Name: atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible light photocatalyst
Uploaded: 2016-04-22T13:00:00.000+00:00
Duration: 6 min 49 s
Description: Watch this Scientific Journal Video about Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst at JoVE.com

The authors would like to acknowledge the University of Colorado Boulder for its support of this work.

注意：このプロトコルで使用される化学物質の多くは、有害物質です。化学物質等安全データシート（MSDS）を参照し、これらの物質を扱う際には、適切な個人用保護具（P​​PE）を使用します。 1.精製、準備、および試薬の保管<ol><li>製造業者のプロトコルに従って、溶媒精製システムを用いて使用される全ての溶媒を精製します。溶媒精製システムが使用できない場合、（ 例えば、モレキュラーシーブをCaH 2 など ）乾燥剤を使用して蒸留。室温でグローブボックス中の窒素雰囲気下で乾燥させ、店舗溶媒一度。 </li><li>製造業者のプロトコルに従って真空蒸留して、すべてのモノマーを精製します。一度冷蔵庫に窒素雰囲気下で暗所ボトルで、店舗モノマーを蒸留しました。 </li><li>製造業者のプロトコルに従って真空蒸留により開始剤を精製します。 、店舗イニシエータで蒸留した後冷蔵庫で窒素雰囲気下で暗いボトル。 </li><li>製造業者のプロトコルに従って、昇華によりペリレンを精製します。昇華した後、室温でベンチトップにペリレンを格納します。 </li><li> CDCl 3中の100グラムボトルに25.0ミリグラムのBHTを添加することにより、重クロロホルム（CDCl 3中）にブチル化ヒドロキシトルエン（BHT）250ppmの溶液を調製します。ベンチトップ上でこのソリューションを準備し、格納します。 </li></ol>光触媒としてペリレンを用いたメタクリル酸メチルの2光重合<ol><li>すべての試薬は室温に戻します。このような固体粒子の変色や形成などの汚染の兆候がないことを確認するために使用する前にすべての試薬を、点検してください。 </li><li>窒素雰囲気のグローブボックス内で、20ミリリットルのシンチレーションバイアルに小さな撹拌棒を配置します。 2.36ミリグラム（9.38モル、1.00当量）ペリレンのを追加します。 </li><li> 1.00ミリリットルのジメチルホルムアミド（DMF）を追加します。 </li><li>この混合物に1.00ミリリットル（9.38ミリモル、追加千当量）、メチルメタクリレート（MMA）。 </li><li> 1600回転に設定されており、白色発光ダイオード（LED）のストリップによって照らさ撹拌プレート上でバイアルを置きます。他の光源（ 例えば 、頭上の照明、近くの窓）から任意の照明を制限します。 </li><li>ピペットを用いて反応を開始し、16.4μlの追加（93.8マイクロモル、10.0当量）をα-エチルブロモフェニル酢酸（EBP）のこと。 注意：自然光を使用して、この反応を実行するには、ステップ2.5を無視して、上記の手順に従って、その後、バイアルを密封グローブボックスの外にそれを持って、自然の太陽光により照明領域にバイアルを置きます。 </li><li>一定の照明の下で24時間反応を撹拌しました。 4.4 - 手順4.1の指示に従って、製品ポリ（MMA）を単離および精製します。 </li></ol>反応の3速度論的解析<ol><li>ベンチトップで、2ミリリットルバイアルにのCDCl 3溶液中のBHTの0.70ミリリットルを分配し、セプタムキャップで密封。