Synthesis of High Refractive Index Polymer Thin Films for Soft, Flexible Optics Through Halomethane Quaternization of Poly(4‐Vinylpyridine)

Huo, Ni; Rivkin, Jeremy; Jia, Ruobin; Zhao, Yineng; Tenhaeff, Wyatt E.

doi:10.1002/adom.202302201

Cited by 5 publications

(1 citation statement)

References 55 publications

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“…To date, it has led to over 70 functional polymer thin films. These high-purity and pinhole-free films are ideal for optoelectronic devices , (e.g., as low-leakage-current dielectric layers) and perm-selective layers for molecular separations . The high density of reactive organic moieties at the surface augments smart behavior in active materials and soft robotics and enables postdeposition functionalization with biomolecules and nanoparticles …”

Section: Introductionmentioning

confidence: 99%

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Chen,

Zhang,

Park

et al. 2024

Chem. Mater.

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Initiated chemical vapor deposition (iCVD) has revolutionized the preparation of high-quality conformal polymer films with excellent control over composition and properties at the nanoscale. It is compatible with over 70 functional monomers. Despite that chemical versatility, side reactions during iCVD are not well understood. For example, chain transfer could happen during the propagation of an important class of monomers that contain nitrogen (N), arresting the polymerization and limiting the molecular weight. Here, we use 1vinylimidazole (1VI) to demonstrate the chain transfer reaction to the imidazole group during iCVD, which leads to unpredictable deposition kinetics, low molecular weight, and undesirable products. We further introduce a strategy that utilizes a vapor solvent to engineer monomer reactivity and suppress side reactions. By replacing the traditional patch flow, Ar, with acetic acid (AcOH), which forms hydrogen bonding with 1VI, chain transfer is suppressed, and the deposition rate is increased by as much as 280% while restoring its linear dependence on the monomer partial pressure. That linear dependence has not been achieved previously for 1VI. The tunable deposition kinetics, in turn, leads to a broader range of attainable material properties, including nearly doubling the maximum attainable molecular weight (from 8 kDa to 16 kDa) and increasing the elastic modulus (from 3.5 to 4.7 GPa). The vapor solvent is also effective at suppressing chain transfer in other N-containing monomers, like (2-dimethylamine) ethyl methacrylate (DMAEMA), leading to a considerable increase in the molecular weight (from 16 kDa to 38 kDa). The vapor solvent selectively increases the reactivity of N-containing monomers during copolymerization, demonstrated using 1VI and divinylbenzene (DVB) or 1,3,5,7-tetravinyl tetramethylcyclotetrasiloxane (V4D4), increasing the reactivity ratio of 1VI by an order of magnitude according to the Fineman−Ross equation. This robust strategy engineers monomer reactivity without the need for chemical modifications. It improves the chemical precision of iCVD polymerization, particularly for an important class of N-containing monomers, which have found broad applications as the polymer− electrolyte interphase in batteries, antifouling coatings in food and water production, and bioactive and functionalizable coatings in sensors.

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Section: Introductionmentioning

confidence: 99%

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Chen,

Zhang,

Park

et al. 2024

Chem. Mater.

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Aromatic Poly(dithioacetal)s: Spanning Degradability, Thermostability, and High Refractive Index Towards Eco‐friendly Optics

Watanabe,

Yano,

et al. 2024

ChemSusChem

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In the quest for eco‐friendly optics, high refractive index polymers (HRIPs) with degradability have been one of the desirable optical materials for realizing eco‐friendly and efficient lighting technologies. However, it has been challenging for HRIPs to simultaneously realize thermostability, high refractive index (RI), visible transparency, and efficient degradability, all of which are essential for their practical use. In this context, we herein focus on aromatic poly(dithioacetal)s, composed of visible‐transparent yet degradable dithioacetal moieties and rigid diphenyl disulfide spacers, exhibiting moderately high Tg (> 60 °C), high RI (> 1.7), and colorless film features. In addition, poly(dithioacetal)s can balance (1) high stability under the operating conditions even upon heating and (2) quantitative degradability that can selectively yield cyclic low‐molecular‐weight products that can be further repolymerized upon further addition of an acid catalyst. These results provide a key concept for high refractive index polymers that allow on‐demand degradability and recyclability without compromising their high potential thermal and optical properties.

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Novel fluorobenzimidazole-assisted heat resistant anticorrosion copper surface for high-density interconnected printed circuit boards

Zhuang,

Weng,

Chen

et al. 2025

Progress in Organic Coatings

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Synthesis of High Refractive Index Polymer Thin Films for Soft, Flexible Optics Through Halomethane Quaternization of Poly(4‐Vinylpyridine)

Cited by 5 publications

References 55 publications

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Curbing Chain Transfer in Initiated Chemical Vapor Deposition (iCVD) via Molecular Vapor Complexation

Aromatic Poly(dithioacetal)s: Spanning Degradability, Thermostability, and High Refractive Index Towards Eco‐friendly Optics

Novel fluorobenzimidazole-assisted heat resistant anticorrosion copper surface for high-density interconnected printed circuit boards

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