A facile route to ketene-functionalized polymers for general materials applications.
Function matters in materials science, and methodologies that provide paths to multiple functionality in a single step are to be prized. Therefore, we introduce a robust and efficient strategy for exploiting the versatile reactivity of ketenes in polymer chemistry. New monomers for both radical and ring-opening metathesis polymerization have been developed, which take advantage of Meldrum's acid as both a synthetic building block and a thermolytic precursor to dialkyl ketenes. The ketene-functionalized polymers are directly detected by their characteristic infrared absorption and are found to be stable under ambient conditions. The inherent ability of ketenes to provide crosslinking via dimerization and to act as reactive chemical handles via addition, provides simple methodology for application in complex materials challenges. Such versatile characteristics are illustrated by covalently attaching and patterning a dye through microcontact printing. The strategy highlights the significant opportunities afforded by the traditionally neglected ketene functional group in polymer chemistry.
Department of Materials, Materials Research Laboratory, University of California, Santa Barbara, California 93106, USA.
Frank A
FA
Leibfarth
Minhyuk
M
Kang
Myungsoo
M
Ham
Joohee
J
Kim
Luis M
LM
Campos
Nalini
N
Gupta
Bongjin
B
Moon
Craig J
CJ
Hawker
D019281:Dimerization; D005030:Ethylenes / Q000737:chemistry*; D005456:Fluorescent Dyes / Q000737:chemistry; D005609:Free Radicals / Q000737:chemistry; D007659:Ketones / Q000737:chemistry*; D010969:Plastics / Q000737:chemistry; D058105:Polymerization; D011108:Polymers / Q000138:chemical synthesis / Q000737:chemistry*; D013057:Spectrum Analysis; D013696:Temperature
D005030:Ethylenes; D005456:Fluorescent Dyes; D005609:Free Radicals; D007659:Ketones; D010969:Plastics; D011108:Polymers; C071464:polynorbornen; C008223:ketene