Polyurethanes with specific functional groups

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Polyurethanes with specific functional groups
Olaru Mihaela 1, 2 1 Petru Poni Institute of
Macromolecular Chemistry, Iasi, Romania 2 Centre
of Polymer Chemistry, Zabrze, Poland
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Structure and characteristics of polyurethanes
Applications petrol-chemical and energy sectors,
packaging, refrigeration industry, marble and
granite resin restoring, panels and composites,
sporting/industrial flooring, structural
adhesives, glues and sealants, civil engineering,
ship building industry, biomedical applications
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Structural modifications of polyurethanes

• influence study of the azomethine group on the
  structure and properties of the resulting
  polyurethanes
• polymer synthesis - polyaddition reaction
• introduction of azomethine and oxime-urethane
  groups in the polymeric main chain
• insertion of anthracene and salicylideneanil
  groups as pendant units
• ionomer polyurethanes with anthracene and
  salicylideneanil moieties

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Eur. Polym. J. 2002, 38, 1079-1086
Synthesis of bisazomethine diol monomers
LC texture of aliphatic bisazomethine diol
Solubilitya, b of poly(azomethine-urethane)s in
various solvents
a 1 g polymer in 10 ml solvent at 40C b ()
soluble, () soluble on heating, (-) partial
soluble, (--) insoluble
Synthesis of poly(azomethine-urethane)s
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Thermogravimetric analysis curves of
poly(azomethine-urethane)s

• a smectic LC behavior was evidenced by optical
  polarizing microspcopy and DSC measurements
• the polymers showed a good solubility and
  thermal stability, better than conventional
  polyazomethines
• two of them were found to form excellent thin
  films with elastomeric characteristics

Thermal behavior of poly(azomethine-urethane)s
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Absorption and fluorescence data of compounds
with anthracene moieties
3D fluorescence spectra of polymer bearing
anthracene units
Cationomer polyurethane with anthracene groups
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R
Dimerization reaction of model compund
UV spectrum of anthracene model compound

• starting from aromatic bisazomethine diol a new
  polyurethane cationomer with fluorescent
  properties was obtained
• such type of polymers can function as
  fluorescent sensor for detection of zinc in
  biological systems

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J. Appl. Polym. Sci. 2004, 94(6), 2324-2332
UV irradiation of PU-1 polymer in DMF solution
Polyurethanes with oxime-urethane groups
Photodecomposition mechanism
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Determination of insoluble fraction of PGMA films
with 1 wt. of PU-1 or 5 wt. PU-3 with
irradiation time
Variation of insoluble fraction with
irradiation/heating of polymer films

• the photolysis of oxime-urethane groups leads to
  the formation of amines that induce the
  crosslinking of epoxy groups from PGMA upon
  heating, irradiation and heating/irradiation
• a fluorescent image was obtained on the
  irradiated polymer film treated with fluorescamine

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Polym. International 2005, 54(9), 1296-1303
Absorption for PUC-M1 (- -), PUC-M3 (--) and
fluorescence spectra for PUC-M1 in DMF (?) and
film (), respectively, for PUC-M3 in DMF
(--)
Absorption of PUC-M2 in DMF (--) and
fluorescence spectra for PUC-M2 in DMF () and
PUC-M2 in film (?)
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Photochromic tautomerism process of
salicylideneanil structures

• the fluorescence spectra of salicylideneanil
  compounds indicate that these ones presented
  different shifts in solution and solid state
• the large Stokes shift between absorption and
  emission argues for a fast proton-transfer
  reaction in the excited state

Absorption and fluorescence data