このバイアル私を持参<html>重合が行われているグローブボックスをNTO。 </li><li>反応混合物の0.20ミリリットルを削除するには、注射器を使用してください。 CDCl 3中のBHT 250ppmの溶液を含む2 mL瓶の中に注射器の内容物を注入します。バック描画し、重合を完全に消光を確保するために、プランジャーに数回押してください。 </li><li> NMR（核磁気共鳴）分光管に2ミリリットルバイアルの内容を転送します。パーセント変換のための1 H NMR分光法を介して、このサンプルを分析します。24 </li><li>ペリレンを使用して、メタクリル酸メチルの重合の具体例については、未反応の単量体（δ= 3.62）（M）のメトキシ水素に相当するピーク下の面積を比較することによって、サンプルの1 H NMRスペクトルから転化率を計算し以下の式を使用してポリマー（δ= 3.50）（P）のメトキシ水素に対応するピーク下の面積。 1 &quot;SRC =&quot; /ファイル/ ftp_upload / 53571 / 53571eq1.jpg &quot;/&gt; </li><li>分析の後、清浄な20mLのシンチレーションバイアルにNMR分光管の内容物を注ぎます。減圧下で溶媒を蒸発させます。テトラヒドロフランの1.00ミリリットル（THF）のサンプルを再溶解します。 </li><li>きれいな2ミリリットルバイアルにシリンジフィルターを通してサンプルを送信します。数平均分子量（M n）、重量平均分子量（Mw）、分散度（DJ）を決定するために多角度光散乱と結合されたゲル浸透クロマトグラフィー（GPC） によって試料を分析する。24 </li></ol>製品ポリマーの4単離および精製<ol><li>メタノールの50倍過剰に反応混合物の内容物を注入し、少なくとも1時間攪拌をさせることにより、重合反応を停止。 </li><li>製造業者の使用による真空濾過によってメタノールからポリ（メチルメタクリレート）を単離しますプロトコル。 注意：単離方法は、製造されるポリマーに依存して変化します。ポリ（メチルメタクリレート）、ポリスチレン、真空をブフナー漏斗を用いて、メタノールから沈殿したポリマーを濾過します。ポリ（アクリル酸ブチル）のために、粘性ポリマーからメタノールをデカント。 </li><li>追加の100ミリリットルのメタノールでポリマーを洗浄します。 </li><li>再溶解し、ジクロロメタンおよびリピート中のポリマーは、二​​回以上の4.3を介して4.1を繰り返します。 </li></ol> -bポリポリ（MMA）を生成するスチレンとMMAマクロ開始剤の5鎖延長（S） <ol><li>すべての試薬は室温に戻します。このような固体粒子の変色や形成などの汚染の兆候がないことを確認するために使用する前にすべての試薬を、点検してください。 </li><li>窒素雰囲気のグローブボックス内で、ポリ（MMA）の136ミリグラム（2.34モル、1.00当量）を配置するマクロ開始剤の小撹拌棒を装着した20ミリリットルのシンチレーションバイアルに。 </li><li> 0.59 mgのペリレン（2.34マイクロモル、1.0を追加します。0当量）。 </li><li> 1.00ミリリットルのDMFを追加します。 </li><li> 1600回転に設定されており、白色LEDのストリップによって照らさ撹拌プレート上でバイアルを置きます。他の光源（ 例えば、頭上の照明、近くの窓）から任意の照明を制限します。 </li><li>この混合物に、ピペットを用いてスチレン（S）の1.24ミリリットル（11.7ミリモル、5000当量）を追加します。 </li><li>一定の照明の下で24時間反応を撹拌しました。 4.4 - 手順4.1の指示に従って、製品ポリ（MMA）-b-ポリ（S）を単離および精製します。 </li></ol>

