A new chemical modification of liquid polybutadienes: Radical addition of aliphatic aldehydes onto pending vinyl groups

Abstract

A new chemical modification of liquid polybutadiene by radical addition of model aldehydes (butanal and hexanal) onto pending vinyls of the polymer is described. The dibenzoyl peroxide/N,N‐dimethylaniline redox system was shown to initiate the hydroacylation more efficiently than the thermal decomposition of 2,2′‐azobis(2‐methylpropanenitrile) because it gives higher conversions (content of hydroacylated monomer units, as determined by NMR) without forming crosslinks or microgels. Typically, the former source of radicals gives the content of modified units as high as 13% related to all monomer units, while the latter only 2–6%. Repeated introduction of the redox system into the reaction mixture resulted in an increased content of the acyl groups. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 3919–3925, 2008

Cycloalkenyl-Functionalized Polymers and Block Copolymers: Syntheses via Selective RAFT Polymerizations and Demonstration of Their Versatile Reactivity

“…For example, incorporation of carbonyl groups (e.g., ketone [10][11][12][13][14] and aldehyde 15 ) enhanced the photodegradability 10 and also allowed for efficient grafting via wellestablished carbonyl chemistries. 11,14,[16][17][18] Alkene-functionalized polymers have attracted considerable attention because the olefin groups undergo transformations by robust, selective, and mild olefin chemistries via thiol-ene UV reaction, [19][20][21][22][23] aldehyde-alkene photoreaction, 24 ring-opening metathesis (ROM) [25][26][27][28][29] and cross-metathesis (CM) reactions, [30][31][32][33][34] electrophilic addition, 35,36 radical polymerization, 37 and so on. Relative to postpolymerization functionalization, selective living polymerization of asymmetrical divinyl monomers has provided well-defined polymers with pendent alkenyl groups directly from alkene-functionalized monomers.…”

Well-Defined Polymers Bearing Pendent Alkene Functionalities via Selective RAFT Polymerization

“…Because properties and performances of polymers greatly depend on the kind and number of functional groups, the development of synthetic strategies that exert excellent control over functionalities of polymers has attracted increased interest. [1][2][3][4][5][6][7][8] Because of the broad applications of vinyl groups in polymerization, 9 cross-linking, [10][11][12][13][14][15][16][17] radical coupling, [18][19][20][21][22] postmodification, and transformations into other useful functionalities, 23 well-defined polymers with pendent vinyl groups have received significant attention. 20,[24][25][26][27][28][29][30][31][32][33][34][35] Similar to most types of polymers with functional side groups, those having multiple pendent vinyl groups have been synthesized by either postpolymerization functionalization or polymerization of vinyl-functionalized monomers.…”

“…The preparation of polymers with accurately controlled structures has become a research theme of modern polymer chemistry. Because properties and performances of polymers greatly depend on the kind and number of functional groups, the development of synthetic strategies that exert excellent control over functionalities of polymers has attracted increased interest. − Because of the broad applications of vinyl groups in polymerization, cross-linking, − radical coupling, − postmodification, and transformations into other useful functionalities, well-defined polymers with pendent vinyl groups have received significant attention. ,− …”

The Power of RAFT for Creating Polymers Having Imbedded Side-Chain Functionalities: Norbornenyl-Functionalized Polymers and their Transformations via ROMP and Thiol-ene Reactions

“…Alkene-functionalized polymers could be converted to polymer materials with new or improved properties through diverse functionalization strategies such as radical cross-linking and polymerization, [5,8,[26][27][28][29][30][31] electrophilic addition, [32,33] cross-metathesis reaction, [34] osmylation, [35,36] and aldehyde-alkene photoreaction. [37] Recently, thiol-ene radical addition has emerged as a robust and orthogonal method for macromolecular synthesis and functionalization. [26][27][28][29][30][38][39][40] A variety of functional polymers have been readily synthesized by thiol-ene reactions of functionalized thiols with polymers having alkene groups.…”