Radical cyclopolymerization of sterically congested acrylic esters bearing bulky α -substituent containing allyl group

Yamada, Bunichiro; Konosu, Osamu

doi:10.1007/s002890050400

Cited by 6 publications

(3 citation statements)

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“…The molecular weights of selected polymers measured by gel permeation chromatography (GPC) with polystyrene calibration are presented in Table . Several trends clearly emerge: (i) other conditions being equal, the molecular weight of the polymer can be controlled by varying monomer concentration in the polymerization mixture (entry 1 vs 2); (ii) as expected polymerizations run in benzene or toluene afford higher molecular weights than polymerization run in tetrahydrofuran (THF), as a result of the differences in chain-transfer constants to solvent (see, for example, entries 7 and 8 vs entry 6); (iii) methallyl-containing monomers afford higher molecular weights than allyl-containing monomers (entries 6 and 8 vs entries 9 and 10) . As expected, the addition of increasing amounts of dodecanethiol as a chain-transfer agent 22 reduces the molecular weight of the polymer (see Table , polymer 39 ).…”

Section: Resultsmentioning

confidence: 92%

“…Similarly, malonate esters containing both an allylic and an acrylic substituent undergo free radical cyclization reactions to afford exclusively cyclopentyl systems . In contrast, a more recent report concerning the cyclopolymerization of dimethyl malonate monomers containing acrylic and methallyl substituents hinted at the presence of both five- and six-membered ring structural units within the backbone of the resulting polymer . To elucidate this point, we prepared model compounds 42 and 45 and allowed them to react under free radical cyclization conditions with TsSePh .…”

Section: Resultsmentioning

confidence: 99%

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Design, Synthesis, and Characterization of Carbon-Rich Cyclopolymers for 193 nm Microlithography

2001

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A series of cyclopolymers designed for use in 193 nm photoresist materials has been synthesized and characterized. These novel materials that provide both optical transparency at 193 nm and also reactive ion etch resistance are obtained via cyclopolymerization of suitably designed bifunctional monomers incorporating acrylic and olefinic double bonds. The approach is highly versatile and allows the preparation of a broad array of structurally related materials with different substituents providing the imaging function and the desired level of etch resistance. The cyclopolymerization process is experimentally forgiving, enabling control of the molecular weight as well as the incorporation of comonomers such as acrylic acid or maleic anhydride to fine-tune the lithographic properties.

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Section: Resultsmentioning

confidence: 92%

Section: Resultsmentioning

confidence: 99%

Design, Synthesis, and Characterization of Carbon-Rich Cyclopolymers for 193 nm Microlithography

2001

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“…51−54 Malonate-based monomers incorporating two functionalities possessing different reactivities toward free radical polymerization have been also the subject of in-depth investigation. In early studies, both Mathias 55 and Yamada 56 reported simple systems able to undergo efficient cyclopolymerization and alternation of the differing reacting groups on the monomer. Mathias was able, with the aid of cyclization experiments on model compounds and sophisticated 13 C NMR structural elucidation, to demonstrate that monomer 10 cyclopolymerize efficiently to afford exclusively five-membered repeating units (P10 in Figure 5), according to the mechanism highlighted in Figure 5, top.…”

Section: -And 6-membered-type Systemsmentioning

confidence: 99%

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

2018

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Monomers possessing two functionalities suitable for polymerization are often designed and utilized in syntheses directed to the formation of cross-linked macromolecules. In this review, we give an account of recent developments related to the use of such monomers in cyclopolymerization processes, in order to form linear, soluble macromolecules. These processes can be activated by means of radical, ionic, or transition-metal mediated chain-growth polymerization mechanisms, to achieve cyclic moieties of variable ring size which are embedded within the polymer backbone, driving and tuning peculiar physical properties of the resulting macromolecules. The two functionalities are covalently linked by a "tether", which can be appropriately designed in order to "imprint" elements of chemical information into the polymer backbone during the synthesis and, in some cases, be removed by postpolymerization reactions. The two functionalities can possess identical or even very different reactivities toward the polymerization mechanism involved; in the latter case, consequences and outcomes related to the sequence-controlled, precision synthesis of macromolecules have been demonstrated. Recent advances in new initiating systems and polymerization catalysts enabled the precision syntheses of polymers with regulated cyclic structures by highly regio- and/or stereoselective cyclopolymerization. Cyclopolymerizations involving double cyclization, ring-opening, or isomerization have been also developed, generating unique repeating structures, which can hardly be obtained by conventional polymerization methods.

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Controlled RAFT Cyclopolymerization of Oriented Styrenic Difunctional Monomers

Sharma

Cornaggia

Pasini

2010

Macro Chemistry & Physics

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We describe the first example of controlled free radical cyclopolymerization of difunctional styrenic monomers. The newly designed monomers are obtained from the introduction of two 4‐vinylbenzyl moieties as malonate or dialkylated malonate esters. The more sterically hindered monomer is particularly efficient in the cyclization and propagation processes, giving cyclopolymers, in diluted solvent conditions, with good yields and degrees of polymerization. In the presence of a suitable RAFT mediator, and, upon careful optimization of the solvent, temperature and monomer concentration, a linear increase in the number average molecular weight with conversion and low polydispersity indexes can be achieved.

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Radical cyclopolymerization of sterically congested acrylic esters bearing bulky α -substituent containing allyl group

Cited by 6 publications

References 0 publications

Design, Synthesis, and Characterization of Carbon-Rich Cyclopolymers for 193 nm Microlithography

Design, Synthesis, and Characterization of Carbon-Rich Cyclopolymers for 193 nm Microlithography

Cyclopolymerizations: Synthetic Tools for the Precision Synthesis of Macromolecular Architectures

Controlled RAFT Cyclopolymerization of Oriented Styrenic Difunctional Monomers

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