Name: synthesis of terpolymers at mild temperatures using dynamic sulfur bonds in poly(s-divinylbenzene)
Uploaded: 2019-05-20T15:00:00
Description: Watch this Scientific Journal Video about Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene at JoVE.com

感谢美国化学学会石油研究基金 (PRF # 58416-uni7) 的财政支持。

1. 聚 (s-二乙烯基苯) 的合成
<ol><li>制备聚 (s-二乙烯基苯)、元素硫 (S8) 和二乙烯基苯 (DVB) 在不同的重量比 (30:70, 40:60, 50:50, 60:40, 70:30, 80:20, 和 90:10 s8:D vb)。根据以下3,25所述的事先方法准备反应。 注: 这里的所有反应都是在1.00 克的范围内进行的。一个典型的反应包含500毫克的 S8和500毫克的 DVB。<ol>
<li>将试剂放入装有磁性搅拌...

<ol>
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该方法的主要优点是能够在温和的温度下形成聚硫化物, 在90°c 相对于 Gt;159 的温度下形成传统的逆硫化。聚 (s-dvb) 中的扩展硫链和硫循环的稳定性低于 s8-23、26中的 s-s 键。较低的温度可用于引起共溶裂解和硫基自由基形成24。对于熔点远低于反应温度的单体, 仍然可以在不需要溶剂的情况下完成。用 1, 4-环己二醇甲醇 CDE、CVE ?...

在石油提炼过程中将有机硫化合物转化为 s8 导致大量硫库存1的积累. 元素硫主要用于生产肥料用硫酸和磷酸盐 2.相对丰度提供了一种现成且价格低廉的试剂, 使元素硫成为材料开发的理想原料。
反向硫化是一种相对较新的聚合技术, 它将硫转化为功能材料3。在159°c 以上加热时,s8环转换为二元基的线性链。然后, 硫基自由基开始与单体聚合, 形成聚硫化物3。除了传统的自由基聚合外, 还利用逆硫化与苯并恶嗪4进行聚合。由此产生的聚合物已被广泛用于各种应用, 包括锂电池1、5、6、7、自愈光学镜头8、9 中的阴极, 汞和油吸附剂 5,10,11,12, 13, 14, 15,热绝缘体15, 以帮助化肥的缓释16以及显示出一些抗菌活性17。一个小组对这些聚硫化物进行了深入的系统分析, 提供了更多关于不同 S 含量18的绝缘特性和机械性能的信息。具体细节可能有助于进一步的应用程序开发。这些材料中存在的动态键也被用来回收改性聚硫化物 19,20。然而, 逆硫化所需的高温 (通常为 185°c) 和与 S8 的相容性不足, 限制了可使用的单体 3.
早期的工作重点是芳烃、扩展烃和高沸点的天然单体的聚合5。利用聚 (s-苯乙烯) 作为预聚物, 提高了 s8和更多极性单体 (包括丙烯酸、烯丙基和功能化苯乙烯单体21) 之间的相容性, 从而扩大了这些方法。另一种方法是利用亲核胺激活剂来提高反应速率和降低反应温度22。然而, 许多单体的沸点远低于 159°c, 因此需要一种替代方法来形成聚硫化物。
在稳定的冠状形式中, S-S 键是最强的, 因此需要高温为裂解23.在聚硫化物中, 硫作为线性链或循环存在, 使 s-s 键在较低的温度1,24下被切割。通过使用聚 (s-dvb) (DVB, 二乙烯基苯) 作为预聚物, 可以引入具有较低沸点的第二单体, 如 1, 4-环己二醇二聚醚 (CDE, 沸点为 126°C), 可以引入24。这项工作表明进一步改善的反应温度降低到90°c 与系列烯丙基和乙烯基醚单体。含有第二单体的反应仍然是无溶剂的。

