The authors acknowledge funding from Fonds de Recherche du Qu&#233;bec - Nature et Technologies, from Conseil Recherches en Sciences Naturelles et G&#233;nie (program INNOV) and PrimaQu&#233;bec.

1.聚（5-降冰片烯-2-羧酸），PNBE制备（CO 2 H） <ol><li> 单体NBE制备（CO 2 H） <ol><li>称出丙烯酸（AA）（327克，4.5摩尔，2当量）和氢醌（4.9克，4.5×10 -2摩尔，0.02当量），并将它们添加到装有冷凝器的2升圆底烧瓶中和磁力搅拌棒。加热使用的硅油浴中在150℃的烧瓶中。 </li><li>一旦回流解决，在一个单一的部分添加的DCPD（300克，2.3摩尔，1当量），然后将温度升至170℃。 </li><li>离开在该温度下16小时的反应。观察由清晰到黄棕色的颜色变化。 </li><li>采取通过用巴斯德吸移管提取一个样本，并通过1 H核磁共振（使用CDCL 3为溶剂）15进行分析。观察NBE的（6.0和6.5 ppm时， 图2顶部之间的双键的信号）的幽灵。 16 </s达&gt; </li></ol></li><li> NBE的纯化（CO 2 H） <ol><li>与连接到在其中冷水循环的冷凝器的简单蒸馏装置（一个平台）替换冷凝器。 </li><li>把反应设置设定为约真空下。 1毫米汞柱。加热在100℃下的混合物中，并收集澄清的液体（ 约 40毫升），其可以被丢弃。 </li><li>更换了500毫升圆底烧瓶中的收集烧瓶。加热油浴至155℃，并观察NBE的滴加蒸馏（CO 2 H）（317克，2.3摩尔产率= 98％）。蒸馏接管7小时。 </li><li>通过1 H NMR分析无色液体，以评估纯度以及具有内切:外切比例（ 图2，底部）。 15 远藤:与用于蒸馏以及与用于粗NBE（CO 2 H）的制备在加热时的时间外型比的变化。通常情况下， 内:外切（在这种情况下，60:40）50:50和80:20，得到之间的比率。 </li></ol></li><li> NBE的聚合（CO 2 H） <ol><li>放置NBE（CO 2 H）300克（2.3摩尔，5000当量）在配备有磁力搅拌棒的500mL圆底烧瓶中。脱气通过鼓泡氮气30分钟的液体。 </li><li>权衡烯丙基钯（Ⅱ）氯化物二聚体，[的PdCl（C 3 H 5）] 2（76毫克，4.2×10 -1毫摩尔，1当量的Pd）并将其添加到该溶液中。添加银锑AgSbF 6（180毫克，5.2×10 -1毫摩尔，1.2当量）。 </li><li>在搅拌下，溶解通过加热钯盐在70℃，并在轻微的氮气通量下维持在70℃的温度。 7至8小时后，搅拌因粘度增加停止。 </li><li>停止36小时后的反应。 </li><li>冷却用液氮的圆底烧瓶中。用抹刀，打破聚合物切成小块。 </li><li>在一个2L烧杯球菌pped有磁性搅拌棒，加入750毫升乙酸乙酯。聚合物块加入到剧烈搅拌下的乙酸乙酯中。继续搅拌2小时。 </li><li>过滤过配备有纸过滤器（413级，直径15厘米）15厘米直径的布氏漏斗将溶液。 </li><li>洗用乙酸乙酯聚合物萃取三次（500毫升，每次洗涤）。干烤箱12小时设定在50℃的真空中的聚合物（123克，9.4×10 -1摩尔，产率= 41％）。 </li></ol></li></ol> 2. PNBE制备（乙烯基） <ol><li> NBE的聚合（乙烯基） <ol><li>脱气甲苯（ 约 200毫升）和NBE（乙烯基）（ 约 200毫升）与N 2鼓泡30分钟，并放置在一个手套箱中。 </li><li>内的手套箱，负载甲苯（100克）的250毫升圆底烧瓶中。 </li><li>中添加Pd 2（DBA）3（76毫克，1.6×10 -1毫摩尔，钯的1当量），AgSbF 6（68毫克，2.0×10 -1米摩尔，1.2当量）和三苯基膦，PPH 3（43毫克，1.6×10 -1毫摩尔，1当量）先后向甲苯溶液。 </li><li>将混合物加热至70℃直至完全溶解发生。它发生在10分钟内。 </li><li> NBE（乙烯基）将100克（8.0×10 -1摩尔，5000当量）添加到该紫色溶液。 </li><li>搅拌在70℃下72小时。 </li><li>除去从手套箱的溶液中，将粘性黑色溶液转移到含磁性搅拌棒的1L玻璃瓶中。 </li><li>添加甲苯（200毫升），并搅拌。 </li><li>添加二氧化硅粉末（硅胶40-63微米，10克）。在室温下搅拌16小时。 </li><li>停止搅拌并让粉末沉降至少2小时，以使二氧化硅粒子到sedimentate。 </li><li>过滤过配备有纸过滤器（413级，直径15厘米）15厘米直径的布氏漏斗将溶液。避免在布氏漏斗浇沉淀二氧化硅颗粒。 </li><li>冲洗二氧化硅相提并论用甲苯（50毫升）ticles并通过布氏漏斗过滤。 </li><li>添加甲醇（1.2L），以装备有磁性搅拌棒的4升烧杯中。 </li><li>添加所有含逐渐下剧烈搅拌聚合物与甲醇的甲苯溶液，并继续搅拌30分钟。 </li><li>过滤过配备有纸过滤器（413级，直径15厘米）15厘米直径的布氏漏斗的聚合物。用甲醇三个等份（400毫升每）洗涤聚合物。改变每次洗涤之间的滤纸。 </li><li>评估通过1 H NMR测定的聚合物的纯度在CDCl 3中，以查看是否残留单体存在（6.0和6.3 ppm的之间的双键信号）。 15，16如果是这样的情况下，继续用甲醇洗涤。 </li><li>干，在室温下真空聚合物（75克，6.3×10 -1摩尔，产率= 78％）中过夜。 </li></ol></li></ol> 3。PNBE的制备（环氧树脂） <ol><li> PNBE的环氧化（乙烯） <ol><li> 150克二氯甲烷添加到配备有磁力搅拌器和冷凝器的500mL圆底烧瓶中。 </li><li>搅拌直至完全溶解添加PNBE（乙烯基）（15克，1.3×10 -1摩尔，1当量）。 </li><li>放置烧瓶在冰浴中，让其冷却15分钟。 </li><li>在一个单独的容器中，混合在一起甲酸（30克，6.5×10 -1摩尔，5当量）和乙酸（5克，8.3×10 -2摩尔，0.6当量）。将合并的酸加入到聚合物溶液中。 </li><li>让它冷却15分钟。 </li><li>添加过氧化氢水溶液（30％）（75克，6.5×10 -1摩尔，5当量）在聚合物溶液中。 </li><li>搅拌18小时。冰浴并不需要被去除，随着温度将逐渐增加至室温。 </li><li>取少量样品，沉淀用丙酮聚合物，并通过1 H NMR中的CD分析它<html> CL 3。 15如果为双键（δ= 4.5-6.0 ppm的）的信号被充分地降低（ 图3），传递给下一个步骤。典型地，该双键的其他质子的积分的比小于1:20（1:83在图3中）。否则，继续反应。 </li><li>添加丙酮（750毫升）到配有磁搅拌棒的4升烧杯中。 </li><li>添加聚合物溶液逐渐丙酮在剧烈搅拌下15分钟。 </li><li>过滤过配备有纸过滤器（413级，直径15厘米）15厘米直径的布氏漏斗的聚合物。 </li><li>用丙酮（每次200毫升）洗涤聚合物的四倍。 </li><li>改变每次洗涤之间的滤纸。 </li><li>干，在室温下真空聚合物7.5克过夜。 </li></ol></li></ol><html> G"/&gt; 图2:粗（顶部）和纯化（底部）NBE（CO 2 H）。1 H NMR光谱。纯化的产物通过简单的蒸馏获得。请注意这是用来评估远藤峰:外型比。 <a href="http://ecsource.jove.com/files/ftp_upload/54552/54552fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图3" src="/files/ftp_upload/54552/54552fig3.jpg" /> 图3:PNBE（乙烯基）（蓝色）和PNBE（环氧基）（红色）的1 H NMR谱。注意比1:乙烯基（δ= 4.5-6.0 ppm的）在PNBE（乙烯基）光谱的积分和其它质子间3。用H 2 O 2的反应后，该比率降低至1:83，从而确认乙烯基的该环氧化已发生。NK"&gt;点击此处查看该图的放大版本。 <img alt="图4" src="/files/ftp_upload/54552/54552fig4.jpg" /> 图4:衰减全反射模式下采集红外光谱PNBE（乙烯）（黑色）和PNBE（环氧树脂）的。将显示PNBE（乙烯）和PNBE（环氧树脂）的特征峰的变焦。 902 -1 992 -1带对应于C = CH外的面外弯曲，而875 -1频带对应于环氧化物环变形。 <a href="http://ecsource.jove.com/files/ftp_upload/54552/54552fig4large.jpg" target="_blank">请点击此处查看该图的放大版本。</a>

