Photolysis of Polyamides Containing Thymine Photodimer Units in the Main Chain and Application to Deep-UV Positive Type Photoresists

Moghaddam, Minoo J.; Inaki, Yoshiaki; Takemoto, Kiichi

doi:10.1295/polymj.22.468

Cited by 14 publications

(5 citation statements)

References 9 publications

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“…For example, caged dimethylpiperidine can catalyze the cross-linking of poly(hydroxyl amide) with bis(activated esters) or bis(vinyl sulfone) as a negative tone resist. Finally, polymers can also be cleaved directly with light − or heat, , eliminating the need for additional reagents. For example, Ionov and co-worker have shown how temperature-dependent polymer solubility can be modulated by photocleavage reactions of o -nitrobenzyl esters, enabling patterning under mild and entirely aqueous conditions …”

Section: Clip Chemistry In Sacrificial Materials Designmentioning

confidence: 99%

Clip Chemistry: Diverse (Bio)(macro)molecular and Material Function through Breaking Covalent Bonds

et al. 2021

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In the two decades since the introduction of the “click chemistry” concept, the toolbox of “click reactions” has continually expanded, enabling chemists, materials scientists, and biologists to rapidly and selectively build complexity for their applications of interest. Similarly, selective and efficient covalent bond breaking reactions have provided and will continue to provide transformative advances. Here, we review key examples and applications of efficient, selective covalent bond cleavage reactions, which we refer to herein as “clip reactions.” The strategic application of clip reactions offers opportunities to tailor the compositions and structures of complex (bio)(macro)molecular systems with exquisite control. Working in concert, click chemistry and clip chemistry offer scientists and engineers powerful methods to address next-generation challenges across the chemical sciences.

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Section: Clip Chemistry In Sacrificial Materials Designmentioning

confidence: 99%

Clip Chemistry: Diverse (Bio)(macro)molecular and Material Function through Breaking Covalent Bonds

et al. 2021

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“…34 Inaki and coworkers have extensively investigated the photocrosslinking of pendant thymine moieties on polymer chains for applications as reversible photo-resists. 11,[35][36][37] Warner and coworkers have reported the synthesis of thymine functionalized water soluble copolymers for photo-resist coatings. 38,39 Warner et al reported a new family of water-soluble photopolymers for their potential use as environmentally benign 'negative working' photoresists.…”

Section: Photo-resistsmentioning

confidence: 99%

“…118 In a similar manner to Chen et al, 118 Inaki et al prepared polyurethanes containing the thymine dimer as a site for photodegradation in a positive-type photo-resist. 121 Again however, Inaki found that the photo-cleavage reactions (performed using 249 nm UV light) were incomplete. 121 Obviously, this "dimer-rst" approach relies on the synthesis of large enough amounts of the cyclobutane compounds for synthetic incorporation into new monomer structures.…”

Section: Linear Polymers Containing Pre-synthesised Cyclobutane Segme...mentioning

confidence: 99%

“…121 Again however, Inaki found that the photo-cleavage reactions (performed using 249 nm UV light) were incomplete. 121 Obviously, this "dimer-rst" approach relies on the synthesis of large enough amounts of the cyclobutane compounds for synthetic incorporation into new monomer structures. While this is not always straightforward, a number of thymine, 122-124 coumarin 125 and cinnamic acid 126 derivatives have already been identied to undergo near-quantitative regiospecic photodimerisation in single crystals of the starting compoundssome of which may be useful for incorporation into new types of monomer/polymer structures.…”

Section: Linear Polymers Containing Pre-synthesised Cyclobutane Segme...mentioning

confidence: 99%

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Photo-reversible dimerisation reactions and their applications in polymeric systems

2014

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“…We further investigated the photoreversibility of Thy‐P n BuA‐Thy polymers. The thymine dimers are generally capable of retro‐[2π + 2π] dimerization upon exposure to UV irradiation with wavelengths shorter than 250 nm . To study the retro‐[2π + 2π] photoreactions of the polymers, thin films were first photopolymerized (at 302 nm, 64 J cm −2 ).…”

Section: Characteristics Of Irradiated Thy‐pnbua‐thy Polymers (Gpc Data)mentioning

confidence: 99%

UV-reversible chain extendable polymers from thymine functionalized telechelic polymer chains

Kaur

Bertrand

Bernard

et al. 2014

J. Polym. Sci. Part A: Polym. Chem.

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Recently, significant attention has been paid to the preparation of polymeric materials that enable the reversible tuning of molecular weights and crosslink densities of polymers. Reversible polymers are of interest for applications in selfhealing 1-4 and reorganizable materials. 5,6 Reversible polymeric systems rely either on covalent or noncovalent bonds. 7These polymeric systems can usually be subdivided into reversibly crosslinkable polymers and reversible linear polymers which include supramolecular polymers and reorganizable polymers. In the reversibly crosslinkable polymers, multiple dynamic bonding units are present either as pendant groups on polymer chains, [8][9][10] or as terminal units in multifunctional macromonomers. 11,12 An external stimulus such as heat, light, or chemical is used to trigger the polymerization and the depolymerization. Supramolecular reversible polymers have been synthesized using noncovalent interactions such as hydrogen bonding, p-p interactions, ionomers, and coordinative bonds. [13][14][15][16][17][18][19][20] There are fewer examples of reversible polymers using dynamic covalent bonding, most of which are based on thermally reversible covalent bonds. 6,[21][22][23] Dynamic polymeric systems using photoreversible covalent reactions, such as photodimerization, are of particular interest because such reactions can be conducted at ambient temperature usually without the need for a solvent. 24 Several researchers have made attempts to polymerize coumarin or cinnamate telechelic oligomers under UV irradiation. 25,26 However, only low molecular weight polymers were obtained for these systems because of the low yield of the photochemical reaction. Thymine makes an interesting choice for incorporation in polymeric materials due to its ability to form hydrogen bonds as well as its propensity to undergo reversible photodimerization upon UV exposure. [27][28][29][30][31][32][33] Furthermore, thymine has demonstrated a high sensitivity and efficiency of photoreversion in comparison with coumarin and cinnamylidene (a derivative of cinnamic acid). 25,34-36In a previous work, 37 a,x-thymine functionalized telechelic poly(n-butyl acrylate)s (Thy-PnBuA-Thy) were synthesized by trithiocarbonate-mediated RAFT polymerization and used to prepare supramolecular block copolymers. In this article, the photoreactivity of thymine moieties in Thy-PnBuA-Thy is exploited to develop UV-reversible chain-extendable polymer chains. During the photopolymerization, the terminal thymines are expected to undergo 2p12p photodimerization upon UV irradiation from 270 to 320 nm, resulting in the formation of chain-extended linear polymer chains (Fig. 1). The cyclobutane rings formed in the resulting polymers should be cleaved when irradiated with shorter wavelength of UV light (<250 nm).To photopolymerize terminally thymine functionalized PnBuA, thin films with a thickness of 6.0 (6 0.5) lm were first prepared on glass substrates from THF solutions. The dried films were then irradiated using a 302-nm UV lamp to ach...

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Photolysis of Polyamides Containing Thymine Photodimer Units in the Main Chain and Application to Deep-UV Positive Type Photoresists

Cited by 14 publications

References 9 publications

Clip Chemistry: Diverse (Bio)(macro)molecular and Material Function through Breaking Covalent Bonds

Clip Chemistry: Diverse (Bio)(macro)molecular and Material Function through Breaking Covalent Bonds

Photo-reversible dimerisation reactions and their applications in polymeric systems

UV-reversible chain extendable polymers from thymine functionalized telechelic polymer chains

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