Global intramolecular hydrogen bonds were installed and manipulated in a rigid artificial synthetic polymer in order to actively control its conformation for synthesis and processing. The polymer solubility was switched on and off by chemically inhibiting and regenerating these preorganized intramolecular hydrogen bonds. Such active manipulation made it possible to synthesize this highly rigid polymer with elevated molecular weights. A well-solubilized, noncoplanar polymer precursor with thermally cleavable Boc groups was synthesized (M_n = 32.4 kg/mol). After processing this precursor into thin films, in situ thermal treatment regenerated the latent intramolecular hydrogen bonds and led to a rigid ladder-type conformation. Such manipulation of the intramolecular hydrogen bonds allowed for multilayer deposition of this polymer, laying the foundation for potential additive manufacturing using this strategy.

中文翻译：

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通过分子内氢键的主动操作实现刚性聚合物的合成和溶液处理

在刚性人造合成聚合物中安装和操纵全局分子内氢键，以主动控制其构象以进行合成和加工。通过化学抑制和再生这些预先组织的分子内氢键来打开和关闭聚合物的溶解度。这种主动操作使得合成这种具有高分子量的高刚性聚合物成为可能。合成了具有可热裂解 Boc 基团的溶解良好的非共面聚合物前体 ( Mn = _32.4 kg/mol)。在将这种前体加工成薄膜后，原位热处理再生了潜在的分子内氢键并导致刚性梯型构象。这种对分子内氢键的操纵允许这种聚合物的多层沉积，为使用这种策略的潜在增材制造奠定了基础。