Abstract
Mesogen-jacketed liquid crystalline polymers (MJLCPs) are rigid side-chain polymers that can form columnar and smectic liquid crystalline (LC) phases. Their liquid crystallinity is dependent on the molecular weights (MWs), and many MJLCPs exhibit reentrant phase behaviors. The size of the structure formed by an MJLCP, either columnar or smectic, is directly correlated with the size of the side chain. While the first MJLCPs have laterally attached mesogenic side chains, bulky side chains that are not mesogenic can also be used to construct MJLCPs. The “jacketing” effect, i.e., the steric hindrance caused by the densely packed side chains, forces the polymer backbone to take an extended-chain conformation. Many factors, such as MW, backbone flexibility, tail length, and architecture, influence the phase behaviors of MJLCPs. With the understanding of the chemical structure-phase behavior relationships, molecular design for MJLCPs can be executed by carefully choosing molecular parameters including the shape and rigidity of the side chain, the structure of the polymer backbone, and so on. MJLCPs can be synthesized by radical polymerizations that do not require highly pure solvents and reagents. Many controlled/living radical polymerization methods, such as nitroxide-mediated radical polymerization (NMRP) and atom transfer radical polymerization (ATRP), can also be employed. Recently, another living polymerization method, ring-opening metathesis polymerization (ROMP), has been applied in the synthesis of MJLCPs with a polynorbornene backbone. With the use of such controlled polymerization methods, the length of the rodlike or sheetlike MJLCP chain can be tuned by adjusting the MW. In addition, MJLCPs can also be synthesized by polymer reactions from prepolymers like poly(methylsiloxane)s. Furthermore, MJLCPs can also be obtained by taking advantage of supramolecular chemistry, with the application of hydrogen bonding, ionic interaction, and other non-covalent interactions. Future directions in the study of MJLCPs will be to address the main challenges by designing monomers that can be more easily synthesized and polymerized, establishing cost- and time-saving synthetic methods, applying calculation and computer simulation that can accurately predict phase behaviors and guide molecular design, and developing functional MJLCP materials.
References
Chai CP, Zhu XQ, Wang P, Ren MQ, Chen XF, Xu YD, Fan XH, Ye C, Chen EQ, Zhou QF (2007) Synthesis and phase structures of mesogen-jacketed liquid crystalline polymers containing 1,3,4-oxadiazole based side chains. Macromolecules 40:9361–9370
Chen L, Chen YW, Zha DJ, Yang Y (2006a) Synthesis and properties of polyacetylenes with directly attached bis(4-alkoxyphenyl)terephthalate mesogens as pendants. J Polym Sci Part A Polym Chem 44:2499–2509
Chen XF, Tenneti KK, Li CY, Bai YW, Zhou R, Wan XH, Fan XH, Zhou QF (2006b) Design, synthesis, and characterization of bent-core mesogen-jacketed liquid crystalline polymers. Macromolecules 39:517–527
Chen S, Gao LC, Zhao XD, Chen XF, Fan XH, Xie PY, Zhou QF (2007) Synthesis and properties of mesogen-jacketed liquid crystalline polymers with asymmetry mesogenic core. Macromolecules 40:5718–5725
Chen S, Zhang L-Y, Gao L-C, Chen X-F, Fan X-H, Shen Z, Zhou Q-F (2009) Influence of alkoxy tail length and unbalanced mesogenic core on phase behavior of mesogen-jacketed liquid crystalline polymers. J Polym Sci Part A Polym Chem 47:505–514
Chen X-F, Shen Z, Wan X-H, Fan X-H, Chen E-Q, Ma Y, Zhou Q-F (2010) Mesogen-jacketed liquid crystalline polymers. Chem Soc Rev 39:3072–3101
Cheng YH, Chen WP, Shen Z, Fan XH, Zhu MF, Zhou QF (2011a) Influences of hydrogen bonding and peripheral chain length on Mesophase structures of Mesogen-jacketed liquid crystalline polymers with amide side-chain linkages. Macromolecules 44:1429–1437