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作者什么都没有透露。

这里提出的方法简单，易于成规模。因为没有任何纯化接收可以使用的所有化学品。注意，由于在处理和收集期间材料的不可避免的损失进行在较低的比例反应（ 如磅秤≤1G）通常会产生低的产率。 在商业钯化合物与阳离子化剂的反应而原位形成的催化剂。在我们手中，该反应的产率，以及该聚合物的特性（ 如分子量分布）没有改变一个人是否具有良好?...

降冰片烯，NBE，乙烯和环戊二烯（以双环戊二烯（DCPD）的"裂化"获得的）的狄尔斯-阿德耳加成物，是用任一自由基聚合，1阳离子聚合，2开环复分解聚合3和催化插入容易聚合聚合。 4，5，6，7不同于其他机制，催化插入聚合导致形成非常高的玻璃化转变温度的（T G）聚合物，由此NBE的双环骨架是保守的。各种催化剂，如金属茂催化剂和后过渡金属催化剂，可以使用促进NBE的聚合。 4，5，6， <suP类="外部参照"&gt; 7然而，由于它的低溶解度，并且由于具有非常高的Tg的聚合物的加工有关的困难，所述PNBE均聚物，就我们所知，从未发现的任何用途。 功能冰片烯（PNBEs）已经相当审查的对象为过去20年来，因为他们结合的双环刚性重复单元以及由它们的功能赋予期望的性能赋予高的Tg。 8，9，10 NBE单体选自相当简单和廉价的原料制得，用环戊二烯和官能化亲二烯体之间一步法Diels-Alder反应。然而，Diels-Alder反应导致两种立体异构体， 内和外 ，它们具有非常不同的反应性。 11,12实际上， 内切立体声异构体比外形式减少被动反应，使催化剂失活。 11,12因此，在过去，功能降冰片烯的制备通常需要的内和外的立体异构体的分离，并仅使用外立体异构体。这种分离程序是耗时的，并导致未反应的内切立体不可取废物的积累。 最近我们已经表明，含有两种立体异构体官能NBEs的聚合实际上是可行的。 13我们就此能够制备各种取代的PNBEs的，含有官能团如酯，酸酐，醛，酰亚胺，醇类和双键。由于它们的高的Tg和功能，这些聚合物显示出理想的性质。我们在这里描述的两种方法来制备功能性聚合物。第一个通向水溶性聚合物聚（5-降冰片烯-2-羧酸）的合成中，PNBE（CO 2 H），使用阳离子钯催化剂（ 图1）。 13，14相同的聚合方法可用于制备具有各种挂件官能团，如酯，醇，酰亚胺，溴烷基，醛和酸酐官能PNBEs。在我们手中，这种阳离子钯催化剂不能用于含有侧链双键如5-乙烯基-2-降冰片烯NBEs。在这种情况下，在聚合过程中吊灯双键的一个部分插入导致交联的材料的形成。因此，我们在这里提出专用于形成聚（5-乙烯基-2-降冰片烯），PNBE（乙烯），采用钯2（DBA）3的第二方法:AgSbF 6:PPH 3作为原位催化剂。 14聚合物的侧链乙烯基基团随后进一步环氧化，导致第Ë形成PNBE（环氧树脂）（ 图1）。无论PNBE（CO 2 H）和PNBE（环氧树脂）已发现导致形成热固性树脂的用的Tg高达350℃。 14因此，这里所描述的简单的方法允许人们有效地具有非常高的Tg和具有各种官能团，其可用于多种应用的制备聚合物。 <img alt="图1" src="/files/ftp_upload/54552/54552fig1.jpg" /> 图1:由钯制得的官能PNBEs催化聚合。 （A）PNBE（CO 2 H）的准备，（B）准备PNBE（乙烯）和PNBE（环氧树脂）。虚线键表示内型和外型异构体的混合物。 <a href="http://ecsource.jove.com/files/ftp_upload/54552/54552fig1large.jpg" target="_blank">请点击此处查看该网络的放大版本</a>古尔。