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The authors have nothing to disclose.

プロトコルはこの重合法の具体例を示していたが、この反応を行う研究者が利用できるオプションはかなり広いです。修飾は、ATRPが実行されている特定のどんなphotoredoxの最適化を可能にするために、プロトコル全体点の個数で製造することができます。新しいモノマー、開始剤、及び調査下に来るこの反応のための触媒として、反応を実行するために使用される化学量論および溶媒は、反?...

The synthesis of technologically advanced polymers requires precise control over polymer molecular weight, dispersity (&#208;), composition, and architecture.1,2 Controlled radical polymerizations (CRPs)3-8 have revolutionized the synthesis of well-defined polymers, with atom transfer radical polymerization (ATRP) being the most used CRP, largely due to operational simplicity and synthetic versatility.9-14 The crux of ATRP is the ability to reversibly deactivate the polymerization, controlling the equilibrium between a propagating radical and a dormant species. Enforcing a low concentration of active radicals greatly minimizes bimolecular termination pathways and allows for the synthesis of well-defined polymers. 
Traditional ATRP relies on a transition metal catalyst to mediate this equilibrium.3 These metal catalysts contaminate the polymer product and impede implementation in biomedical or electronic applications while also raising environmental concerns. Although significant strides have been made to reduce the catalyst concentration to ppm levels, these methodologies require more demanding experimental conditions and metal contamination is still not entirely eliminated.15,16
Reversible addition-fragmentation transfer17,18 and nitroxide-mediated polymerizations19,20 are CRPs that do not require metal catalysts, although they have been used less often than ATRP.3 Recently, reversible chain-transfer21 and reversible complexation22,23 variants of ATRP that can use organic catalysts were reported. However, these methodologies require the use of alkyl iodide initiators and are not effective with the alkyl bromides commonly employed in ATRP. A highly desirable CRP would match the performance, feasibility, and robustness of traditional ATRP while being catalyzed by an organic catalyst under mild conditions.
Here, we describe a methodology for the radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst. Through optimization of parameters such as stoichiometry, concentration, time, and light flux, the molecular weight of the polymers can be controlled.24, 25 Similar methodologies have been recently introduced using phenothiazine derivatives as photocatalysts for metal-free ATRP.26, 27 Because researchers in the field of polymerization catalysis are constantly developing new catalytic systems, the ability to compare catalyst performance across a number of metrics is vital. This ability to make comparisons relies heavily upon procedural consistency and clarity on the part of the researchers performing the experiments. As such, it is our goal that this video will be used to help precisely communicate the methods by which these polymers are synthesized and characterized.

<table><tbody><tr><td>perylene, min 98.0%</td><td>TCI America</td><td>TCP0078-025G</td><td>purify by sublimation</td></tr><tr><td>&lt;em&gt;N,N&lt;/em&gt;-dimethylformamide</td><td>VWR</td><td>EM-DX1726-1</td><td>Omnisolv</td></tr><tr><td>methyl methacrylate, 99%</td><td>VWR</td><td>200000-678</td><td>distilled prior to use, stored in refrigerator</td></tr><tr><td>ethyl &amp;alpha;-bromophenyl acetate&amp;nbsp;</td><td>Aldrich</td><td>554065</td><td>distilled prior to use stored in refrigerator</td></tr><tr><td>butylated hydroxytoluene&amp;nbsp;</td><td>Aldrich</td><td>W218405</td><td></td></tr><tr><td>Chloroform-D</td><td>Cambridge Isotope Labs</td><td>DLM-7-100</td><td></td></tr><tr><td>tetrahydrofuran</td><td>VWR</td><td>EM-TX0279-1</td><td>Omnisolv</td></tr><tr><td>methanol</td><td>VWR</td><td>BDH1135</td><td></td></tr><tr><td>dichloromethane</td><td>VWR</td><td>EM-DX0831-1</td><td>Omnisolv</td></tr><tr><td>styrene, 99%</td><td>VWR</td><td>AAAA18481-0F</td><td>distilled prior to use, stored in refrigerator</td></tr><tr><td>glass scintillation vial, 20&amp;nbsp;ml</td><td>VWR</td><td>66022-065</td><td></td></tr><tr><td>screw top vial, 2 ml</td><td>Agilent</td><td>5182-0715</td><td></td></tr><tr><td>septum cap for screw top vial</td><td>Agilent</td><td>5182-0717</td><td></td></tr><tr><td>heavy wall pressure vessel, 100 ml</td><td>Synthware</td><td>P160005&amp;nbsp;</td><td></td></tr><tr><td>syringe, 1 ml norm-ject</td><td>VWR</td><td>89174-491</td><td></td></tr><tr><td>NMR tube</td><td>New Era</td><td>NE-UL5-7&#039;</td><td></td></tr><tr><td>nylon syringe filter, 0.45&amp;nbsp;&amp;#956;m</td><td>VWR</td><td>28143-240</td><td></td></tr><tr><td>glovebox</td><td>Mbraun</td><td>LABstar</td><td></td></tr><tr><td>solvent purification system</td><td>Mbraun</td><td>MB-SPS-800</td><td></td></tr><tr><td>stirplate</td><td>IKA</td><td>3582401</td><td></td></tr><tr><td>light-emitting diodes</td><td>Creative Lighting Solutions</td><td>CL-FRS1210-5M-12V-WH</td><td>2x 12-inch strips of 5500 K white LEDs were used for illumination</td></tr><tr><td>12 V DC power supply for LEDs</td><td>Creative Lighting Solutions</td><td>CL-PS16001-40W</td><td></td></tr><tr><td>high performance liquid chromatograph&amp;nbsp;</td><td>Agilent</td><td>G1310B, G1322A, G1329B, G1316A</td><td></td></tr><tr><td>gel permeation size-exclusion columns</td><td>Agilent</td><td>PL1110-6500</td><td></td></tr><tr><td>multi-angle light scattering detector</td><td>Wyatt</td><td>WTREOS</td><td></td></tr><tr><td>differential refractometer</td><td>Wyatt</td><td>WTREX</td><td></td></tr></tbody></table>

atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible light photocatalyst

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The procedure is performed under an inert atmosphere using air- and water-exclusion techniques. The outcome of the polymerization is affected by the ratios of monomer, initiator, and catalyst used as well as the reaction concentration, solvent, and nature of the light source. Temporal control over the polymerization can be exercised by turning the visible light source off and on. Low dispersities of the resultant polymers as well as the ability to chain-extend to form block copolymers suggest control over the polymerization, while chain end-group analysis provides evidence supporting an atom-transfer radical polymerization mechanism.

表1は、このメソッドを介して達成可能な重合結果の範囲を示しています。これらのデータは、ペリレンが官能ビニルモノマーの数の重合のための触媒として機能することが可能であることを示しています。特定のモノマー、溶媒、化学量論量、開始剤のような反応パラメーターの数のいずれかの調整、光源が非常に良いからではなく広い範囲の分子量及...

Watch this Scientific Journal Video about Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst at JoVE.com

Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

可視光応答型光触媒としてペリレンを使用した官能ビニルモノマーの原子移動ラジカル重合

A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

A standardized technique for atom transfer radical polymerization of vinyl monomers using perylene as a visible-light photocatalyst is presented. The ...

atom-transfer-radical-polymerization-functionalized-vinyl-monomers

Research

Education

JoVE Journal

JoVE Core

Organic Chemistry

Chemistry

Unit 1

Reactions of Alkenes

SCIENTISTS IN ACTION

11.6K ビュー.  University of Colorado Boulder. A method for the atom transfer radical polymerization of functionalized vinyl monomers using perylene as a visible-light photocatalyst is described.

ビデオ: Atom Transfer Radical Polymerization of Functionalized Vinyl Monomers Using Perylene as a Visible Light Photocatalyst

Reductive Electropolymerization of a Vinyl-containing Poly-pyridyl Complex on Glassy Carbon and Fluorine-doped Tin Oxide Electrodes

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is one surface modification technique that electrodeposits a polymeric film at the surface of an electrode by utilizing an applied potential to initiate the polymerization of substrates in the Helmholtz layer. This useful technique was first established by a Murray-Meyer collaboration at the University of North Carolina at Chapel Hill in the early 1980s and utilized to study numerous physical phenomena of films containing inorganic complexes as the monomeric substrate. Here, we highlight a procedure for coating electrodes with an inorganic complex by performing reductive electropolymerization of the vinyl-containing poly-pyridyl complex onto glassy carbon and fluorine doped tin oxide coated electrodes. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization but are far less sensitive to oxygen and water.

A procedure for performing reductive electropolymerization of vinyl-containing compounds onto glassy carbon and fluorine doped tin-oxide coated electrodes is presented. Recommendations on electrochemical cell configurations and troubleshooting procedures are included. Although not explicitly described here, oxidative electropolymerization of pyrrole-containing compounds follows similar procedures to vinyl-based reductive electropolymerization.

グラッシーカーボンとフ​​ッ素ドープ酸化スズ電極上にビニル含有ポリピリジル錯体の還元電解重合

Controllable electrode surface modification is important in a number of fields, especially those with solar fuels applications. Electropolymerization is ...

化学

Electroactive Polymer Nanoparticles Exhibiting Photothermal Properties

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step process that finishes with Negishi coupling. Negishi coupling is a cross-coupling process in which a chemical precursor is first lithiated, followed by transmetallation with ZnCl2. The resultant organozinc compound can be coupled to a dibrominated aromatic precursor to give the conjugated monomer. Polymer films can be prepared via electropolymerization of the monomer and characterized using cyclic voltammetry and ultraviolet-visible-near infrared (UV-Vis-NIR) spectroscopy. Nanoparticles (NPs) are prepared via emulsion polymerization of the monomer using a two-surfactant system to yield an aqueous dispersion of the polymer NPs. The NPs are characterized using dynamic light scattering, electron microscopy, and UV-Vis-NIR-spectroscopy. Cytocompatibility of NPs is investigated using the cell viability assay. Finally, the NP suspensions are irradiated with a NIR laser to determine their effectiveness as potential materials for photothermal therapy (PTT).