Cheng YH, Chen WP, Zheng C, Qu W, Wu HL, Shen ZH, Liang DH, Fan XH, Zhu MF, Zhou QF (2011b) Synthesis and phase structures of Mesogen-jacketed liquid crystalline polyelectrolytes and their ionic complexes. Macromolecules 44:3973–3980
Cui JX, Lu XC, Liu AH, Wan XH, Zhou QF (2009) Long-range chirality transfer in free radical polymerization of bulky vinyl monomers containing laterally attached p-Terphenyl groups. Macromolecules 42:7678–7688
Cui JX, Liu AH, Cao HQ, Wan XH, Zhou QF (2010) Unusual chiral transfer in radical copolymerization of vinyl monomers bearing side-on p-Terphenyl pendants. Chemistry-an Asian J 5:1139–1145
Finkelmann H, Ringsdorf H, Wendorff JH (1978) Model considerations and examples of enantiotropic liquid-crystalline polymers – Polyreactions in ordered systems. 14. Makromol Chem-Macromol Chem Phys 179:273–276
Gao L-C, Fan X-H, Shen Z-H, Chen X, Zhou Q-F (2009) Jacketed polymers: controlled synthesis of mesogen-jacketed polymers and block copolymers. J Polym Sci Part A Polym Chem 47:319–330
Gopalan P, Ober CK (2001) Highly reactive 2,5-disubstituted styrene-based monomer polymerized via stable free radical polymerization: effect of substitution and liquid crystallinity on polymerization. Macromolecules 34:5120–5124
Gopalan P, Andruzzi L, Li XF, Ober CK (2002) Fluorinated mesogen-jacketed liquid-crystalline polymers as surface-modifying agents: design, synthesis and characterization. Macromol Chem Phys 203:1573–1583
Hardouin F, Mery S, Achard MF, Noirez L, Keller P (1991) Evidence for a jacketed nematic polymer. J Phys II 1:511–520
Hardouin F, Leroux N, Mery S, Noirez L (1992) Small-angle neutron-scattering experiments on side-on fixed liquid –crystal polysiloxanes. J Phys II 2:271–278
Hessel F, Finkelmann H (1985) A new class of liquid-crystal side-chain polymers – mesogenic groups laterally attached to the polymer backbone. Polym Bull 14:375–378
Hessel F, Finkelmann H (1986) Optical biaxiality of nematic LC-side chain polymers with laterally attached mesogenic groups. Polym Bull 15:349–352
Jin H, Xu YD, Shen ZH, Zou DC, Wang D, Zhang W, Fan XH, Zhou QF (2010) Jacketed polymers with dendritic carbazole side groups and their applications in blue light-emitting diodes. Macromolecules 43:8468–8478
Lin JP (1997) Re-entrant isotropic transition of polypeptide liquid crystal. Polymer 38:4837–4841
Liu P, Xie H, Tang H, Zhong G, Zhang H (2012) Unusual effect of molecular weight and concentration on thermoresponsive behaviors of well-defined water-soluble semirigid polymers. J Polym Sci Part A Polym Chem 50:3664–3673
Liu P, Tan Q, Xiang L, Zhang H (2013) Steric hindrance effect on thermo-responsive behaviors of well-defined water-soluble semi-rigid polymers. J Polym Sci Part A Polym Chem 51:3429–3438
Ma ZY, Zheng C, Shen ZH, Liang DH, Fan XH (2012) Synthesis and properties of comb polymers with semirigid mesogen-jacketed polymers as side chains. J Polym Sci Part A Polym Chem 50:918–926
McArdle CB (1989) Side chain liquid crystal polymers. Blackie and Son Ltd, Glasgow
Mei X, Liu AH, Cui JX, Wan XH, Zhou QF (2008) Synthesis and characterization of branched mesogen-jacketed liquid crystal polymers based on 2,5-bis[(4-methoxyphenyl)oxycarbonyl]styrene and 4-chloromethylstyrene. Macromolecules 41:1264–1272
Mei X, Chu Y, Cui J, Shen Z, Wan X (2010) Steric interaction between flexible main chain and nonmesogenic cyclic pendants leading to thermotropic liquid crystalline property. Macromolecules 43:8942–8949
Mei X, Zhang J, Shen ZH, Wan XH (2012) Synthesis, liquid crystalline properties, and lithium complexes of vinyl polymers with cyclic pendants containing ethylene oxide units. Polym Chem 3:2857–2866
