Study of Photopolymers XXXXII. Synthesis and Photochemical Reaction of Water Soluble Self-Sensitized Photoreactive Polymers Using 1,8-Diazabicyclo-[5.4.0]-7-undecene (DBU) Method

Abstract

is a very useful and interesting reagent for modifying anionic polymers. Recently, some anionic polymers such as poly(methacrylic acid) 1 -3 and poly(4-hydroxystyrene) 4 have been converted to corresponding photosensitive polymers by the reaction with alkyl halides containing photoreactive groups using DBU. These reactions proceeded very smoothly under mild conditions. The reaction of poly(methacrylic acid) and propargyl bromide proceeded especially well at room temperature. DBU can also be used as a suitable reagent for polycondensation between dicarboxylic acids and alkylene dihalides 5 and for intra-molecular condensation of polyamic acids. 6 This article reports on the application of this quite unique method for the syntl)esis of water soluble self-sensitized photosensitive polymers by the reaction of poly(acrylic acid) (PAA) with propargyl bromide (PB) and 2-bromomethylanthraquinone (BMAQ).t To whom all correspondence should be addressed. EXPERIMENT AL ReagentsPAA ·was prepared by the radical polymerization of acrylic acid using 4,4' -azobisisobutylonitlile in ethanol, purified by reprecipitation from ethanol into diethyl ether, and dried in vacuo at 50°C. The yield of PAA was 100%. Reduced viscosity measured at 0.5 g dl-1 in dimethylformamide (DMF) at 30°C was 0.34dlg-1 . BMAQ was synthesized in 50% yield by the reaction of 2-methylanthraquinone and N-bromosuccinylimide according to the reported method. 7Typical Procedure for the Reaction of PAA with PB to obtain Polymer with Pendant Propargyl Group (P-1) Partially propargylated PAA (P-1) was prepared as follows: 17.29g (0.24mol) of PAA was dissolved in 200ml ofDMSO and 17.13g (0.14mol; 60mol% to PAA) of PB and 40.19 g (0.26 mol) of DBU were added into the PAA/DMSO solution and stirred for l h at

Clustering of Poly(methacrylic acid) around Appended Binaphthyl Labels As Reflected by the Disruption of γ-Cyclodextrin Complexation and Racemization Kinetics

“…The product was dissolved in dried DMF and precipitated into diethyl ether. This alternating copolymer 20 was hydrolyzed by heating in water at 80 °C for 4 h followed by tumbling at room temper-ature for 24 h. A small fraction of the carboxyl groups of these polymers was reacted with either the racemic 4-bromomethyl-1,1′-binaphthyl or its enantiomer obtained by chiral chromatography (see below) to append the binaphthyl (BN) label to the polymer as follows: 21 To the solution of PMA (20 mg, 0.233 mmol) in DMF (2.5 mL) were added 1,8-diazabicyclo [5,4,0]undec-7-ene (DBU) (35 µL, 0.233 mmol) at 0 °C and the resolved (R)-or (S)-4-bromo-1,1′-binaphthalene (0.95 mg, 0.0027 mmol). For the racemic system, the temperature was 50 °C and the reaction was conducted in DMSO.…”

Simultaneous construction of polymer backbone and side chains by three‐component polycondensation. Synthesis of polyethers with propargyl side chains from dialdehydes, alkylene bis(trimethylsilyl) ethers, and allenyltrimethylsilane

“…Polymer having propargyl side chains is expected to applicable for a variety of cross‐linking reactions. For example, photo cross‐linking of a polyimide having propargyl side chains has been reported 1. Furthermore, carbon‐carbon triple bond is easily transformed to other functional groups2 and acetylides of bidentate metals 3–6.…”

“…Furthermore, carbon‐carbon triple bond is easily transformed to other functional groups2 and acetylides of bidentate metals 3–6. To the best of our knowledge, a polymer having the propargyl side chains was synthesized by the polymerization of a monomer bearing the propargyl group,1 but it has not been hitherto reported that the propargyl group is directly introduced to polymer during polymerization.…”

A water‐developable negative photoresist based on the photocrosslinking of N‐phenylamide groups with reduced environmental impact

“…Aoki et al [17][18] developed a silicon-containing photoresist which can be developed by water. Nishikubo et al 19 studied water-soluble self-sensitized photocrosslinkable polymers by the radical coupling reaction between anthraquinone and propagyl groups. Hult et al 20 -21 and Willson et al 1 reported a water-soluble chemically amplified negative-tone photoresist.…”