A protocol is presented for the synthesis and preparation of nanoparticles consisting of electroactive polymers.

電気活性ポリマーナノ粒子出展光熱プロパティ

A method for the synthesis of electroactive polymers is demonstrated, starting with the synthesis of extended conjugation monomers using a three-step ...

工学

Facile Synthesis of Worm-like Micelles by Visible Light Mediated Dispersion Polymerization Using Photoredox Catalyst

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins with the synthesis of a hydrophilic poly(oligo(ethylene glycol) methyl ether methacrylate) (POEGMA) homopolymer using reversible addition-fragmentation chain-transfer (RAFT) polymerization. Under mild visible light irradiation (&#955; = 460 nm, 0.7 mW/cm2), this macro-chain transfer agent (macro-CTA) in the presence of a ruthenium based photoredox catalyst, Ru(bpy)3Cl2 can be chain extended with a second monomer to form a well-defined block copolymer in a process known as Photoinduced Electron Transfer RAFT (PET-RAFT). When PET-RAFT is used to chain extend POEGMA with benzyl methacrylate (BzMA) in ethanol (EtOH), polymeric nanoparticles with different morphologies are formed in situ according to a polymerization-induced self-assembly (PISA) mechanism. Self-assembly into nanoparticles presenting POEGMA chains at the corona and poly(benzyl methacrylate) (PBzMA) chains in the core occurs in situ due to the growing insolubility of the PBzMA block in ethanol. Interestingly, the formation of highly pure worm-like micelles can be readily monitored by observing the onset of a highly viscous gel in situ due to nanoparticle entanglements occurring during the polymerization. This process thereby allows for a more reproducible synthesis of worm-like micelles simply by monitoring the solution viscosity during the course of the polymerization. In addition, the light stimulus can be intermittently applied in an ON/OFF manner demonstrating temporal control over the nanoparticle morphology.

This article describes a process for producing polymeric self-assembled nanoparticles using visible light mediated dispersion polymerization. Using low energy visible light to control the polymerization allows for the reproducible formation of self-assembled worm-like micelles at high solids content.

Photoredox触媒を用いた可視光媒介分散重合によるワームのようなミセルの簡便な合成

Presented herein is a protocol for the facile synthesis of worm-like micelles by visible light mediated dispersion polymerization. This approach begins ...

A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic nature of the monomer is conserved. The resulting polymer, polynorbornene, has a very high glass transition temperature, Tg, and interesting optical and electrical properties. However, the polymerization of functional norbornenes by this mechanism is complicated by the fact that the endo substituted norbornene monomer has, in general, a very low reactivity. Furthermore, the separation of the endo substituted monomer from the exo monomer is a tedious task. Here, we present a simple protocol for the polymerization of substituted norbornenes (endo:exo ca. 80:20) bearing either a carboxylic acid or a pendant double bond. The process does not require that both isomers be separated, and proceeds with low catalyst loadings (0.01 to 0.02 mol%). The polymer bearing pendant double bonds can be further transformed in high yield, to afford a polymer bearing pendant epoxy groups. These simple procedures can be applied to prepare polynorbornenes with a variety of functional groups, such as esters, alcohols, imides, double bonds, carboxylic acids, bromo-alkyls, aldehydes and anhydrides.

We describe the catalytic insertion polymerization of 5-norbornene-2-carboxylic acid and 5-vinyl-2-norbornene to form functional polymers with a very high glass transition temperature.

機能性ノルボルネンの触媒挿入重合のためのシンプルで効率的なプロトコル

Norbornene can be polymerized by a variety of mechanisms, including insertion polymerization whereby the double bond is polymerized and the bicyclic ...

Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic polymers, with the aim of photo-activating oxygen-evolving manganese oxide catalysts, which are important components in artificial photosynthesis. The cross-linking technique was applied to obtain a self-standing membrane with a high PW12O403- content. Incorporation and structure retention of PW12O403- within the polymer matrix were confirmed by FT-IR and micro-Raman spectroscopy, and optical characteristics were investigated by UV-Vis spectroscopy, which revealed successful construction of the metal-to-metal charge transfer (MMCT) unit. After deposition of MnOx oxygen evolving catalysts, photocurrent measurements under visible light irradiation verified the sequential charge transfer, Mn &#8594; MMCT unit &#8594; electrode, and&#160;the photocurrent intensity was consistent with the redox potential of the donor metal (Ce or Co). This method provides a new strategy for preparing integrated systems involving catalysts and photon-absorption parts for use with photo-functional materials.