<table>
	<tbody>
		<tr>
			<td>Sulfur, 99.5%, sublimed, ACROS Organics</td>
			<td>Fisher Scientific</td>
			<td>AC201250250SDS</td>
			<td></td>
		</tr>
		<tr>
			<td>divinylbenzene</td>
			<td>Fisher Scientific</td>
			<td>AA4280422</td>
			<td></td>
		</tr>
		<tr>
			<td>1,4-Cyclohexanedimethanol divinyl ether, mixture of isomers</td>
			<td>Sigma Aldrich</td>
			<td>406171</td>
			<td></td>
		</tr>
		<tr>
			<td>Cyclohexyl vinyl ether</td>
			<td>Fisher Scientific</td>
			<td>AC395420500</td>
			<td></td>
		</tr>
		<tr>
			<td>Allyl ether</td>
			<td>Sigma Aldrich</td>
			<td>259470</td>
			<td></td>
		</tr>
		<tr>
			<td>maleimide</td>
			<td>Sigma Aldrich</td>
			<td>129585</td>
			<td></td>
		</tr>
		<tr>
			<td>dichlormethane</td>
			<td>Fisher Scientific</td>
			<td>D37</td>
			<td></td>
		</tr>
		<tr>
			<td>N,N-dimethylformamide</td>
			<td>Fisher Scientific</td>
			<td>D119</td>
			<td></td>
		</tr>
		<tr>
			<td>Auto sampler Aluminum Sample Pans, 50&#181;L, 0.1mm, Sealed</td>
			<td>Perkin Elmer</td>
			<td>B0143017</td>
			<td></td>
		</tr>
		<tr>
			<td>Auto sampler Aluminum Sample Covers</td>
			<td>Perkin Elmer</td>
			<td>B0143003</td>
			<td></td>
		</tr>
		<tr>
			<td>EMD Millipore 13mm Nonsterile Millex Syringe Filters - Hydrophobic PTFE Membrane, 0.45 um</td>
			<td>Fisher Scientific</td>
			<td>SLFHX13NL</td>
			<td></td>
		</tr>
	</tbody>
</table>

synthesis of terpolymers at mild temperatures using dynamic sulfur bonds in poly(s-divinylbenzene)

元素硫 (S8) 是石油工业的副产品, 年产量达数百万吨。如此丰富的生产和有限的应用导致硫作为聚合物合成的经济高效的试剂。反向硫化结合元素硫和各种单体, 形成功能性聚硫化物, 无需溶剂。反应时间短, 合成方法直接, 导致逆硫化迅速膨胀。然而, 高反应温度 (和 gt;160 °c) 限制了可以使用的单体类型。在这里, 聚 (s-二乙烯基苯) 中的动态硫键被用来在更低的温度下引发聚合。预聚物中的 S-S 键比 s8 中的 S-S 键稳定, 允许在90°c 而不是159°c 时形成自由基。各种烯丙基和乙烯基醚已被结合形成三聚体。所得到的材料采用1h 核磁共振、凝胶渗透色谱、差示扫描量热法以及检测溶解度变化的方法进行了表征。该方法扩展了逆硫化利用的无溶剂、硫基自由基化学, 在温和的温度下产生了聚硫化物。这一发展扩大了可合并的单体的范围, 从而扩大了可访问的材料特性和可能的应用。

根据已发布的协议, 利用高温 (185°c) 合成了 poly (S-DVB), 以启动s8环裂解形成自由基3。这些自由基然后启动与 DVB 聚合。熔融硫磺和液体 DVB 消除了对溶剂的需求。在30分钟内, 硫磺和 DVB 完全反应形成聚 (S-DVB)。从小瓶中去除后, 聚合物是一种硬性、易碎的材料, 含硫量较低 (30-40)。中端硫含量 (50-60)生产出具有可塑性和较高含硫量 (70-90%) 的俗气材料?...

Watch this Scientific Journal Video about Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene at JoVE.com

Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in PolyS-Divinylbenzene

该协议的目的是在温和的温度 (90°c) 下, 在温和的温度 (90°c) 下, 使用聚 (s-二乙烯基苯) 中的动态硫键进行聚合, 而无需使用溶剂。三聚体的特征是 GPC、DSC 和1h 核磁共振, 并测试了溶解度的变化。

在高温下利用聚苯 (s-二硝基苯) 动态硫键合成三聚体

Elemental sulfur (S8) is a byproduct of the petroleum industry with millions of tons produced annually. Such abundant production and limited applications ...

