Name: designed for molecular recycling: a lignin-derived semi-aromatic biobased polymer
Uploaded: 2020-11-30T14:00:00
Description: Watch this Scientific Journal Video about Designed for Molecular Recycling: A Lignin-Derived Semi-aromatic Biobased Polymer at JoVE.com

저자는 과학 연구를위한 네덜란드 기구 (NWO)의 재정 지원에 감사드립니다 (보조금 023.007.020 잭 반 Schijndel에 수여).

1. 5 mol% 중탄산염을 가진 시리갈데히드의 녹색 Knoevenagel 응축
<ol><li>250mL 라운드 하단 플라스크에 실로산(20.81g, 200.0 mmol)과 주사기알데히드(36.4g, 200.0 mmol)를 추가합니다. 에틸 아세테이트 20.0 mL에 두 성분을 녹이고 플라스크에 암모늄 중탄산염(790 mg, 10.0 mmol)을 추가한다. 참고: 응축 반응의 완전한 완성을 보장하기 위해, 회전 증발기를 사용하여 에틸 아세테이트를 증류하고 반응 혼합물을 농축?...

<ol>
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디하이드로시나피닉산이 반응용기에서 가열되었을 때, 시동물질의 승화가 발생했으며, 진공이 적용되었을 때 이러한 효과가 향상되었다. 아세틸화는 승화를 피하기 위해 디하이드로시나피닉 산에서 수행되었습니다. 크리첼도르프 외12,27은 아세틸화뿐만 아니라 유사하게 디고머화가 발생했다는 것을 인식했다. 그러나, 이러한 에스테르화된 단량체와 ...

중합체 폐기물의 소각과는 달리 화학 적 재활용은 단량체를 회수 할 수있는 가능성을 제공합니다. 화학적 재활용은 이러한 중합체 물질이 화학적으로1을생산되기 때문에 중합체 물질의 기술적 수명이 끝날 때 논리적인 선택이다. 중합체 물질을 화학적으로 재활용하는 방법에는 두 가지가 있다, 용해 및 분자 재활용2. 열분해를 통해 중합체 물질은 극한 조건3,4를사용하여 더 높은 가치의 제품으로 변형된다. 분자 재활용은 중합화를 사용하여 시작 물질을 회수하는 효율적인 방법입니다. 중합 후, 단황 단위는 처녀 중합물질로 재중화될 수있다 5. 더 큰 규모로 분자 재활용을 적용하는 적절한 단량제의 가용성이 원하고 있습니다. 현재의 플라스틱 문제는 사회가 튼튼하고 견고한 중합체 물질을 요구한다고 규정하고 있습니다. 동시에, 동일한 중합체 물질이 쉽게 재활용가능하고 환경에서 견디지 못하는 것이 바람직하다. 현재 열 및 기계적 특성이 좋은 현재 중합재료는 쉽게 폴리머화하지 않는다6.
혈관 식물에서 흔히 발견되는 Lignin은 세계 천연 탄소 함량의 30%를 담당하며 셀룰로오스 다음으로 두 번째로 풍부한 바이오 폴리머입니다. Lignin은 복잡한 비정질 구조를 가지고 있으며 화석 물질에서 추출한 방향족을 대체하기에 적합한 대안으로 보입니다. 리그닌의 입체 구조는 나무에 강도와 강성뿐만 아니라 저하에 대한 저항을 제공합니다. 화학적으로 말하자면, 리그닌은 매우 복잡한 폴리페놀 열집합입니다. 그것은 세 가지 다른 메톡시 페닐 프로판 구조의 다양한 구성으로 구성되어 있습니다. 시링일, 구아실 및 p-하이드록시페닐(종종 S, G, H로 약식)은 모노리그놀 시나필 알코올, 침엽수 알코올 및 p-쿠메릴 알코올7에서유래된다. 이러한 단위의 분포는 바이오매스 유형마다 다르며, 예를 들어, 대부분 과아실 단위와 과아실 및 실링일 유닛8,9의나무로 구성된 과아실 단위로 구성된다. 나무나 식물과 같은 재생 가능한 천연 공급원은 혁신적인 폴리머소재(10)를위해 재설계된 단량체의 생산에 바람직하다. 천연 공급원으로부터 분리되고 합성된 이들 모노머는 소위 바이오기반폴리머(11)로중합된다.
방향족 카복실산은전자상의이유로 동등한 알리팔성 카복실산보다 여러 주 의 크기가 적다. 다양한 상업용 폴리에스테르는 알리팔성 카복실산 대신 방향족 카복실산을 사용합니다. 그 결과, 폴리에스테르섬유(에틸렌 테레프탈레이트)(PET) 섬유로 만든 섬유는 세척 중 가수 분해에 거의 민감하지 않거나, 예를 들어,비(13)에민감하다. 폴리에스테르의 분자 재활용이 원할 때, 폴리머의 축적에 알리파성 에스테르를 사용하는 것이 좋습니다.
언급 된 이유로, 우리는 4 하이드록시 -3,5-디하이드로신산14에서폴리 에스테르를 만드는 가능성을 조사했다. Kricheldorf15,마이어16및 밀러17,18에 의한 이전 연구는 4-하이드록시-3,5-디메톡시 디하이드로신산을 사용하여 폴리머를 구축하는 것이 어렵다는 것을 보여줍니다. 탈카복틸화와 교차 연결은 중합을 방해하고, 그래서 이러한 합성의 성공을 제한. 또한 다결도의 메커니즘은 불분명했습니다. 제시된 논문은 폴리에스테르 폴리(dihydrosinapinic acid)가 정기적으로 고수율로 합성될 수 있는 조건을 설명하므로 분자재활용가능한 반 방향족 폴리에스테르를 사용하는 길을 열어줍니다.
우리는 주사기알데히드와 말론산19,20사이의 응축 반응을 사용하여 시나피닉 산을 합성하는 녹색이고 효율적인 방법을 개발했습니다. 이 녹색 Knoevenagel 후, 수소화는 가역 다결관화에 적합한 디하이드로시나피닉 산을 생성합니다. 이 간행물은 폴리-S라고 불리는 리그닌의 기체를 지칭하는 분자 재활용 가능한 폴리머 폴리(dihydrosinapinicacid)에 합성 단계를 시각화합니다. 중합체 물질을 분석한 후, 폴리-S는 비교적 유리한 조건하에서 단량제 디하이드로시나피닉산으로 비합화되고 거듭 재중화된다.