Here, we present a protocol to prepare charge transfer chromophores based on a polyoxometalate/polymer composite membrane.

マンガン酸化物触媒の光活性化用ポリ酸を用いた光応答性膜の作製

This paper presents a method to prepare charge-transfer chromophores using polyoxotungstate (PW12O403-), transition metal ions (Ce3+ or Co2+), and organic ...

[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the activation of a broad variety of organic halides, including unactivated ones. These can then participate in various radical transformations such as reduction and cyclization reactions, as well as in the direct arylation of several (hetero)arenes. These transformations provide a straightforward access to a range of small molecules of interest in synthetic chemistry, as well as to biologically active natural products. Altogether, [(DPEPhos)(bcp)Cu]PF6 acts as a convenient photoredox catalyst which appears to be an attractive, cheap and complementary alternative to the state-of-the-art iridium- and ruthenium-based photoredox catalysts. Here, we report a detailed protocol for the synthesis of [(DPEPhos)(bcp)Cu]PF6, as well as NMR and spectroscopic characterizations, and we illustrate its use in synthetic chemistry for the direct arylation of (hetero)arenes and radical cyclization of organic halides. In particular, the direct arylation of N-methylpyrrole with 4-iodobenzonitrile to afford&#160;4-(1-methyl-1H-pyrrol-2-yl)benzonitrile and the radical cyclization of N-benzoyl-N-[(2-iodoquinolin-3-yl)methyl]cyanamide to afford natural product luotonin A are detailed. The scope and limitations of this copper-based photoredox catalyst are also briefly discussed.

[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst

Detailed and general protocols are presented for the synthesis of [(DPEPhos)(bcp)Cu]PF6, a general copper-based photoredox catalyst, and for its use in synthetic chemistry for the direct arylation of C-H bonds in (hetero)arenes and radical cyclization of organic halides.

[(DPEPhos) (bcp) Cu]PF6: 一般的で広く適用される銅系 Photoredox 触媒

Our group recently reported the use of [(DPEPhos)(bcp)Cu]PF6 as a general copper-based photoredox catalyst which proved efficient to promote the ...

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties dependent on the chemical composition of the resin. In the current work, 3D printed materials are post-functionalized using the 3D printer hardware via a secondary surface-initiated polymerization process, thus providing independent control over the bulk and interfacial material properties. This process begins with preparing liquid resins, which contain a monofunctional monomer, a crosslinking multifunctional monomer, a photochemically labile species that enables initiation of polymerization, and critically, a thiocarbonylthio compound which facilitates reversible addition-fragmentation chain transfer (RAFT) polymerization. The thiocarbonylthio compound, known commonly as a RAFT agent, mediates the chain growth polymerization process and provides polymeric materials with more homogeneous network structures. The liquid resin is cured in a layer-by-layer fashion using a commercially available digital light processing 3D printer to give three-dimensional materials having spatially controlled geometries. The initial resin is removed and replaced with a new mixture containing functional monomers and photoinitiating species. The 3D printed material is then exposed to light from the 3D printer in the presence of the new functional monomer mixture. This allows photoinduced surface-initiated polymerization to occur from the latent RAFT agent groups on the surface of the 3D printed material. Given the chemical flexibility of both resins, this process allows a wide range of 3D printed materials to be produced with tailorable bulk and interfacial properties.

3D Printing and In Situ Surface Modification via Type I Photoinitiated Reversible Addition-Fragmentation Chain Transfer Polymerization

The present protocol describes the digital light processing-based 3D printing of polymeric materials using type I photoinitiated reversible addition-fragmentation chain transfer polymerization and the subsequent in situ material post-functionalization via surface-mediated polymerization. Photoinduced 3D printing provides materials with independently tailored and spatially controlled bulk and interfacial properties.

タイプI光開始可逆的付加フラグメンテーション連鎖移動重合による3DプリンティングおよびIn Situ表面改質

3D printing provides facile access to geometrically complex materials. However, these materials have intrinsically linked bulk and interfacial properties ...

