Liquid Crystalline Polymers XIII Main Chain Thermotropic Copoly (Arylidene-Ether)s Containing 4-Teriary Butyl-Cyclohexanone Moiety Linked with Polymethylene Spacers

Abstract

A new homologous series of thermotropic liquid crystalline copoly(arylidene-ether)s based on 4-teriary butyl cyclohexanone moiety were synthesized by solution polycondensation of 4,4’-diformyl-α,ω-diphenoxyalkanes, Ia-d or 4,4’- diformyl-2,2’-dimethoxy-α,ω-diphenoxyalkanes IIa-d with the 4-teriary butyl-cyclohexanone III and cyclopentanone. A model compound IV was synthesized from the monomer III with benzaldehyde and characterized by elemental and spectral analyses. The inherent viscosities of the resulting polymers were in the range 0.22 - 0.92 dI/g. All the copoly(arylidene-ether)s were insoluble in common organic solvents but dissolved completely in concentrated H2SO4 and formic acid. The mesomorphic properties of these polymers were studied as a function of the diphenoxyalkane space length. Their thermotropic liquid crystalline properties were examined by DSC and optical polarizing microscopy and demonstrated that the resulting polymers form nematic mesophases over wide temperature ranges. The thermogravimetric analyses of those polymers were evaluated by TGA and DSC measurements and correlated to their structural units. X-Ray analysis showed that copolymers having some degree of crystallinity in the region 2q = 5° -60°. In addition, the morphological properties of selected examples were tested by Scanning electron microscopy.

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N. Al-Muaikel and K. Aly, "Liquid Crystalline Polymers XIII Main Chain Thermotropic Copoly (Arylidene-Ether)s Containing 4-Teriary Butyl-Cyclohexanone Moiety Linked with Polymethylene Spacers," Open Journal of Organic Polymer Materials, Vol. 3 No. 1, 2013, pp. 19-26. doi: 10.4236/ojopm.2013.31004.

