals are present in the thermograms of poly-S and their successive generations. GPC analysis after forced amorphicity with a tactic polystyrene displays a constant length of polymeric material throughout the different generations. While attempting the Green Knoevenagel reaction, please keep in mind that a correct temperature is used.A slightly higher temperature can lead to different site reactions. We have explored an example of a molecularly recyclable polymer. Closely related building blocks can follow the same procedure, or while maintaining thermal and mechanical properties.This method can be used in organic catalysis by demonstrating of the catalytic intermediates, as well in the still unexplored area of molecular recycling.

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JoVE Journal

Organic Chemistry

Chemistry

Unit 1

&alpha;-Carbon Chemistry: Enols, Enolates, and Enamines

SCIENTISTS IN ACTION

Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

ジブロック共重合体超分子からジャイロイドニッケルナノ構造

Nanoporous metal foams possess a unique combination of properties - they are catalytically active, thermally and electrically conductive, and furthermore, ...

化学

Preparation of Highly Porous Coordination Polymer Coatings on Macroporous Polymer Monoliths for Enhanced Enrichment of Phosphopeptides

リン酸化ペプチドの強化充実のためのマクロポーラスポリマーモノリスの高度に多孔性配位高分子コーティングの製造

We describe a protocol for the preparation of hybrid materials based on highly porous coordination polymer coatings on the internal surface of macroporous ...

Photodynamic Therapy with Blended Conducting Polymer/Fullerene Nanoparticle Photosensitizers

ポリマー/フラーレンナノ粒子の光増感を実施ブレンドと光線力学療法

In this article a method for the fabrication and reproducible in-vitro evaluation of conducting polymer nanoparticles blended with fullerene as the next ...

Functionalization of Single-walled Carbon Nanotubes with Thermo-reversible Block Copolymers and Characterization by Small-angle Neutron Scattering

小角中性子散乱による熱可逆性ブロック共重合体と特性を持つ単層カーボンナノチューブの機能化

We demonstrate a protocol for single-walled carbon nanotube functionalization using thermo-sensitive PEO-PPO-PEO triblock copolymers in an aqueous ...

The Preparation and Properties of Thermo-reversibly Cross-linked Rubber Via Diels-Alder Chemistry

サーモ可逆架橋ゴム経由アルダー化学の合成と性質

A method for using Diels Alder thermo-reversible chemistry as cross-linking tool for rubber products is demonstrated. In this work, a commercial ...

Direct Imaging of Laser-driven Ultrafast Molecular Rotation

レーザー駆動の超高速分子回転のダイレクトイメージング

We present a method for visualizing laser-induced, ultrafast molecular rotational wave packet dynamics. We have developed a new 2-dimensional Coulomb ...

Microfluidic Dry-spinning and Characterization of Regenerated Silk Fibroin Fibers

マイクロ流体ドライ回転と再生絹フィブロイン繊維の特性

The protocol demonstrates a method for mimicking the spinning process of silkworm. In the native spinning process, the contracting spinning duct enables ...

Electrochemical Impedance Spectroscopy as a Tool for Electrochemical Rate Constant Estimation

電気化学インピー ダンス分光電気化学定数推定法のためのツールとして

Electrochemical impedance spectroscopy (EIS) was used for advanced characterization of organic electroactive compounds along with cyclic voltammetry (CV). ...

Time-resolved Photophysical Characterization of Triplet-harvesting Organic Compounds at an Oxygen-free Environment Using an iCCD Camera

時間分解光物性評価のトリプレット収穫有機化合物無酸素環境使用、iCCD カメラ

Here, we present a sensible method of the acquisition and analysis of time-resolved photoluminescence using an ultrafast iCCD camera. This system enables ...