Photochemical Initiation Of Radical Polymerization Reactions

Source: David C. Powers, Tamara M. Powers, Texas A&#38;M
In this video, we will carry out the photochemically initiated polymerization of styrene to generate polystyrene, which is an important commodity plastic. We will learn the fundamentals of photochemistry and use simple photochemistry to initiate radical polymerization reactions. Specifically, in this module we will examine the photochemistry of benzoyl peroxide and its role as a photo-initiator of styrene polymerization reactions. In the described experiments, we will investigate the role of wavelength, photon absorption, and excited state structure on the efficiency (measured as quantum yield) of photochemical reactions.

根本的な重合反応の光化学開始

Source: David C. Powers, Tamara M. Powers, Texas A&#38;M
In this video, we will carry out the photochemically initiated polymerization of styrene to ...

JoVE Science Education

無機化学

Free-Radical Chain Reaction and Polymerization of Alkenes

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a repeating unit, while the terminal groups are considered insignificant. The average degree of polymerization represents the number of repeating units in the polymer molecule and is denoted by the subscript n.
<img alt="Polymer chain structure diagram; hydrocarbon backbone with side groups, chemistry, material science." src="/files/ftp_upload/11773/11773_PT_Figure_1.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure1">
Alkenes undergo polymerization via a free-radical mechanism involving three steps: initiation, propagation, and termination. 
Radicals are generated in the initiation step by heating a small quantity of free-radical initiators such as benzoyl peroxide. The benzoyloxy radical loses CO2 and forms a phenyl radical (Ph·), which adds to the double bond of the alkene to initiate the polymerization process. One of the electrons of the alkene π bond pairs with one electron from the phenyl radical to form a new C–C bond.
<img alt="Radical reaction mechanism diagram, benzoyl peroxide decomposition into radicals, chemical process." src="/files/ftp_upload/11773/11773_PT_Figure_2.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure2">
<img alt="Chemical reaction diagram of phenyl cation formation via decarboxylation process with equations." src="/files/ftp_upload/11773/11773_PT_Figure_3.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure3">
<img alt="Chemical reaction diagram showing radical polymerization steps with benzene and propylene." src="/files/ftp_upload/11773/11773_PT_Figure_4.svg" style="text-align: center; height: 80px;" data-altupdatedat="1747908711000" data-alt="Figure4">
In the propagation step, the carbon radical generated in the initiation step adds to another molecule of alkene to generate a new radical. The continuous addition of alkene monomers at the radical site yields the polymer.
<img alt="Allylic polymerization process, chemical reaction equation, polymer chain formation." src="/files/ftp_upload/11773/11773_PT_Figure_5.svg" style="text-align: center; height: 80px;" data-altupdatedat="1747908711000" data-alt="Figure5">
The termination step of the free-radical mechanism occurs via recombination or disproportionation. In a recombination step, two growing chains form a bond at their radical sites.
<img alt="Polymerization process diagram with structural formulas and reaction arrows." src="/files/ftp_upload/11773/11773_PT_Figure_6.svg" style="text-align: center; height: 60px;" data-altupdatedat="1747908711000" data-alt="Figure6">
In termination by disproportionation, a β-hydrogen atom is transferred from one radical to another radical center, resulting in two non-radical products.
<img alt="Free radical reaction diagram; benzyl radical formation; organic chemistry mechanism." src="/files/ftp_upload/11773/11773_PT_Figure_7.svg" style="text-align: center; height: 300px;" data-altupdatedat="1747908711000" data-alt="Figure7">
The free-radical polymerization of ethylene yields low-density polyethylene (LDPE), where the low density is a consequence of significant branching in the polymer chains. Articles made from polymers surround us in various forms, such as food packaging materials, plastic bags, bottles, stationery, and automotive parts.

Free-radical Polymerization Reaction of Alkenes

フリーラジカル連鎖反応とアルケンの重合

The conversion of alkenes to macromolecules called polymers is a reaction of high commercial importance. The structure of the polymer is defined by a ...