<table><tbody><tr><td>acrylic acid</td><td>Sigma-Aldrich</td><td>147230</td><td></td></tr><tr><td>hydroquinone</td><td>Sigma-Aldrich</td><td>H9003</td><td></td></tr><tr><td>dicyclopendadiene</td><td>Sigma-Aldrich</td><td>454338</td><td></td></tr><tr><td>palladium allyl dichloride dimer</td><td>Sigma-Aldrich</td><td>222380</td><td></td></tr><tr><td>silver hexfluoro antimonate</td><td>Sigma-Aldrich</td><td>227730</td><td></td></tr><tr><td>liquid nitrogen</td><td>Local Facility</td><td>NA</td><td></td></tr><tr><td>ethyl acetate</td><td>Fischer Scientific</td><td>E14520</td><td></td></tr><tr><td>5-vinyl-2-norbornene</td><td>Sigma-Aldrich</td><td>148679</td><td></td></tr><tr><td>toluene</td><td>Fischer Scientific</td><td>T290-4</td><td></td></tr><tr><td>palladium dba</td><td>Sigma-Aldrich</td><td>227994</td><td></td></tr><tr><td>triphenyl phosphine</td><td>Sigma-Aldrich</td><td>93090</td><td></td></tr><tr><td>silica gel 40-63 microns</td><td>Silicycle</td><td>Siliaflash</td><td></td></tr><tr><td>methanol</td><td>Fischer Scientific</td><td>BPA412-20</td><td></td></tr><tr><td>dichloromethane</td><td>EMD Millipore</td><td>DX08311</td><td></td></tr><tr><td>formic acid</td><td>Sigma-Aldrich</td><td>F0507</td><td></td></tr><tr><td>acetic acid</td><td>Sigma-Aldrich</td><td>320099</td><td></td></tr><tr><td>hydrogen peroxide solution</td><td>Sigma-Aldrich</td><td>216763</td><td></td></tr><tr><td>acetone</td><td>Fischer Scientific</td><td>A18-200</td><td></td></tr></tbody></table>

a simple and efficient protocol for the catalytic insertion polymerization of functional norbornenes

降冰片烯可以通过多种机制，包括插入聚合由此双键聚合和单体的双环性质是保守的聚合。所得到的聚合物，降冰片烯，具有非常高的玻璃化转变温度，T g，且有趣的光学和电学性能。然而，功能降冰片烯的由该机构的聚合是通过该内型取代的降冰片烯单体有，在一般情况下，非常低的反应性的事实而复杂化。此外，来自外单体的内型取代的单体的分离是一项乏味的任务。在这里，我们提出了一个简单的协议，用于取代降冰片烯聚合:轴承无论是羧酸或吊坠双键（ 内 约 外 80:20）。该过程不要求两种异构体中分离出来，并用低催化剂负载量（0.01至0.02摩尔％）进行。聚合物轴承挂起蚂蚁双键可以以高收率进一步转化，以得到聚合物轴承环氧侧基。这些简单的程序可以应用于具有各种官能团，如酯，醇，酰亚胺，双键，羧酸，溴烷基，醛和酸酐的制备降冰片烯。

的NBE单体通过的DCPD的简单Diels-Alder反应和合适的亲二烯体，例如丙烯酸（AA）来制备。通常情况下，DCPD被破解的反应之前，产生环戊二烯（CPD）。然后17破获新鲜CPD从事Diels-Alder反应。然而，在该协议中，都伴随执行既裂化和狄尔斯 - 阿德耳步骤，在单罐反应。因此，只要形成的CPD，其与AA反应以得到5-降冰片烯-2-羧酸，NBE（CO 2 H）（ 图1A）?...