我们开发了一种方法，在90摄氏度下使用聚（硫-二苯）中的动态硫键启动聚合，无需溶剂。这大大低于要求温度超过160摄氏度的传统方法。降低聚合温度可扩大单体的范围，通过反向硫化可以融入多硫化物。这扩展了可能的材料属性和可能的应用。反向硫化产生了用于硫化锂电池的聚硫化物，如红外透明透镜，如汞和油吸附剂等应用。这种方法将支持新材料的开发和可能的其他应用。这种方法的主要优点之一是合成的相对容易性。此视频提供了一个机会，以演示反应如何随着时间的推移，以及演示聚合物可以根据硫含量和存在的单体的比例变化多少。在装有磁性搅拌棒的一干菌瓶中，以所需的重量比准备聚（S-二苯）元素硫和二苯。将小瓶放在185摄氏度的油浴中，30分钟。反应完成后，从油浴中取出小瓶，立即将小瓶放入液氮中淬火。然后打破打开小瓶去除聚合物，并重复此步骤，为每个聚合物准备。要合成三聚体，首先用砂浆粉碎聚体（S-二苯），使其表面面积与单体1、4-Cyclohexanedmethanol二乙醚或CDE相互作用。然后在600毫克的尺度上以所需的重量比结合聚（S-二苯）和CDE。将样品在 90 摄氏度的油浴中放置 24 小时。然后将样品冷却至室温。对于不导致完全单体结合的反应，将可溶性聚合物部分溶解在二氯甲烷中，并在冷甲醇中沉淀。对于溶解度有限的样品，用冷甲醇清洗固体聚合物样品，以去除任何未反应的单体。要使用马莱米胺合成三聚酯，请将硫和二苯结合在 30-70 重量比下，如前所述，比例为 5 克。在装有磁力搅拌棒的一干玻璃瓶中，以三比一的重量比将预聚合物与马莱米德结合。将混合物溶解在每微升二甲基甲酰胺10毫克中。然后将小瓶放在100摄氏度的油浴中24小时。接下来，将聚（S-二苯）和所需的单体组合在一对一的重量比下，如前所述，以准备各种三聚酯。在反应过程中去除不同时间点的混合物样品，将聚合物溶解在600微升的脱化氯仿中，用于质子 NMR 分析。为了确认聚合物的硫而不是元素硫的聚合需要，请单独准备硫样品，并准备好使用CDE、二苯和甲苯乙醚，如前所述。用质子 NMR 分析脱化氯仿中的聚合物。整合产生的质子 NMR 光谱以确定反应的程度。由于大多数三聚酯的溶解度相对较低，多聚物含量高，因此以每毫升75毫克的高浓度将每种聚合物溶解在二氯甲烷中。然后使用 0.45 微米疏水过滤器清除可溶性部分的颗粒物。使用二氯甲烷作为叶绿素，按序列排列两个中索波列和一个折射率检测器，通过凝胶渗透色谱分析样品。根据聚苯乙烯标准的校准曲线确定平均数和重量平均分子量。为了研究热性能，请向铝锅中填充每聚合物 30 到 50 毫克，提供足够的样品，以充分识别由此产生的热图中的玻璃过渡温度。扫描样品，然后从第二次扫描中获取热图值。对于溶解度研究，将每种聚合物约150毫克重入预称重小瓶中，并溶解在二氯甲烷中，浓度达到每毫升75毫克。八小时后，取出可溶性部分，用二氯甲烷洗涤不溶性部分两次。将剩余的不溶性样品在烤箱中干燥10分钟，以去除剩余的溶剂。将小瓶冷却到室温后，称重小瓶，通过确定起始重量和最终重量的差异来计算溶解度百分比。聚（S-二苯）是利用高温合成的，以启动硫环裂解形成基，然后启动与二苯的聚合。聚（S-二苯）内的动态硫键可用于在低得多的温度下用额外的单体启动聚合。评价了单功能和二功能乙烯基和全醇单体，并成功聚合，经核磁共振确认。在所有聚合的单体含量在48小时内进行监测。控制反应用于确定聚（S-二苯）与硫在聚合中的作用。质子 NMR 和 TLC 对产品进行了检查，以检查聚合物结构、单体结合的变化，并确定硫是否完全结合。进行了各种聚合，以检查聚（S-二苯）CDE的聚合物结构。硫含量增加，CDE的加入导致玻璃过渡温度降低。在分子量最初减少后，CDE的加入导致链长度的整体增加。以40%至50%硫为合成的聚（二苯）达到最大溶解度。CDE 的加入导致聚合物溶解度降低。对于高硫含量聚（S-二苯苯）低溶解度，观察到，但加入CDE大大提高了溶解度。开发一种无溶剂聚合，其温度比之前报告低得多，从而扩大了可纳入多硫化物的单体范围。这可能为新的应用打开大门，或使材料更好地为所需的功能量身定做。合成聚（硫-二苯）过程中产生的少量气体，只应填充半满，以防止压力积聚。样品应在从发动机罩中去除之前通风，以确保气体不吸入。

