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Enabling Directional Sequence‐Control via Step‐Growth Polymerization of Heterofunctionalized Precision Macromonomers
Macromolecular Rapid Communications ( IF 4.6 ) Pub Date : 2018-11-22 , DOI: 10.1002/marc.201800735
Christoph Gerke 1 , Patrick Siegfeld 1 , Klaus Schaper 1 , Laura Hartmann 1
Affiliation  

The synthesis of periodic copolymers with a regularly recurring sequence in one direction along the polymeric backbone is presented, applying a step‐growth polymerization of heterofunctionalized precision macromonomers derived from solid phase synthesis (SPS) via photoinduced thiol‐ene coupling (TEC). Heterofunctional macromonomers with monomer sequence‐control of the AB type present a terminal alkene and a terminal thiol group carrying a photolabile protecting group to avoid uncontrolled polymerization by self‐initiation. As protecting group, 3,4‐methylenebisoxy‐6‐nitrobenzyl is attached onto the thiol via its bromide derivative directly on solid support. The protected heterofunctionalized macromonomer is polymerized in a two‐step procedure, first cleaving the photolabile group and subsequent polymerization of the macromonomer via TEC, giving a high molecular weight polymer with M ¯ n of 23.8 kDa corresponding to a X ¯ n of 10 with one directional sequence‐control due to their consistent head‐to‐tail linkage.

中文翻译:

通过异官能化的精密大分子单体的逐步增长聚合来实现方向性序列控制

提出了沿着聚合物主链在一个方向上有规律地重复出现的周期性共聚物的合成方法,该方法通过光诱导的硫醇-烯偶联(TEC)的应用,逐步衍生了固相合成(SPS)衍生的杂功能化精密大分子单体。具有AB型单体序列控制的杂功能大分子单体具有一个末端烯烃和一个末端巯基,该末端带有一个对光不稳定的保护基,从而避免了由于自引发而导致的不受控制的聚合反应。作为保护基,3,4-亚甲基双氧基-6-硝基苄基通过其溴化物衍生物直接连接在硫醇上,并位于固体载体上。受保护的杂官能化大分子单体通过两步过程进行聚合,首先裂解光不稳定基团,然后通过TEC聚合大分子单体, 中号 ¯ ñ 23.8 kDa对应于 X ¯ ñ 由于它们始终如一的头对尾链接,因此具有方向定向控制的10个传感器中的10个具有可比性。
更新日期:2018-11-22
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