Intramolecular Cross-linking of Polymers Using Difunctional Acetylenes via Click Chemistry

Abstract

An efficient approach was described for the intramolecular cross-linking of azide-functionalized poly(styrene-co-chloromethyl styrene) co-polymers (PS-N 3 ) via click chemistry at room temperature. Reaction of PS-N 3 with the appropriate diacetylene functional compounds such as 1,4-diethynylbenzene (DEB) and 1,10-dipropargyloxy decane (DPD) in ultra-dilute solutions led to unimolecular particle-like structures. The resulting polymers were characterized in detail by 1 H-NMR, FT-IR, GPC and DSC measurements.

Advances in Click Chemistry for Single-Chain Nanoparticle Construction

“…I agree with the suggested changes, that can be made easily by the editorial office. [7,22,28,29], poly(styrene) [3,22,23,[30][31][32], poly(haloalkyl styrene) [3,33], poly(4-N-Boc-vinylaniline) [33], poly(sodium 4-styrenesulfonate) [22], poly(N-alkyl acrylamide) [22,34,35] Atom transfer radical polymerization ATRP Poly(alkyl methacrylates) [14], poly(alkyl acrylates) [11,12], poly(styrene) [36], poly(N-hydroxyethyl acrylamide) [37] Nitroxide mediated radical polymerization NMP Poly(alkyl methacrylates) [9,[38][39][40], poly(alkyl acrylates) [40], poly(styrene) [2,38,40], poly(haloalkyl styrene) [40], poly(fluorene) [41] Ring opening metathesis polymerization ROMP Poly(-caprolactone) [38], poly(carbonates) [42] poly(norbornenes) [13,43,44] * For SCNP copolymer and terpolymer precursors, only the nature of the main component is indicated.…”

“…Covalent bonding interactions Vinyl [33,38,39,42] Radical coupling & Cross-Metathesis Benzocyclobutene [40,53] Diels-Alder reaction * Benzosulfone [9,28,41] Diels-Alder reaction * Azide + Protected alkyne [3,10,21,22,30,34] Copper-catalyzed [3+2] cycloaddition ** Carboxilic acid [54] Amide formation Isocyanate [23] Urea formation ** Enediyne [11,12,24,29] Bergman & Photo-Bergman cyclization Sulfonyl azide [31] Nitrene-mediated cross-linking Benzoxazine [36] Ring opening polymerization Alkyne [25] Glaser-Hay coupling * * C-C click chemistry. ** N-C click chemistry.…”

“…Very recently, this method has been employed by Cengiz et al [30] for the synthesis of polystyrene single-chain nanoparticles showing a 10-fold reduction in solution viscosity at 250 s −1 of shear rate when compared to the precursor polymer. This difference, that was even higher at very low shear rate, was attributed to the particle-like nature of the collapsed chains.…”

Synthesis, characterization, and hydrolytic degradation of graft copolymers of polystyrene and aliphatic polyesters

“…[33,34] Many examples of click reactions involving macromolecules were reported. In this laboratory, we have focused on the use of such click reactions for the synthesis of various macromolecular architectures [34][35][36][37][38][39][40][41] and functionalization of polymers [42][43][44][45][46][47], microspheres [48], clays [49,50], and silsesquioxanes [51] with thermal-, photo-, and electro-active groups.…”

Photoinduced grafting of polystyrene onto silica particles by ketene chemistry

“…[22][23][24][25][26][27][28][29][30][31][32][33][34][35][36][37][38] The copper-catalyzed click reactions, Diels-Alder reactions, and thiol-ene reactions are such click reactions with very high yields and nearly no by-product formation. Recently, the ketene chemistry is also announced as a promising route for the modification of macromolecular structures with significant yields.…”