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1] L. L. Chapoy, “Recent advances in Liquid Crystalline Polymers,” Elsevier, London, 1986.
[2] A. Blumstein, “Polymeric Liquid Crystals,” Plenum Press, New York, 1985.
[3] A. G. Grin and J. F. Johnson, “Liquid Crystals and Ordered Fluids,” Plenum Press, New York, 1984. doi10.1007/978-1-4613-2661-8
[4] W. J. Jackson Jr., “Liquid Crystal Polymers. XI. Liquid Crystal Aromatic Polyesters: Early History and Future Trends,” Molecular Crystals and Liquid Crystals, Vol. 169, 1989, pp. 23-49.
[5] A. C. Grien and S. J. Haren, Journal of Polymer Science Part B-Polymer Physics, Vol. 19, 1986, p. 951.
[6] W. J. Jackson Jr., Polymer Journal, Vol. 12, 1980, p. 154.
[7] D. Acierno, F. P. La Mantina, G. Polizzotti, A. Giferri, W. R. Krigbaum and R. Koiek, “Thermotropic Homopolyesters. IV. Study of Fiber Formation,” Journal of Polymer Science Part B-Polymer Physics, 1983, Vol. 21, No. 10, pp. 2027-2036.
[8] J. J. Ge, M. Guo, Z. Zhang, P. S. Honigfort, S.-Y. Wang, F. W. Harris, et al., “Phase Structures, Transition Behavior, and Surface Alignment in Polymers Containing Rigid-Rod Backbones with Flexible Side Chains. 4. Solid-State 13C NMR Studies of Molecular Motions in PEFBPs(n) (n = 10 and 11),” Macromolecules, Vol. 33, No. 11, 2000, pp. 3983-3992. doi10.1021/ma981970y
[9] J. Ruan, J. J. Ge, A. Zhang, S. Jin, S.-Y. Wang, F. W. Harris, et al., “Polymorphous Structures and Their Phase Relationships in a Main-Chain/Side-Chain Liquid Crystalline Polyester,” Macromolecules, Vol. 35, No. 3, 2002, pp. 736-745. doi10.1021/ma0115702
[10] Y. S. Hu, R. Y. F. Liu, D. A. Schiraldi, A. Hiltner and E. Baer, “Solid-State Structure of Copolyesters Containing a Mesogenic Monomer,” Macromolecules, Vol. 37, No. 6, 2004, pp. 2128-2135. doi10.1021/ma030439m
[11] J. Watanabe and M. Hayashi, “Thermotropic Liquid Crystals of Polyesters Having a Mesogenic P,P’-Bibenzoate Unit. 2. X-Ray Study on Smectic Mesophase Structures of BB-5 and BB-6,” Macromolecules, Vol. 22, No. 10, 1989, pp. 4083-4088. doi10.1021/ma00200a046
[12] J. Watanabe, Y. Nakata and K. Simizu, “Frustrated Bilayer Smectic Phase in Main-Chain Polymers with Two Different Spacers,” Journal de Physique II, Vol. 4, 1994, pp. 581-588
[13] J. Watanabe, M. Hayashi, A. Morita and M. Tokita, “Thermotropic Liquid Crystals of Main-Chain Polyesters Having a Mesogenic 4,4’-Biphenyldicarboxylate Unit. 6. Chiral Mesophases of Polyesters with a (S)-2-Methylbutylene Spacer,” Macromolecules, Vol. 28, No. 24, 1995, pp. 8073-8079. doi10.1021/ma00128a015
[14] K. I. Aly, “Liquid Crystalline Polymers: 2. Synthesis and Thermotropic Studies of Poly(Arylidene-Ether)s Containing a Cyclopentanone Moiety in the Main Chain,” High Performance Polymers, Vol. 11, No. 4, 1999, pp. 437-452. doi10.1088/0954-0083/11/4/308
[15] K. I. Aly and A. S. Hammam, “Liquid Crystalline Polymers: I. Main Chain Thermotropic Poly(Arylidene-Ether)s Containing Cyclopentanone Moiety Linked with Polymethylene Spacers,” European Polymer Journal, Vol. 36, No. 9, 1999, pp. 1933-1942. doi10.1016/S0014-3057(99)00253-0
[16] K. I. Aly “Liquid Crystalline Polymers 3. Synthesis and Liquid Crystal Properties of Thermotropic Poly(Arylidene-Ether)s and Copolymers Containing Cycloalkanones Moiety in the Polymer Backbone,” Journal of Macromolecular Science Chemistry A, Vol. 37, 2000, pp. 93-115
[17] K. I. Aly, Ahmed, R.A. “Liquid Crystalline Polymers V. Thermotropic Liquid Crystalline Poly(Azomethine-Ether)s Containing a Cycloalkanone Moiety in the Polymer Backbone,” Liquid Crystals, Vol. 27, No. 4, 1999, pp. 451-458. doi10.1080/026782900202633
[18] K. I. Aly, M. A. Hussein and M. M. Sayed, “Liquid Crystalline Polymers X. Main Chain thermotropic Poly (Arylidene-Ether)s Containing 4-Teriary Butyl-Cyclohexanone Moiety Linked With Polymethylene Spacers,” Liquid Crystals, under Publication, 2013.
[19] B.-K. Chen, S.-Y. Tsay and J.-Y. Chen, “Synthesis and Properties of Liquid Crystalline Polymers with Low Tm and Broad Mesophase Temperature Ranges” Polymer, Vol. 46, No. 20, 2005, pp. 8624-8633. doi10.1016/j.polymer.2005.06.084
[20] H. Catalgil-Giz and A. T. Giz, “Compensating the Composition Drift in Reactivity Ratio Calculations for Copolymerizations Carried to High Conversions,” Macromolecular Chemistry and Physics, Vol. 195, No. 3, 1994, pp. 855-864. doi10.1002/macp.1994.021950304
[21] A. Ravikrishnan, P. Sudhakara and P. Kannan, “Liquid Crystalline and Photoactive Poly[4,4’-Stilbeneoxy]Alkylbiphenylphosphates,” Polymer Degradation and Stability, Vol. 93, No. 8, 2008, pp. 1564-1570. doi10.1016/j.polymdegradstab.2008.05.017
[22] S. Y. Lu and I. Hamerton, “Recent Developments in the Chemistry of Halogen-Free Flame Retardant Polymers,” Progress in Polymer Science, Vol. 27, No. 8, 2002, pp. 1661-1712. doi10.1016/S0079-6700(02)00018-7
[23] J. Canadell, A. Mantecón and V. Cádiz “Phosphorus-Containing Thermosets Obtained by Cationic Copolymerisation of Glycidyl Compounds with a Spiroorthoester or γ-Butyrolactone,” Polymer Degradation and Stability, Vol. 93, No. 1, 2008, pp. 59-67. doi10.1016/j.polymdegradstab.2007.10.023
[24] X. H. Du, Y. Z. Wang, X. T. Chen and X. D. Tang, “Properties of Phosphorus-Containing Thermotropic Liquid Crystal Copolyester/Poly(Ethylene Terephthalate) Blends,” Polymer Degradation and Stability, Vol. 88, No. 1, 2005, pp. 52-56. doi10.1016/j.polymdegradstab.2004.02.018
[25] D. Srividhya, S. Senthil and P. Kannan, “Thermotropic Liquid-Crystalline Polyphosphate Esters Containing Phenolphthalein Moiety,” Journal of Applied Polymer Science, Vol. 92, No. 1, 2004, pp. 194-200. doi10.1002/app.13431

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