Watch this Scientific Journal Video about A Simple and Efficient Protocol for the Catalytic Insertion Polymerization of Functional Norbornenes at JoVE.com

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

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 ...

a-simple-efficient-protocol-for-catalytic-insertion-polymerization

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10.3K 次观看.  Université de Sherbrooke. 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. 

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

Particles without a Box: Brush-first Synthesis of Photodegradable PEG Star Polymers under Ambient Conditions

Convenient methods for the rapid, parallel synthesis of diversely functionalized nanoparticles will enable discovery of novel formulations for drug delivery, biological imaging, and supported catalysis. In this report, we demonstrate parallel synthesis of brush-arm star polymer (BASP) nanoparticles by the &#34;brush-first&#34; method. In this method, a norbornene-terminated poly(ethylene glycol) (PEG) macromonomer (PEG-MM) is first polymerized via ring-opening metathesis polymerization (ROMP) to generate a living brush macroinitiator. Aliquots of this initiator stock solution are added to vials that contain varied amounts of a photodegradable bis-norbornene crosslinker. Exposure to crosslinker initiates a series of kinetically-controlled brush+brush and star+star coupling reactions that ultimately yields BASPs with cores comprised of the crosslinker and coronas comprised of PEG. The final BASP size depends on the amount of crosslinker added. We carry out the synthesis of three BASPs on the benchtop with no special precautions to remove air and moisture. The samples are characterized by gel permeation chromatography (GPC); results agreed closely with our previous report that utilized inert (glovebox) conditions. Key practical features, advantages, and potential disadvantages of the brush-first method are discussed.

Poly(ethylene glycol) (PEG) brush-arm star polymers (BASPs) with narrow mass distributions and tunable nanoscopic sizes are synthesized in via ring opening metathesis polymerization (ROMP) of a PEG-norbornene macromonomer followed by transfer of portions of the resulting living brush initiator to vials containing varied amounts of a rigid, photo-cleavable bis-norbornene crosslinker.

颗粒无箱：可光降解的PEG星形聚合物在环境条件刷第一个合成

Convenient methods for the rapid, parallel synthesis of diversely functionalized nanoparticles will enable discovery of novel formulations for drug ...

科研

化学

Microwave-assisted Functionalization of Poly(ethylene glycol) and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation

One of the main benefits to using poly(ethylene glycol) (PEG) macromers in hydrogel formation is synthetic versatility. The ability to draw from a large variety of PEG molecular weights and configurations (arm number, arm length, and branching pattern) affords researchers tight control over resulting hydrogel structures and properties, including Young&#8217;s modulus and mesh size. This video will illustrate a rapid, efficient, solvent-free, microwave-assisted method to methacrylate PEG precursors into poly(ethylene glycol) dimethacrylate (PEGDM). This synthetic method provides much-needed starting materials for applications in drug delivery and regenerative medicine. The demonstrated method is superior to traditional methacrylation methods as it is significantly faster and simpler, as well as more economical and environmentally friendly, using smaller amounts of reagents and solvents. We will also demonstrate an adaptation of this technique for on-resin methacrylamide functionalization of peptides. This on-resin method allows the N-terminus of peptides to be functionalized with methacrylamide groups prior to deprotection and cleavage from resin. This allows for selective addition of methacrylamide groups to the N-termini of the peptides while amino acids with reactive side groups (e.g.&#160;primary amine of lysine, primary alcohol of serine, secondary alcohols of threonine, and phenol of tyrosine) remain protected, preventing functionalization at multiple sites. This article will detail common analytical methods (proton Nuclear Magnetic Resonance spectroscopy (;H-NMR) and Matrix Assisted Laser Desorption Ionization Time of Flight mass spectrometry (MALDI-ToF)) to assess the efficiency of the functionalizations. Common pitfalls and suggested troubleshooting methods will be addressed, as will modifications of the technique which can be used to further tune macromer functionality and resulting hydrogel physical and chemical properties. Use of synthesized products for the formation of hydrogels for drug delivery and cell-material interaction studies will be demonstrated, with particular attention paid to modifying hydrogel composition to affect mesh size, controlling hydrogel stiffness and drug release.

