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

小心:许多在此协议中使用的化学品是有害物质。查阅材料安全数据表（MSDS），并与这些物质时使用适当的个人防护装备（PPE）。 1.净化，准备和试剂的存储<ol><li>提纯，使用根据制造商的协议的溶剂纯化系统中使用的所有溶剂。如果溶剂净化系统不可用时，使用干燥剂（ 例如，分子筛，氢化钙2 等 ）和蒸馏。一旦干燥，储存溶剂在氮气氛下在室温下的手套箱。 </li><li>根据制造商的协议通过真空蒸馏纯化所有单体。一旦蒸馏，储存单体在黑暗的瓶子氮气氛下在冰箱中。 </li><li>根据制造商的协议通过真空蒸馏纯化引发剂。一旦蒸馏，储存在发起人在氮气氛下黑暗瓶在冰箱中。 </li><li>根据制造商的协议通过升华纯化苝。一旦升华，储存在室温下的台式苝。 </li><li>通过加入25.0毫克BHT到100g的瓶CDCL 3的制备二丁基羟基甲苯（BHT）在氘化氯仿（CDCL 3）的250ppm的溶液。准备并存储在台式此解决方案。 </li></ol> 2.光聚合甲基丙烯酸甲酯的使用苝作为光触媒<ol><li>允许所有试剂来室温。检查用来确保没有污染的迹象，如变色或形成固体颗粒前所有试剂。 </li><li>在氮气氛手套箱，放置在20mL闪烁瓶中的小搅拌棒。添加2.36毫克苝（9.38微摩尔，1.00当量）。 </li><li>添加1.00毫升二甲基甲酰胺（DMF）中。 </li><li>向该混合物中，添加1.00毫升（9.38毫摩尔，1000当量）甲基丙烯酸甲酯（MMA）。 </li><li>放置在小瓶上的搅拌盘设定为1600转和由白色发光二极管（LED）的条带照明。限制从其他光源（ 例如 ，高架灯，附近窗户）的照明。 </li><li>为了引发反应，加入16.4微升（93.8微摩尔，10.0当量） 通过吸管α -乙基醋酸溴苯（EBP）。 注意:要执行使用自然的阳光这个反应，按照上面的步骤，忽略步2.5，然后密封小瓶，把它拿出来手套箱中，并将小瓶通过自然阳光照射的区域。 </li><li>搅拌下恒定光照24小时的反应。隔离并按照步骤4.1的说明纯化产物聚（MMA） - 4.4。 </li></ol> 3.反应的动力学分析<ol><li>在台式，分配0.70毫升在CDCl 3中的溶液的的BHT到2ml小瓶中，并用隔片盖密封。提起这瓶我<html>扎成，其中正在执行聚合手套箱。 </li><li>用注射器除去0.20毫升反应混合物。注入注射器的内容物到含有在CDCl 3中的的BHT 250ppm的溶液的2个管形瓶中。退，并在柱塞推几次，以确保聚合反应的彻底骤冷。 </li><li>转的2个管形瓶中的内容传送到一个​​NMR（核磁共振）光谱法管。 通过分析1小时核磁共振光谱的转化率这个样本。24 </li><li>对于使用苝甲基丙烯酸甲酯聚合的具体例子，由区域对应于未反应的单体（δ= 3.62）（M）的甲氧基的氢的峰下比较计算从样品的1 H NMR谱百分转化率和对应于使用下面的公式聚合物（δ= 3.50）（P）的甲氧基的氢的峰下面积: 1"SRC ="/文件/ ftp_upload / 53571 / 53571eq1.jpg"/&gt; </li><li>分析后，倒入NMR谱管中的内容到一个干净的20mL闪烁瓶中。在减压下蒸发溶剂。重新溶解1.00毫升四氢呋喃（THF）中的样品。 </li><li>送通过注射滤器样品放入一个干净的2管形瓶中。分析通过加上多角度光散射来确定数均分子量（M n）的重均分子量（M w）和分散度（DJ）凝胶渗透色谱（GPC）的样品。24 </li></ol> 4.分离和产物聚合物的纯化<ol><li>淬火通过倾倒在反应混合物中的内容到50倍过量的甲醇中，并让搅拌至少1小时的聚合反应。 </li><li>根据制造商的通过真空过滤分离从甲醇有机玻璃协议。 注意:隔离方法将根据所生产的聚合物的不同而不同。对于聚甲基丙烯酸甲酯和聚苯乙烯，真空过滤来自使用布氏漏斗在甲醇中沉淀聚合物。为聚（丙烯酸丁酯），滗从所述粘性的聚合物的甲醇。 </li><li>冲洗用额外的100毫升甲醇的聚合物。 </li><li>再溶于二氯甲烷并重复步骤聚合物4.1至4.3的两倍以上。 </li></ol> MMA的大分子引发剂的5链延伸与苯乙烯以产生聚（甲基丙烯酸甲酯）-b-聚（S） <ol><li>允许所有试剂来室温。检查用来确保没有污染的迹象，如变色或形成固体颗粒前所有试剂。 </li><li>在氮气氛中的手套箱，放置136毫克（2.34微摩尔，1.00当量）的聚（甲基丙烯酸甲酯）的大分子引发剂到配备有小搅拌棒的20ml闪烁管中。 </li><li>添加0.59毫克苝（2.34微摩尔，1.00当量）。 </li><li>加入1.00毫升DMF。 </li><li>将小瓶上的轰动板设置为1600 RPM和白光LED照明条。限制从其他光源（ 例如，高架灯，附近窗户）的照明。 </li><li>向该混合物中， 通过移液管添加苯乙烯（S）1.24毫升（11.7毫摩尔，5000当量）。 </li><li>搅拌下恒定光照24小时的反应。分离和纯化产物的聚（甲基丙烯酸甲酯）-b-聚（S）由以下步骤4.1中的说明 - 4.4。 </li></ol>