Research

Education

JoVE Journal

JoVE Core

Organic Chemistry

Chemistry

Synthesis of Terpolymers at Mild Temperatures Using Dynamic Sulfur Bonds in Poly(S-Divinylbenzene)

Unit 1

Reactions of Alkenes

SCIENTISTS IN ACTION

Synthesis of Hypervalent Iodonium Alkynyl Triflates for the Application of Generating Cyanocarbenes

高价碘鎓炔基三氟甲磺酸酯的生成Cyanocarbenes的合成应用

The procedures described in this article involve the synthesis and isolation of hypervalent iodonium alkynyl triflates (HIATs) and their subsequent ...

科研

化学

Synthesis of Immunotargeted Magneto-plasmonic Nanoclusters

Immunotargeted的合成磁等离子团簇

Magnetic and plasmonic properties combined in a single nanoparticle provide a synergy that is advantageous in a number of biomedical applications ...

Synthesis, Characterization, and Functionalization of Hybrid Au/CdS and Au/ZnS Core/Shell Nanoparticles

合成，表征和混合金/硫化镉和Au / ZnS核/壳纳米颗粒功能化

Plasmonic nanoparticles are an attractive material for light harvesting applications due to their easily modified surface, high surface area and large ...

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

Protocol for the Synthesis of Ortho-trifluoromethoxylated Aniline Derivatives

协议的合成<em&gt;邻</em&gt; -trifluoromethoxylated苯胺类化合物

Molecules bearing trifluoromethoxy (OCF3) group often show desired pharmacological and biological properties. However, facile synthesis of ...

Synthesis of Ligand-free CdS Nanoparticles within a Sulfur Copolymer Matrix

a硫磺共聚物基质内的免费配体硫化镉纳米粒子的合成

Aliphatic ligands are typically used during the synthesis of nanoparticles to help mediate their growth in addition to operating as high-temperature ...

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

Synthesis of Protein Bioconjugates via Cysteine-maleimide Chemistry

蛋白质生物缀合物的合成<em&gt;通过</em&gt;半胱氨酸马来酰亚胺化学

The chemical linking or bioconjugation of proteins to fluorescent dyes, drugs, polymers and other proteins has a broad range of applications, such as the ...

Synthesis of Cyclic Polymers and Characterization of Their Diffusive Motion in the Melt State at the Single Molecule Level

环状聚合物的合成及其在熔融状态扩散运动的表征在单分子水平

We demonstrate a method for the synthesis of cyclic polymers and a protocol for characterizing their diffusive motion in a melt state at the single ...

Synthesis of a Water-soluble Metal&#8211;Organic Complex Array

Synthesis of a Water-soluble MetalÃƒÆ’Ã‚Â¢ÃƒÂ¢Ã¢â‚¬Å¡Ã‚Â¬ÃƒÂ¢Ã¢â€šÂ¬Ã…â€œOrganic Complex Array

一个水溶性金属 - 有机络合物阵列合成

We demonstrate a method for the synthesis of a water-soluble multimetallic peptidic array containing a predetermined sequence of metal centers such as ...

DNA-magnetic Particle Binding Analysis by Dynamic and Electrophoretic Light Scattering

动态和电泳光散射的 DNA-磁性颗粒结合分析

Isolation of DNA using magnetic particles is a field of high importance in biotechnology and molecular biology research. This protocol describes the ...

Synthesis of a Thiol Building Block for the Crystallization of a Semiconducting Gyroidal Metal-sulfur Framework

半导体回转金属硫框架结晶的硫醇构建块的合成

We present a method for preparing thioester molecules as the masked form of the thiol linkers and their utilization for accessing a semiconducting and ...