Microwave-assisted Functionalization of Polyethylene glycol and On-resin Peptides for Use in Chain Polymerizations and Hydrogel Formation

This video will illustrate a rapid, efficient method to methacrylate poly(ethylene glycol), enabling chain polymerizations and hydrogel synthesis. It will demonstrate how to similarly introduce methacrylamide functionalities into peptides, detail common analytical methods to assess functionalization efficiency, provide suggestions for troubleshooting and advanced modifications, and demonstrate typical hydrogel characterization techniques.

保利的微波辅助功能化（乙二醇）和On-树脂链聚合反应，并形成水凝胶的肽使用

One of the main benefits to using poly(ethylene glycol) (PEG) macromers in hydrogel formation is synthetic versatility. The ability to draw from a large ...

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium Under Mild Reaction Conditions

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family of easy accessible, very cheap, and air stable, but highly active and universally applicable C-C cross-coupling catalysts with an excellent functional group tolerance. Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1), the least stable complex within this series towards protons; e.g. in the form of water, allows an eased nanoparticle formation and hence, proved to be the most active Heck catalyst within this series at 100 &#176;C and is a very rare example of an effective and versatile catalyst system that efficiently operates under mild reaction conditions. Rapid and complete catalyst degradation under work-up conditions into phosphonates, piperidinium salts and other, palladium-containing decomposition products assure an easy separation of the coupling products from catalyst and ligands. The facile, cheap, and rapid synthesis of 1,1',1"-(phosphinetriyl)tripiperidine and 1 respectively, the simple and convenient use as well as its excellent catalytic performance in the Heck reaction at 100 &#176;C make 1 to one of the most attractive and greenest Heck catalysts available.
We provide here the visualized protocols for the ligand and catalyst syntheses as well as the reaction protocol for Heck reactions performed at 10 mmol scale at 100 &#176;C and show that this catalyst is suitable for its use in organic syntheses.

Mizoroki-Heck Cross-coupling Reactions Catalyzed by Dichloro{bis[1,1',1''-phosphinetriyltripiperidine]}palladium Under Mild Reaction Conditions

Dichloro{bis[1,1',1''-(phosphinetriyl)tripiperidine]}palladium [(P(NC5H10)3)2Pd(Cl)2] (1) is an easy accessible, cheap, and air stable, but highly active Heck catalyst with an excellent functional group tolerance that efficiently operates under mild reaction conditions to give the coupling products in very high yields.

Mizoroki-哎呀交叉偶联反应由二氯{双[1,1&#39;，1&#39;&#39;  - （phosphinetriyl）tripiperidine]}钯催化在温和的反应条件

Dichloro-bis(aminophosphine) complexes of palladium with the general formula of [(P{(NC5H10)3-n(C6H11)n})2Pd(Cl)2] (where n = 0-2), belong to a new family ...

Ethylene Polymerizations Using Parallel Pressure Reactors and a Kinetic Analysis of Chain Transfer Polymerization

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel &#945;-diimine ethylene polymerization catalyst. Initial polymerizations with the catalyst lead to optimized reaction conditions, including catalyst concentration, ethylene pressure and reaction time. Using gas-uptake data for these reactions, a procedure to calculate the initial rate of propagation (kp) is presented. Using the optimized conditions, the ability of the nickel &#945;-diimine polymerization catalyst to undergo chain transfer with diethylzinc (ZnEt2) during ethylene polymerization was investigated. A procedure to assess the ability of the catalyst to undergo chain transfer (from molecular weight and 13C NMR data), calculate the degree of chain transfer, and calculate chain transfer rates (ke) is presented.

A protocol for the high-throughput analysis of polymerization catalyst, chain transfer polymerizations, polyethylene characterization, and reaction kinetic analysis is presented.

乙烯聚合中使用并联电抗器的压力和链转移聚合的动力学分析

We demonstrate a method for high-throughput catalyst screening using a parallel pressure reactor starting from the initial synthesis of a nickel ...