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The authors have nothing to disclose.

虽然该协议演示此聚合技术的一个具体的例子，提供给研究者进行该反应的选择相当广阔。修饰可以在若干点进行整个协议，以允许任何特定photoredox的正在执行的ATRP的优化。随着新的单体，引发剂，以及用于该反应在调查来催化剂中，化学计量学和溶剂用于执行能够反应并且应修改的反应条件的优化的一部分。此外，从个人实验者可以选择使用表1作为一个准则来修改其他参数，如?...

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 border="0" cellpadding="0" cellspacing="0" width="572">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">perylene, min 98.0%</td>
			<td style="width:92px;">TCI America</td>
			<td style="width:128px;">TCP0078-025G</td>
			<td style="width:147px;">purify by sublimation</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">N,N-dimethylformamide</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">EM-DX1726-1</td>
			<td style="width:147px;">Omnisolv</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:205px;">methyl methacrylate, 99%</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">200000-678</td>
			<td style="width:147px;">distilled prior to use, stored in refrigerator</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">ethyl &#945;-bromophenyl acetate&#160;</td>
			<td style="width:92px;">Aldrich</td>
			<td style="width:128px;">554065</td>
			<td style="width:147px;">distilled prior to use stored in refrigerator</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;">butylated hydroxytoluene&#160;</td>
			<td style="width:92px;">Aldrich</td>
			<td style="width:128px;">W218405</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;">Chloroform-D</td>
			<td style="width:92px;">Cambridge Isotope Labs</td>
			<td style="width:128px;">DLM-7-100</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">tetrahydrofuran</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">EM-TX0279-1</td>
			<td style="width:147px;">Omnisolv</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">methanol</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">BDH1135</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">dichloromethane</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">EM-DX0831-1</td>
			<td style="width:147px;">Omnisolv</td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:205px;">styrene, 99%</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">AAAA18481-0F</td>
			<td style="width:147px;">distilled prior to use, stored in refrigerator</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">glass scintillation vial, 20 mL</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">66022-065</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">screw top vial, 2 mL</td>
			<td style="width:92px;">Agilent</td>
			<td style="width:128px;">5182-0715</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">septum cap for screw top vial</td>
			<td style="width:92px;">Agilent</td>
			<td style="width:128px;">5182-0717</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:205px;">heavy wall pressure vessel, 100 mL</td>
			<td style="width:92px;">Synthware</td>
			<td style="width:128px;">P160005&#160;</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">syringe, 1 mL norm-ject</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">89174-491</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">NMR tube</td>
			<td style="width:92px;">New Era</td>
			<td style="width:128px;">NE-UL5-7&#39;</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">nylon syringe filter, 0.45 um</td>
			<td style="width:92px;">VWR</td>
			<td style="width:128px;">28143-240</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">glovebox</td>
			<td style="width:92px;">Mbraun</td>
			<td style="width:128px;">LABstar</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">solvent purification system</td>
			<td style="width:92px;">Mbraun</td>
			<td style="width:128px;">MB-SPS-800</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">stirplate</td>
			<td style="width:92px;">IKA</td>
			<td style="width:128px;">3582401</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="84">
			<td height="84" style="height:84px;width:205px;">light-emitting diodes</td>
			<td style="width:92px;">Creative Lighting Solutions</td>
			<td style="width:128px;">CL-FRS1210-5M-12V-WH</td>
			<td style="width:147px;">2x 12-inch strips of 5500 K white LEDs were used for illumination</td>
		</tr>
		<tr height="63">
			<td height="63" style="height:63px;width:205px;">12V DC power supply for LEDs</td>
			<td style="width:92px;">Creative Lighting Solutions</td>
			<td style="width:128px;">CL-PS16001-40W</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:205px;">high performance liquid chromatograph&#160;</td>
			<td style="width:92px;">Agilent</td>
			<td style="width:128px;">G1310B, G1322A, G1329B, G1316A</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:205px;">gel permeation size-exclusion columns</td>
			<td style="width:92px;">Agilent</td>
			<td style="width:128px;">PL1110-6500</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="42">
			<td height="42" style="height:42px;width:205px;">multi-angle light scattering detector</td>
			<td style="width:92px;">Wyatt</td>
			<td style="width:128px;">WTREOS</td>
			<td style="width:147px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:205px;">differential refractometer</td>
			<td style="width:92px;">Wyatt</td>
			<td style="width:128px;">WTREX</td>
			<td style="width:147px;"></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示出了聚合结果通过该方法达到的范围内。这些数据表明，苝能够用作许多官能化的乙烯基单体的聚合的光催化剂。对于一个特定的单体中的任一数目的反应参数，如溶剂，化学计量，引发剂，和光源的调整导致聚合物具有不同的分子量和分散度从非常好到相当宽的。 图1示出了链-的结果延伸实验如在第4部分描述的，并表明使用该方法形成的...

