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

Abstract

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.

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

“…8 The composite resins must have at least cross-linkages of 1,3-and Chemical reactions of a terminal bromine atom of the 2-oxahexamethylene spacer of such polyoxetane resins as VIIIC were previously reported by using KOAc, amines, and alcohols as a nucleophilic reagent. 12 These substitution reactions gave the required product polymers with satisfactorily high degrees of functionalization (D.F) in fairly good yields. Chemical reactions of the bromide at the 1-oxapentamethylene spacer-end of the 7a unit in a resin are also investigated in this study using phenols 14, 9, and to and KOAc as nucleophiles to give several functional groups regarded as key substituents for designing various functionalized polymers.…”

“…In these postpolymerizations with the cationic initiator, 3 and oxetane (12) were used as comonomers. Table II.…”

Synthesis and characterization of polyoxetanes containing 4‐cyanobiphenyl‐based side groups for nonlinear optical applications, 2. Synthesis, characterization and polymerization of 3,3‐bis(4‐cyano‐4′‐biphenylyloxymethyl)oxetane

“…s 5,35 6,45 15,s 18,7 16,4 19,3 24,9 27,l 22,2 15,7 14,8 17,15 16,8 6,4 4,9 5,9 9,s 12,s 10,25 9,65 12,45 15,95 13,45 9 2 7 12,25 10,s a) Samples 7 and 9 were annealed for 30 min at 175 "C and 150°C, resp., before poling. b, Sample 13 has become milky after poling.…”