Solvent Selective Hydrogen–Deuterium Exchange on Saturated Polyolefins
Solvent Selective Hydrogen–Deuterium Exchange on Saturated Polyolefins
复制标题
饱和聚烯烃上的溶剂选择性氢-氘交换
DOI：
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
F. Bates
中科院分区：
文献类型：
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作者：
Brian M. Habersberger;T. Lodge;F. Bates
采用非均相Pt-Re/SiO2催化剂，在饱和烃溶剂十氢萘、癸烷、庚烷和异辛烷中，对线性饱和聚烯烃聚乙烯、聚（乙烯-交替-丙烯）和全同立构聚丙烯进行了H-D交换反应。在直链和支链烷烃溶剂用于聚（乙烯）和聚（乙烯-交替-丙烯）的情况下，使用氘气的交换反应对聚合物具有选择性，而在萘烷中进行的反应导致几乎没有与聚合物的同位素交换。基本上，在线性（癸烷）或支化（异辛烷）溶剂中与聚（丙烯）没有发生交换。在所有情况下，聚合物主链键未受干扰，保持分子量分布。这些结果表明，聚合物和溶剂之间的竞争吸附在聚合物的多相催化中起着重要的作用。此外，这一战略提供了一个简单而有效的方法，合成后标记选定的聚烯烃…
A heterogeneous Pt–Re/SiO2 catalyst was used to perform H–D exchange reactions on the linear saturated polyolefins poly(ethylene), poly(ethylene-alt-propylene), and isotactic poly(propylene) in the saturated hydrocarbon solvents decalin, decane, heptane, and isooctane. Exchange reactions using deuterium gas were selective toward the polymer in the case of linear and branched alkane solvents for poly(ethylene) and poly(ethylene-alt-propylene), whereas reactions conducted in decalin result in virtually no isotope exchange with the polymer. Essentially, no exchange occurred with poly(propylene) in either linear (decane) or branched (isooctane) solvents. In all cases, polymer backbone bonds were unperturbed, preserving the molecular weight distribution. These results suggest that competitive adsorption between the polymer and solvent plays a significant role in heterogeneous catalysis of polymers. Furthermore, this strategy provides a simple and efficient method for postsynthesis labeling selected polyolefins...