Kinetics of photopolymerization-induced phase separation and morphology development in mixtures of a nematic liquid crystal and multifunctional acrylate

Photopolymerization behavior and reaction kinetics for a series of multifunctional acrylate monomer(s) and eutectic liquid crystal blends were investigated with particular emphasis on determination of the reaction rate coefficients for propagation and termination steps of photopolymerization. Reaction rate coefficients were determined via real-time infrared spectroscopy and compared with those obtained by photo-differential scanning calorimetry. Effects of various parameters such as LC concentration, light intensity, and monomer functionality on the kinetics were investigated. Phase transition temperature versus composition phase diagrams were established by means of optical microscopy and differential scanning calorimetry for mixtures of triacrylate/liquid crystal (LC) before photopolymerization and after exposing to ultra violet (UV) irradiation under various reaction times. The snapshot phase diagram of the reacting mixtures exhibited isotropic gel, isotropic liquid + nematic, and narrow pure nematic coexistence regions. These coexistence regions were further confirmed by morphological changes of the polymer dispersed liquid crystal films as functions of temperature and concentration using polarized optical microscopy.

[1]  P. Flory Thermodynamics of High Polymer Solutions , 1941 .

[2]  Igor V. Khudyakov,et al.  Kinetics of Photopolymerization of Acrylates with Functionality of 1−6 , 1999 .

[3]  Kristi S. Anseth,et al.  Reaction behaviour and kinetic constants for photopolymerizations of multi(meth)acrylate monomers , 1994 .

[4]  J. W. Doane,et al.  Polymer dispersed liquid crystals for display application , 1988 .

[5]  T. Kyu,et al.  Morphology Development and Dynamics of Photopolymerization-Induced Phase Separation in Mixtures of a Nematic Liquid Crystal and Photocuratives , 2000 .

[6]  K. Moussa,et al.  Real-time kinetic study of laser-induced polymerization , 1989 .

[7]  Birendra Bahadur,et al.  Liquid Crystals — Applications and Uses , 1992 .

[8]  D. Neckers,et al.  Photopolymerization studies using visible light photoinitiators , 1992 .

[9]  A. McCormick,et al.  A Kinetic Model for Radical Trapping in Photopolymerization of Multifunctional Monomers , 2000 .

[10]  S. P. Pappas,et al.  Radiation curing: Science and technology , 1992 .

[11]  C. Bowman,et al.  Reaction Diffusion Enhanced Termination in Polymerizations of Multifunctional Monomers , 1993 .

[12]  C. Bowman,et al.  The effect of primary cyclization on free radical polymerization kinetics: experimental characterization , 2003 .

[13]  S. D. Hudson,et al.  Morphology of diacrylate copolymer networks formed in liquid crystalline media , 1998 .

[14]  Young-Hye Cho,et al.  Effect of polymer structure on the morphology and electro-optic properties of UV curable PNLCs , 2000 .

[15]  T. Kyu,et al.  Influence of acrylate arm topology on phase diagrams of mixtures of multiarm acrylate photocurative monomers and nematic liquid crystals. , 2007, The journal of physical chemistry. B.

[16]  A. J. Lovinger,et al.  Morphological Investigation of UV-Curable Polymer-Dispersed Liquid-Crystal (PDLC) Materials , 1994 .

[17]  K. Kim,et al.  Phase Diagram and Photopolymerization Behavior of Mixtures of UV-Curable Multifunctional Monomer and Low Molar Mass Nematic Liquid Crystal , 1998 .

[18]  A. R. Shultz,et al.  A calorimetric study of acrylate photopolymerization , 1979 .

[19]  C. Macosko,et al.  Kinetic model for crosslinking free radical polymerization including diffusion limitations , 1992 .

[20]  R. G. Gossink,et al.  The effects of volume relaxation and thermal mobilization of trapped radicals on the final conversion of photopolymerized diacrylates , 1984 .

[21]  C. Decker,et al.  Interpenetrating polymer networks. I. Photopolymerization of multiacrylate systems , 1994 .

[22]  B. Kim,et al.  Polymer network liquid crystals from u.v. curable polyurethane acrylate , 1998 .

[23]  M. Huggins Solutions of Long Chain Compounds , 1941 .

[24]  R. Sutherland,et al.  Influence of photopolymerization reaction kinetics on diffraction efficiency of H-PDLC undergoing photopatterning reaction in mixtures of acrylic monomer/nematic liquid crystals , 2007 .

[25]  L. V. Natarajan,et al.  Holographic Polymer-Dispersed Liquid Crystals (H-PDLCs)1 , 2000 .

[26]  S. D. Hudson,et al.  Morphology of Polymer-Stabilized Liquid Crystals , 1995 .

[27]  C. Decker Photoinitiated Curing of Multifunctional Monomers , 1993, Chimia (Basel).

[28]  Kristi S. Anseth,et al.  Kinetic evidence of reaction diffusion during the polymerization of multi(meth)acrylate monomers , 1994 .

[29]  J. Lindsey,et al.  PhotochemCAD ‡ : A Computer‐Aided Design and Research Tool in Photochemistry , 1998 .

[30]  William B. Liechty,et al.  The influence of N-vinyl-2-pyrrolidinone in polymerization of holographic polymer dispersed liquid crystals (HPDLCs) , 2006 .

[31]  K. Moussa,et al.  A new method for monitoring ultra‐fast photopolymerizations by real‐time infra‐red (RTIR) spectroscopy , 1988 .

[32]  N. Clark,et al.  Phase behaviour and electro-optic characteristics of a polymer stabilized ferroelectric liquid crystal , 1995 .

[33]  T. Kyu,et al.  Phase Behavior of Mixtures of Low Molar Mass Nematic Liquid Crystal and in Situ Photo-Cross-Linked Polymer Network , 1999 .