Preparation of Novel Hydrolyzing Urethane Modified Thiol-Ene Networks 英文参考文献.docVIP

Polymers 2011, 3, 1849-1865; doi:10.3390/polym3041849 OPEN ACCESS polymers ISSN 2073-4360 /journal/polymers Article Preparation of Novel Hydrolyzing Urethane Modified Thiol-Ene Networks Nicole M. Mackey 1, Bridget S. Confait 1, James H. Wynne 2 and J. Paige Buchanan 1,*,? 1 Department of Chemistry and Biochemistry, University of Southern Mississippi, 118 College Drive, Hattiesburg, MS 39406, USA; E-Mails: nicole.mackey@ (N.M.M.); bridget.confait@ (B.S.C.) 2 Chemistry Division, Naval Research Laboratory, 4555 Overlook Ave, SW, Washington, DC 20375, USA; E-Mail: james.wynne@ (J.H.W.) * Author to whom correspondence should be addressed; E-Mail: paige.buchanan@; Tel.: +1-601-266-4083; Fax: +1-601-266-6075. ? J. Paige Buchanan was formerly known as J. Paige Phillips. Received: 11 August 2011; in revised form: 6 October 2011 / Accepted: 21 October 2011 / Published: 25 October 2011 Abstract: Novel tetra-functional hydrolyzing monomers were prepared from the reaction of TEOS and select alkene-containing alcohols, ethylene glycol vinyl ether or 2-allyloxy ethanol, and combined with trimethylolpropane tris(3-mercaptopropionate) (tri-thiol) in a thiol-ene “click” polymerization reaction to produce clear, colorless thiol-ene networks using both radiation and thermal-cure techniques. These networks were characterized for various mechanical characteristics, and found to posses Tg’s (DSC), hardness, tack, and thermal stability (TGA) consistent with their molecular structures. A new ene-modified urethane oligomer was prepared based on the aliphatic polyisocyanate Desmodur? N 3600 and added to the thiol-ene hydrolyzable network series in increasing amounts, creating a phase-segregated material having two Tg’s. An increase in water absorption in the ene-modified urethane formulations leading to a simultaneous increase in the rate of hydrolysis was supported by TGA data, film hardness measurements, and