A Facile Synthesis of Oxetane Derivatives for Preparing Cross-Linked Polyoxetane Resins Bearing the Bromide at the Spacer End

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ABSTRACT:Uncross-and cross-linked polyoxetanes bearing o-, m-, and p-phenolic residual groups at the terminals of moderately long pendant spacers -CH2O(CH2).-, where n = 4 and 6, were prepared. The prepolymers having the pendant O-acetylated phenols were made by the BF 3 -initiated cationic ring-opening polymerization and then the pendant phenyl acetates were hydrolyzed with 2N aqueous NaOH in methanol to give the desired phenolic polyoxetanes. The pendant phenols were subjected to the diazocoupling reaction with 3 equiv of benzenediazonium chloride to examine their reactivities in aqueous media. Model polyoxetanes with the pendant phenyl benzoates containing the azo group were also prepared to confirm the structures of the diazocoupling product polymers.

Section: Methodsmentioning

confidence: 99%

“…These polymerizations were carried out with 8 mol % of BF 3 THF due to the presence of the azo group capable of acting as a Lewis Base. 4 Poly(S) and poly (9) • Estimated by GPC relative to the polystyrene standards. b Obtained by the alkaline hydrolysis of poly (8).…”

Section: Diazocoupling Reaction Of the Pendant Phenolsmentioning

confidence: 99%

Preparation and Characterization of Polyoxetanes Anchoring the Pendant Spacer-Separated Phenolic Residues and Their Derivatives

Hiruma

Kanoh

Yamamoto

et al. 1995

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“…3-(6-Bromo-2-oxahexyl)-3-methyloxetane (3), l .8-bis(3-methyl-3-oxetanyl)-2, 7-dioxaoctane ( 4), and an isomeric mixture of m-and p-[3-(3-methyl-3-oxetanyl)-2-oxapropyl]styrenes (5) were prepared under phasetransfer catalytic conditions, following the method reported by us previously. 5 • 8 p- styrene (7a).…”

Section: Methodsmentioning

confidence: 99%

Synthesis, Polymer Reactions, and Characterization of Polystyrene-Polyoxetane Composite Resins Having a Pendant Terminal Bromide of 1-Oxapolymethylene Spacers Bound to the Styryl Group at the Para Position

Motoi

Saito

Kyoda

et al. 1991

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ABSTRACT:Polystyrene-polyoxetane composite resins were prepared via two-stage polymerizations using p-substituted styrenes CH2 =CHC6 HcO(CH 2 ).Br (7a or 7b), where n=4 or 6, and an isomeric mixture of m-and p-[3-(3-methyl-3-oxetanyl)-2-oxapropyl]styrenes (5) as a cross-linking agent. The terminal bromide linked to a styryl ring at the para position through an 1-oxapentamethylene spacer of7a (n = 4) was applicable to a starting substrate on polymer reactions with some nucleophiles, such as phenols, potassium acetate, and tributylamine, for obtaining polymeric derivatives via several reaction steps. These resins with a pendant quaternary ammonium bromide moiety were also used as phase-transfer catalysts. On the basis of their catalytic activities, qualities and spacer effects of these supporting resins were compared with those of resins obtained by using chloromethylstyrenes instead of 7a or divinylbenzenes instead of 5.

“…The oxetane derivatives 3a, 3b, 4a, and 4b were prepared in 63~76% yield, following the method reported previously by us. 11 Tetra-(2a) and hexamethylene dibromides (2b), benzyl alcohol (11), N-methyl-aniline (12), nicotinamide (13), potassium acetate (KOAc), tributylamine (14), and tetrabutylammonium bromide (TBAB) were of guaranteed grade and used without further purification. Dichloromethane (DCM) as a polymerization solvent was twice distilled over calcium hydride in an atmosphere of dry nitrogen.…”

Section: Experiments Almentioning

confidence: 99%

“…In order to avoid disadvantages in using the hard, hydrophobic chloromethylated polystyrene supports in the polymer modification, we prepared soft, more polar polymer supports carrying pendant alkyl halides which are convertible into desired functional groups by proper polymer reactions; we found a facile preparation method of oxetane monomers with a terminal bromide in the side chain (3a and 3b) and bifunctional oxetane derivatives ( 4a and 4b ). 11 These bisoxetanes were successfully used to give elastic polyoxetane resins with the bromide at the 2-oxapolymethylene spacer-end by cationic ring-opening copolymerization with 3a or 3b. We have thus been interested in the investigation of the chemical reactions of the pendant alkyl bromide of the uncross-and cross-linked polyoxetanes to obtain various functionalized polyethers.…”

mentioning

confidence: 99%

Polymer Reactions of the Pendant Alkyl Bromides of Soluble and Insoluble Polyoxetanes for the Preparation of Chemically Modified Polyethers

Motoi

Suda

Kijima

et al. 1989

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ABSTRACT:Soluble and insoluble polyoxetanes with w-brom-2-oxaalkyl side chains of -CH2O(CH2).Br (n=4 or 6) were prepared by cationic ring-opening polymerization of 3-(wbromo-2-oxaalkyl)-3-methyloxetanes and by their co-or terpolymerizations with other oxetanes and/or cross-linking agents such as bisoxetanes X-CH2O(CH2),,OCH,-X (X = 3-methyl-3-oxetanyl and n=4 or 6). The bromine at the 2-oxapolymethylene-spacer end of the soluble polymers were converted into the corresponding functional groups by polymer reactions with several nucleophiles such as anions of carboxylates and alkoxides, and amines. The pendant acetoxyl and cyclic acetal groups, thus introduced, were hydrolyzed to give the corresponding hydroxyl groups. Quaternization of the pendant bromides of the uncross-and cross-linked polyoxetanes took place with nicotinamide or tributylamine. The product polymers with a tetraalkylammonium moiety showed catalytic activity for a phase-transfer catalytic reaction of alcohols and alkyl bromides giving ether compounds in satisfactory yields. Electrophilic substitutions such as bromination, nitration, and acylation were examined in pendant aromatic rings of poly(3-benzyloxetane)s. The electrophilic substitutions occurred at 70 to 90%, although some decrease in the molecular weight of the product polymer was observed owing to ether cleavage of the polymer chain under acidic conditions.