Postpolymerization modification of reactive polymers derived from vinylcyclopropane. III. Polymer sequential functionalization using a combination of amines with alkoxyamines, hydrazides, isocyanates, or acyl halides

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2014-10, Vol.52 (19), p.2841-2849
• Main Authors: Seuyep Ntoukam, Denis Hervé, Luinstra, Gerrit Albert, Theato, Patrick
• Format: Article
• Language: English
• Subjects: 1,1‐disubstituted‐2‐vinylcyclopropane; 1-disubstituted-2-vinylcyclopropane; acyl halides; Amines; Chains (polymeric); Conversion; Esters; functionalization of polymers; Halides; hydrazide; Hydrazides; hydroxylamine; isocyanate; Isocyanates; Ketones; modification; pentafluorophenyl ester; ring-opening polymerization; sequential post-modification
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.27311

ABSTRACT A new 1,1‐disubstituted‐2‐vinylcyclopropane monomer bearing a ketone and a pentafluorophenyl ester was synthesized and successfully polymerized to yield a polymer with two side chain moieties readily available for post‐polymerization modification. After a quantitative modification of the pentafluorophenyl moiety with amines, a subsequent second functionalization reaction was successfully performed on the ketone moiety leading to a double side‐chain functionalized polymer using two different routes. The first route utilized hydrazide and hydroxylamine derivatives leading to a ketone conversion of 25 to 85%. In the second route, the ketone moiety was first reduced to alcohol (reduction conversion up to 100%) and then converted into the corresponding ester or urethane using acyl halides or isocyanates, respectively, with a conversion ratio of up to 90%. A library of functionalized polymers was synthesized to confirm the effectiveness of this approach. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 2841–2849 1,1‐Disubtitutedvinylcyclopropane were used to prepare a polymer with two readily functionalizable side chain consisted of pentaflourophenyl and ketone. Sequential post‐modification was successfully performed and a library of double functional polymers was prepared with a precise positioning of the functionality in the polymer backbone.