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, allowing for the synthesis of isotactic poly(&#945;-hydroxy acids) with expected molecular weights (&#62;140 kDa) and narrow molecular weight distributions (Mw/Mn &#60; 1.1). This ring-opening polymerization is mediated by Ni and Zn complexes in the presence of an alcohol initiator and a photoredox Ir catalyst, irradiated by a blue LED (400 - 500 nm). The polymerization is performed at a low temperature (-15 &#176;C) to avoid undesired side reactions. The complete monomer consumption can be achieved within 4 - 8 hours, providing a polymer close to the expected molecular weight with narrow molecular weight distribution. The resulted number-average molecular weight shows a linear correlation with the degree of polymerization up to 1000. The homodecoupling 1H NMR study confirms that the obtained polymer is isotactic without epimerization. This polymerization reported herein offers a strategy for achieving rapid, controlled O-carboxyanhydrides polymerization to prepare stereoregular poly(&#945;-hydroxy acids) and its copolymers bearing various functional side-chain groups.

Controlled Photoredox Ring-Opening Polymerization of O-Carboxyanhydrides Mediated by Ni/Zn Complexes

A protocol for the controlled photoredox ring-opening polymerization of O-carboxyanhydrides mediated by Ni/Zn complexes is presented.

镍/锌配合物介导的O-Carboxyanhydrides 的控制 Photoredox 环开聚合

Here, we describe an effective protocol that combines photoredox Ni/Ir catalysis with the use of a Zn-alkoxide for efficient ring-opening polymerization, ...

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes and determine the corresponding photochemical mechanism. Then, we describe a protocol to perform ring-opening metathesis polymerization (ROMP) in solution and in miniemulsion using this NHC-photogenerating system. To photogenerate IMes, a system comprising 2-isopropylthioxanthone (ITX) as the sensitizer and 1,3-dimesitylimidazolium tetraphenylborate (IMesH+BPh4-) as the protected form of NHC is employed. IMesH+BPh4- can be obtained in a single step by anion exchange between 1,3-dimesitylimidazolium chloride and sodium tetraphenylborate. A real-time steady-state photolysis setup is described, which hints that the photochemical reaction proceeds in two consecutive steps: 1) ITX triplet is photo-reduced by the borate anion and 2) subsequent proton transfer takes place from the imidazolium cation to produce the expected NHC IMes. Two separate characterization protocols are implemented. Firstly, CS2 is added to the reaction media to evidence the photogeneration of NHC through formation of the IMes-CS2 adduct. Secondly, the amount of NHC released in situ is quantified using acid-base titration. The use of this NHC photo-generating system for the ROMP of norbornene is also discussed. In solution, a photopolymerization experiment is conducted by mixing ITX, IMesH+BPh4-, [RuCl2(p-cymene)]2 and norbornene in CH2Cl2, then irradiating the solution in a UV reactor. In a dispersed medium, a monomer miniemulsion is first formed then irradiated inside an annular reactor to produce a stable poly(norbornene) latex.

We describe a protocol to photogenerate N-heterocyclic carbenes (NHCs) by UV irradiation of a 2-isopropylthioxanthone/imidazolium tetraphenylborate salt system. Methods to characterize the photoreleased NHC and elucidate the photochemical mechanism are proposed. The protocols for ring-opening metathesis photopolymerization in solution and miniemulsion illustrate the potential of this 2-component NHC photogenerating system.

n-杂环卡本的光生成在光致环开环转移聚合中的应用

We report a method to generate the N-heterocyclic carbene (NHC) 1,3-dimesitylimidazol-2-ylidene (IMes) under UV-irradiation at 365 nm to characterize IMes ...

Depolymerizable Olefinic Polymers Based on Fused-Ring Cyclooctene Monomers

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. Achieving a closed-loop polymer economy via chemical recycling to monomer (CRM) is one such promising route. Our group recently reported a new CRM system based on polymers prepared by ring-opening metathesis polymerization (ROMP) of trans-cyclobutane fused cyclooctene (tCBCO) monomers. This system offers several key advantages, including the ease of polymerization at ambient temperatures, quantitative depolymerization to monomers under mild conditions, and a broad range of functionalities and thermomechanical properties. Here, we outline detailed protocols for the preparation of tCBCO-based monomers and their corresponding polymers, including the preparation of elastic polymer networks and compression molding of linear thermoplastic polymers. We also outline the preparation of high ring strain E-alkene tCBCO monomers and their living polymerization. Finally, the procedures for the depolymerization of linear polymers and polymer networks are also demonstrated.