<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

화학적으로 재활용 가능한 바이오 폴리머의 개발은 순환 경제를 추구하는 기회를 제공합니다. 화학적으로 재활용 가능한 바이오폴리머는 사용 단계 후 폐기 단계에서 폴리머 물질의 문제를 해결하기 위해 긍정적인 노력을 기울입니다. 본 논문에서, 리닌과 같은 바이오매스로부터 완전히 추출될 수 있는 생체 기반 반 방향족 폴리에스테르의 생산이 설명되고 시각화된다. 이 백서에 기재된 폴리머 폴리-S는 PET와 같은 특정 일반적으로 사용되는 플라스틱과 유사한 열 특성을 갖는다. 우리는 방향족 알데히드와 말론산에서 단량체를 효율적으로 생산할 수 있는 녹색 Knoevenagel 반응을 개발했습니다. 이 반응은 확장 가능한 것으로 입증되었으며 현저하게 낮은 계산 된 전자 계수를 가지고 있습니다. 리그노 파이토케미칼이 있는 폴리에스테르는 최소한의 손실로 효율적인 분자 재활용을 보여줍니다. 폴리에스테르 폴리(dihydrosinapinicacid) (poly-S)는 이러한 반 방향족 폴리에스테르의 예로 제시되고, 중합화, 비합합화 및 재중합이 설명된다.

시나피닉산은 그린 크노벤나겔 응축을 이용하여 주사기알데히드로부터 고순도 및 고수율(> 95%)으로 합성되었다. (지원 정보: 그림 S1) E-팩터는 폐기물 생산의 지표로, 더 많은 수의 폐기물이 더 많은 폐기물을 나타냅니다. E-계수는 총 재료 입력을 취하고 원하는 최종 제품의 양을 빼고 전체를 최종 제품의 양으로 나누어 계산합니다. 이 녹색 Knoevenagel 응축은 계산할 수 있는 1.0의 E 계수...

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

원형 재료 경제에 대한 폐쇄 루프 접근 방식의 예는 여기에 설명되어 있습니다. 전체 지속 가능한 주기는 생물 기반 반 방향족 폴리 에스테르는 중합, 폴리머화에 의해 설계 된 다음 수확량 또는 최종 특성에 약간의 변화만으로 다시 중합화되는 곳을 제시합니다.

분자 재활용을 위해 설계: 리닌 유래 반 방향족 생물 기반 폴리머

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

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Gyroid Nickel Nanostructures from Diblock Copolymer Supramolecules

디 블록 공중 합체의 초분자에서 Gyroid 니켈 나노 구조

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

연구

화학

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

포스 포의 향상된 농축을위한 거대 다공성 고분자 모노리스에 다공성 조정 폴리머 코팅의 제조

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

혼합 폴리머 / 풀러렌 나노 입자 감광제를 실시와 광 역학 치료

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

작은 각도 중성자 산란에 의한 열 가역적 블록 공중 합체 및 특성 단일 벽 탄소 나노 튜브의 기능화

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

열 가역적 가교 고무 통해 딜스 - 알더 화학의 준비 및 등록

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

레이저 기반 초고속 분자 회전의 직접 이미징

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

미세 드라이 회전 및 재생성된 실크 Fibroin 섬유의 특성

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

전기 화학 임피던스 분 광 전기 화학 속도 상수 추정을 위한 도구로

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

시간 해결 Photophysical 특성화 Triplet 수확 유기 화합물은 산소가 없는 환경을 사용 하 여는 iCCD 카메라

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