Title page for ETD etd-04262004-150913

Type of Document Dissertation
Author Trenor, Scott Russell
Author's Email Address strenor@vt.edu
URN etd-04262004-150913
Title Synthesis and Characterization of Tailored Photoactive Macromolecules
Degree PhD
Department Macromolecular Science and Engineering
Advisory Committee
Advisor Name Title
Long, Timothy E. Committee Co-Chair
Love, Brian J. Committee Co-Chair
Dillard, David A. Committee Member
Riffle, Judy S. Committee Member
Ward, Thomas C. Committee Member
  • Coumarin
  • Polymer Photochemistry
  • Adhesives
  • Alkyl Acrylates
  • Cinnamates
Date of Defense 2004-04-16
Availability unrestricted
Coumarin and cinnamate derivatives were positioned as either polymer chain ends or side groups to synthesize photoactive macromolecules and gain the ability to reversibly control molecular weight and crosslink density using UV light. The cinnamates and coumarins were reacted onto the polymers via multiple reaction pathways. Polymers were functionalized with coumarin or cinnamate groups via an esterification reaction between hydroxyl functionalities and an acid chloride derivatized coumarin group. In addition to the esterification reaction, cinnamates were also coupled to polymers via a ring opening reaction between a hydroxyl functionalized cinnamate derivative and a maleic anhydride repeat unit copolymerized into the polymer. Both functional groups undergo a [2p + 2p] photodimerization reaction (coumarin groups in the UVA and cinnamate groups in the UVB), which was utilized to crosslink and chain-extend macromolecules. Coumarin dimers possess the additional ability to photocleave and thus reverse when irradiated at 254 nm.

The coumarin reversible photodimerization reaction was utilized to reversibly increase the molecular weight and molecular weight distribution of coumarin-functionalized PEG monols and diols. For example, the number average molecular weight of the coumarin-functionalized PEG diol doubled and the

molecular weight distribution increased from 1.08 to 2.75 when exposed to 110 J cm-2 of UVA irradiation. Subsequent photocleavage (UVC irradiation, 2 J cm-2) of the chain-extended PEGs, cleaved coumarin dimers decreasing the molecular weight and molecular weight distribution to their original values.

A number of poly(alkyl acrylate) and poly(methyl acrylate) systems were functionalized with coumarin groups to study the effect of the glass transition temperature and alkyl ester side group composition on the photodimerization reaction and subsequent crosslinking. The glass transition temperature (Tg) acted as an on/off switch for the photodimerization reaction. While the absolute difference between Tg and irradiance temperature did not affect the rate or extent of photodimerization reaction, polymers with a Tg greater than the irradiance temperature displayed less reaction than those with a Tg lower than the irradiance temperature. The final extent of conversion was controlled by a complex combination of factors including alkyl ester side chain steric bulkiness. Coumarin-functionalized alkyl acrylates based on ethylhexyl acrylate were tested as detachable PSAs. A 98% decrease in the adhesive peel strength was observed after exposure to UVA irradiation.

Cinnamate groups were utilized in the design and synthesis of UV-curable hot melt pressure sensitive adhesives (PSAs). The cinnamate groups were attached to the PSAs to provide a method to increase molecular weight and add a small amount of crosslinking leading to an increase the adhesive strength of the PSAs. Broadband UV irradiation from a laboratory scale industrial lamp increased the peel strength of the adhesives. Postcure of the irradiated cinnamate-functionalized UV-curable hot melt PSAs was reduced compared to photoinitiated free-radical photocurable UV-curable hot melt PSAs.

  Filename       Size       Approximate Download Time (Hours:Minutes:Seconds) 
 28.8 Modem   56K Modem   ISDN (64 Kb)   ISDN (128 Kb)   Higher-speed Access 
  ScottRTrenorDissertation.pdf 6.49 Mb 00:30:03 00:15:27 00:13:31 00:06:45 00:00:34

Browse All Available ETDs by ( Author | Department )

dla home
etds imagebase journals news ereserve special collections
virgnia tech home contact dla university libraries

If you have questions or technical problems, please Contact DLA.