Here, we describe protocols for the preparation of trans-cyclobutane fused cyclooctenes (tCBCO),&#160;their polymerization to prepare depolymerizable olefinic polymers, and the depolymerization of these polymers under mild conditions. Additionally, protocols for the preparation of depolymerizable networks and compression molding of rigid linear plastics based on this system are described.

基于熔环环辛烯单体的可解聚烯烃聚合物

The growing consumption of synthetic polymers and the accumulation of polymer waste have led to a pressing need for new routes to sustainable materials. ...

Controlling Particle Fraction in Microporous Annealed Particle Scaffolds for 3D Cell Culture

Microgels are the building blocks of microporous annealed particle (MAP) scaffolds, which serve as a platform for both in vitro cell culture and in vivo tissue repair. In these granular scaffolds, the innate porosity generated by the void space between microgels enables cell infiltration and migration. Controlling the void fraction and particle fraction is critical for MAP scaffold design, as porosity is a bioactive cue for cells. Spherical microgels can be generated on a microfluidic device for controlled size and shape and subsequently freeze-dried using methods that prevent fracturing of the polymer network. Upon rehydration, the lyophilized microgels lead to controlled particle fractions in MAP scaffolds. The implementation of these methods for microgel lyophilization has led to reproducible studies showing the effect of particle fraction on macromolecule diffusion and cell spreading. The following protocol will cover the fabrication, lyophilization, and rehydration of microgels for controlling particle fraction in MAP scaffolds, as well as annealing the microgels through bio-orthogonal crosslinking for 3D cell culture in vitro.

Minimizing the variability in the particle fraction within granular scaffolds facilitates reproducible experimentation. This work describes methods for generating granular scaffolds with controlled particle fractions for in vitro tissue engineering applications.

控制用于3D细胞培养的微孔退火颗粒支架中的颗粒分数

Microgels are the building blocks of microporous annealed particle (MAP) scaffolds, which serve as a platform for both in vitro cell culture and in vivo ...

生物工程

Cationic Chain-Growth Polymerization: Mechanism

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization process, the &#960; bond of a monomer gets protonated by the Lewis acid catalyst, which is formed from boron trifluoride and water. The protonation of the &#960; bond generates a carbocation stabilized by the electron&#8208;donating group. In the propagation step, the &#960; bond of the second monomer acts as a nucleophile and attacks the generated carbocation, thereby producing a dimer that acts as a new carbocation. The propagation step repeats itself and builds the polymer chain. In the termination step, the propagating chain gets terminated either by adding a base that deprotonates the carbocation and forms a new &#960; bond or by the attack of a nucleophile on the carbocation, where the nucleophile adds to the cationic end of the chain.

阳离子链生长聚合:机理

The cationic polymerization mechanism consists of three steps: initiation, propagation, and termination. In the initiation step of the polymerization ...

教育

有机化学

Unit 1

Synthetic Polymers

关键术语与概念

Ziegler&ndash;Natta Chain-Growth Polymerization: Overview

Ziegler&#8211;Natta polymerization is another form of addition or chain&#8208;growth polymerization used for synthesizing linear polymers over branched polymers. The catalyst used for polymerization is the Ziegler&#8211;Natta catalyst, named after Karl Ziegler and Giulio Natta, who developed it in 1953. This catalyst is an organometallic complex of titanium tetrachloride and triethyl aluminum, with the active form of the catalyst being an alkyl titanium compound. Using the Ziegler&#8211;Natta catalyst, high molecular weight and stereochemically controlled linear polymers can be synthesized at a large scale. For example, high molecular weight and ultrahigh molecular weight polyethylene, used for making underground pipes and bulletproof vests, are synthesized using the Ziegler&#8211;Natta catalyst. This catalyst also facilitates the synthesis of polymers of specific tacticity. For instance, isotactic&#160;polypropylene, with chiral centers on the same side, can be synthesized using a specific Ziegler&#8211;Natta catalyst.

Ziegler&amp;#8211;Natta Chain-Growth Polymerization: Overview

Ziegler-Natta 链生长聚合:概述

Ziegler&#8211;Natta polymerization is another form of addition or chain&#8208;growth polymerization used for synthesizing linear polymers over branched ...