Development of optically transparent cyclic olefin photoresist binder resins

Rhodes, Larry F.; Chang, Chun Yen; Burns, Cheryl; Barnes, Dennis A.; Bennett, Brian; Seger, L.; Wu, Xiaoming; Sobek, Andy; Mishak, Mike; Peterson, C.A.; Langsdorf, Leah J.; Hada, Hideo; Shimizu, Hiroaki; Sasaki, Kazuhito

doi:10.1117/12.600051

Cited by 3 publications

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“…A cationic complex with a weakly coordinated anion and a labile phosphine ligand is the necessary attribute of a highly active Pd catalyst for norbornene polymerization. 65 A phosphine stabilizes the Pd complex which can be heated during polymerization without decomposition. The weakly coordinated anion is required for charge compensation and the formation of an easily accessible coordination site.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships

et al. 2019

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We studied the addition polymerization of readily available bifunctional norbornene derivatives, 5-alkylidene-2-norbornenes, in the presence of modified Pd complexes with N-heterocyclic carbene ligands activated by borates. The Pd−N-heterocyclic carbene complex/phosphine/borate systems selectively catalyze the addition polymerization of 5methylene-2-norbornene and 5-ethylidene-2-norbornene with the participation of the endocyclic norbornene double bond, whereas the exocyclic double bond remained intact. The catalysts exhibited extremely high activity and durability: the activity was higher than 1 × 10 8 g polymer / (mol Pd •h) and some catalysts were active at a very high monomer/Pd molar ratio of 2 × 10 7 or at a Pd complex concentration of 5 × 10 −6 mol %. The structure−catalytic activity relationships were established for Pd−N-heterocyclic carbene complexes: the Pd complexes bearing five-membered heterocyclic rings and/or less sterically hindered aryl groups at nitrogen atoms in carbene ligands exhibited the highest activity. The polymerization can be performed in an atmosphere of air and in wet solvents. The resulting polymers are amorphous and high-molecular-weight products consisting of rigid saturated main chains and reactive side groups. Thus, they can be considered as promising intermediates in the production of polymeric materials with high glass-transition temperatures and desired properties by targeted modifications.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships

et al. 2019

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The Effect of End Group Modification on the Transparency of Vinyl Addition Norbornene Polymers at 193 nm

Chang

Lipian

Barnes

et al. 2005

Macro Chemistry & Physics

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Summary: Homopolymers of a bis‐trifluorocarbinol substituted norbornene (1) (α,α‐bis(trifluoromethyl)bicyclo[2.2.1]hept‐5‐ene‐2‐ethanol or HFANB) and copolymers of 1 with t‐butyl ester of 5‐carboxylic acid (2, t‐BuEsNB) were produced using palladium catalysts and olefinic chain transfer agents such as 1‐hexene and ethylene to control molecular weight. However, these low‐molecular‐weight polymers exhibited relatively low optical transparencies at 193 nm. In fact, the opacity (measured as optical densities in absorbance units per micron) of thin films of these homo‐ and co‐polymers was inversely proportional to their molecular weight. This relationship is consistent with an end group contribution to the film opacity. Spectroscopic analysis of these polymers by 1H NMR and MALDI‐TOF MS confirmed that 1‐hexene and ethylene chain transfer agents generated olefin‐terminated vinyl addition polymers. The olefinic end group contribution to optical density can be eliminated by appropriate chemical modification. Both epoxidation and hydrogenation of the polymer olefinic end groups generated very low optical density materials, independent of molecular weight, that are suitable as 193‐nm photoresist binder resins.End group modification of vinyl and hexenyl‐terminated homopolymers of 1 by epoxidation or hydrogenation.magnified imageEnd group modification of vinyl and hexenyl‐terminated homopolymers of 1 by epoxidation or hydrogenation.

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Addition polymerization of functionalized norbornenes as a powerful tool for assembling molecular moieties of new polymers with versatile properties

Бермешев

Chapala

2018

Progress in Polymer Science

126

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Development of optically transparent cyclic olefin photoresist binder resins

Cited by 3 publications

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Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships

Polymerization of 5-Alkylidene-2-norbornenes with Highly Active Pd–N-Heterocyclic Carbene Complex Catalysts: Catalyst Structure–Activity Relationships

The Effect of End Group Modification on the Transparency of Vinyl Addition Norbornene Polymers at 193 nm

Addition polymerization of functionalized norbornenes as a powerful tool for assembling molecular moieties of new polymers with versatile properties

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