有機化学

ユニット １

アルケンの反応

KEY TERMS AND CONCEPTS

Radical Chain-Growth Polymerization: Overview

Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the reaction proceeds via a free-radical intermediate. The free radical is formed from radical initiators, which spontaneously generate free radicals by homolytic fission. Organic peroxides (such as dibenzoyl peroxide, as shown in Figure 1) or azo compounds are popular radical initiators. A low concentration ratio of radical initiator to monomer is used to minimize radical coupling.
<img alt="Figure1" src="/files/ftp_upload/12920/12920_PT_Figure_1.svg" style="text-align: center; height: 75px;" />
Figure 1: The homolytic fission reaction of radical initiator dibenzoyl peroxide to generate benzoyloxy radicals and the subsequent decomposition to phenyl radicals
This free radical initiates polymerization by reacting with a monomer molecule. Unsaturated monomers are suitable for radical chain-growth polymerization; a substituent group across the unsaturated bond that stabilizes the free radical increases the reaction feasibility. Ethylene, propylene, vinyl chloride, and styrene are examples of monomers that can be polymerized via free-radical chain-growth polymerization.
The reaction between a monomer and a free radical generates a new free radical. This new radical reacts with another monomer and creates yet another free radical. The polymer chain grows as the reaction between free-radical intermediates and monomers repeats sequentially. Typically, the propagation step repeats one thousand to ten thousand times before the termination of polymerization.
Often, chain transfer reagents, such as thiol, are used to control the molecular weight (Figure 2). A chain transfer agent must be sufficiently reactive to transfer a hydrogen atom to the growing chain to terminate the polymer growth. The resultant radical must add to a double bond in the monomer to initiate polymerization.
<img alt="Figure2" src="/files/ftp_upload/12920/12920_PT_Figure_2_.svg" style="text-align: center; height: 150px;" />
Figure 2: (Top): The termination reaction of chain transfer agent thiol and a growing polymer chain; (Bottom): Subsequent reaction of thiol radical and monomer molecule to initiate polymer growth
Inhibitors are the reagents used to reduce the reactivity of radicals in the growing polymer chain. Figure 3 depicts the reaction of benzoquinone as an inhibitor.
<img alt="Figure3" src="/files/ftp_upload/12920/12920_PT_Figure_3.svg" style="text-align: center; height: 200px;" />
Figure 3: The reaction between chain inhibitor benzoquinone and a growing polymer chain to generate a less reactive free radical

ラジカル連鎖成長重合:概要

Chain-growth or addition polymerization is successive addition reactions of monomers with a polymer chain. In radical chain-growth polymerization, the ...

可視光応答型光触媒としてペリレンを使用した官能ビニルモノマーの原子移動ラジカル重合

要約

さらに動画を探す

この動画の章

グラッシーカーボンとフッ素ドープ酸化スズ電極上にビニル含有ポリピリジル錯体の還元電解重合

電気活性ポリマーナノ粒子出展光熱プロパティ

Photoredox触媒を用いた可視光媒介分散重合によるワームのようなミセルの簡便な合成

機能性ノルボルネンの触媒挿入重合のためのシンプルで効率的なプロトコル

マンガン酸化物触媒の光活性化用ポリ酸を用いた光応答性膜の作製

[(DPEPhos) (bcp) Cu]PF₆: 一般的で広く適用される銅系 Photoredox 触媒

タイプI光開始可逆的付加フラグメンテーション連鎖移動重合による3DプリンティングおよびIn Situ表面改質

根本的な重合反応の光化学開始

フリーラジカル連鎖反応とアルケンの重合

ラジカル連鎖成長重合:概要

可視光応答型光触媒としてペリレンを使用した官能ビニルモノマーの原子移動ラジカル重合

要約

さらに動画を探す

この動画の章

グラッシーカーボンとフ​​ッ素ドープ酸化スズ電極上にビニル含有ポリピリジル錯体の還元電解重合

電気活性ポリマーナノ粒子出展光熱プロパティ

Photoredox触媒を用いた可視光媒介分散重合によるワームのようなミセルの簡便な合成

機能性ノルボルネンの触媒挿入重合のためのシンプルで効率的なプロトコル

マンガン酸化物触媒の光活性化用ポリ酸を用いた光応答性膜の作製

[(DPEPhos) (bcp) Cu]PF6: 一般的で広く適用される銅系 Photoredox 触媒

タイプI光開始可逆的付加フラグメンテーション連鎖移動重合による3DプリンティングおよびIn Situ表面改質

根本的な重合反応の光化学開始

フリーラジカル連鎖反応とアルケンの重合

ラジカル連鎖成長重合:概要

グラッシーカーボンとフッ素ドープ酸化スズ電極上にビニル含有ポリピリジル錯体の還元電解重合

[(DPEPhos) (bcp) Cu]PF₆: 一般的で広く適用される銅系 Photoredox 触媒