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

使用苝作为可见光光催化功能化的乙烯基单体原子转移自由基聚合

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 次观看.  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.

视频: 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.

在玻碳和氟掺杂的氧化锡电极的含乙烯基聚吡啶基复合还原电聚合

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

科研

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.

电活性聚合物纳米粒子参展光热特性

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

工程学

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.

使用Photoredox催化剂蠕虫状胶束的简便合成可见光介导的分散聚合

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.

功能性降冰片烯的催化聚合插入一种简单高效的协议

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.

氧化锰催化剂光活化 Polyoxometalate 基光响应膜的制备

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.

[(Dpepphos) (bcp) Cu]PF6: 一种通用的、广泛适用的铜基光氧催化剂

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.

通过I型光引发可逆加成-碎片链转移聚合进行3D打印和原位表面改性

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.

自由基聚合反应的光化学引发

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 ...

教育

JoVE Science Education

无机化学

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="Figure1" src="/files/ftp_upload/11773/11773_PT_Figure_1.svg" style="text-align: center; height: 60px;" />
Alkenes undergo polymerization via a free-radical mechanism involving three steps: initiation, propagation, and termination.&#160;
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&#183;), which adds to the double bond of the alkene to initiate the polymerization process. One of the electrons of the alkene &#960; bond pairs with one electron from the phenyl radical to form a new C&#8211;C bond.
<img alt="Figure2" src="/files/ftp_upload/11773/11773_PT_Figure_2.svg" style="text-align: center; height: 60px;" />
<img alt="Figure3" src="/files/ftp_upload/11773/11773_PT_Figure_3.svg" style="text-align: center; height: 60px;" />
<img alt="Figure4" src="/files/ftp_upload/11773/11773_PT_Figure_4.svg" style="text-align: center; height: 80px;" />
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="Figure5" src="/files/ftp_upload/11773/11773_PT_Figure_5.svg" style="text-align: center; height: 80px;" />
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="Figure6" src="/files/ftp_upload/11773/11773_PT_Figure_6.svg" style="text-align: center; height: 60px;" />
In termination by disproportionation, a &#946;-hydrogen atom is transferred from one radical to another radical center, resulting in two non-radical products.
<img alt="Figure7" src="/files/ftp_upload/11773/11773_PT_Figure_7.svg" style="text-align: center; height: 300px;" />
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

烯烃的自由基链式反应和聚合

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

有机化学

烯烃的反应

关键术语与概念

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

自由基链生长聚合:概述

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