Pan QW, Gao LC, Chen XF, Fan XH, Zhou QF (2007) Star mesogen-jacketed liquid crystalline polymers with silsesquioxane core: synthesis and characterization. Macromolecules 40:4887–4894
Papkov VS, Ilina MN, Zhukov VP, Tsvankin DJ, Tur DR (1992) UNUSUAL PHASE-BEHAVIOR OF SOME POLY(DIALKOXYPHOSPHAZENES). Macromolecules 25:2033–2040
Peng H, Chen Y, Chen L, He X, Li F (2010) Luminescent Mesogen jacketed poly(1-alkyne) bearing lateral Terphenyl with Hexyloxy tail. J Polym Sci Part A Polym Chem 48:5679–5692
Percec V, Tomazos D (1992) Molecular engineering of side-chain liquid-crystalline polymers by living cationic polymerization. Adv Mater 4:548–561
Pragliola S, Ober CK, Mather PT, Jeon HG (1999) Mesogen-jacketed liquid crystalline polymers via stable free radical polymerization. Macromol Chem Phys 200:2338–2344
Pugh C, Schrock RR (1992) Synthesis of side-chain liquid-crystal polymers by living ring-opening metathesis polymerization. 3. Influence of molecular-weight, interconnecting unit, and substituent on the mesomorphic behavior of polymers with laterally attached mesogens. Macromolecules 25:6593–6604
Qu W, Zhu XQ, Chen JH, Niu L, Liang DH, Fan XH, Shen ZH, Zhou QF (2014) Synthesis and characterization of a Mesogen-jacketed polyelectrolyte. Macromolecules 47:2727–2735
Rosen BM, Wilson CJ, Wilson DA, Peterca M, Imam MR, Percec V (2009) Dendron-mediated self-assembly, disassembly, and self-organization of complex systems. Chem Rev 109:6275–6540
Rudick JG, Percec V (2008) Induced helical backbone conformations of self-organizable dendronized polymers. Acc Chem Res 41:1641–1652
Tu HL, Zhang D, Wan XH, Chen XF, Liu YX, Zhang HL, Zhou QF (1999) Mesogen-jacketed liquid crystalline polymer with flexible dicyclopentyl terephthalate as side group. Macromol Rapid Commun 20:549–551
Tu HL, Wan XH, Liu YX, Chen XF, Zhang D, Zhou QF, Shen ZH, Ge JJ, Jin S, Cheng SZD (2000) Self-assembly-induced supramolecular hexagonal columnar liquid crystalline phase using laterally attached nonmesogenic templates. Macromolecules 33:6315–6320
Wan XH, Zhang F, Wu PQ, Zhang D, Feng XD, Zhou QF (1995) Characterization of the chain stiffness for a mesogen-jacketed liquid-crystal polymer – poly(2,5-bis[(4-methoxybenzoyl)oxy]styrene). Macromol Symp 96:207–218
Wan XH, Tu HL, Tu YF, Zhang D, Sun L, Zhou QF, Dong YP, Tang M (1999) Nitroxide-mediated free radical synthesis of mesogen-jacketed liquid crystal polymers. Chin J Polym Sci 17:189–192
Wang X-J, Zhou Q-F (2004) Liquid crystalline polymers. World Scientific Publishing Co. Pte. Ltd, Singapore
Wang XZ, Zhang HL, Shi DC, Chen JF, Wang XY, Zhou QF (2005) Synthesis of a novel star liquid crystal polymer using trifunctional initiator via atom transfer radical polymerization. Eur Polym J 41:933–940
Xu GZ, Wu W, Shen DY, Hou JN, Zhang SF, Xu M, Zhou QF (1993a) Morphological-study of oriented films obtained from side-chain liquid-crystalline polymers. Polymer 34:1818–1822
Xu GZ, Wu W, Xu M, Zhou QF (1993b) Banded texture in oriented films of a side-chain liquid-crystalline polymer. J Polym Sci B Polym Phys 31:229–230
Xu YD, Yang Q, Shen ZH, Chen XF, Fan XH, Zhou QF (2009) Effects of mesogenic shape and flexibility on the phase structures of mesogen-jacketed liquid crystalline polymers with bent side groups containing 1,3,4-oxadiazole. Macromolecules 42:2542–2550
Xu YD, Qu W, Yang Q, Zheng JK, Shen ZH, Fan XH, Zhou QF (2012) Synthesis and characterization of mesogen-jacketed liquid crystalline polymers through hydrogen-bonding. Macromolecules 45:2682–2689
Yang Q, Jin H, Xu YD, Wang P, Liang XC, Shen ZH, Chen XF, Zou DC, Fan XH, Zhou QF (2009) Synthesis, photophysics, and electroluminescence of mesogen-jacketed 2D conjugated copolymers based on fluorene-thiophene-oxadiazole derivative. Macromolecules 42:1037–1046
Yang H, Zhang F, Lin B-P, Keller P, Zhang X-Q, Sun Y, Guo L-X (2013) Mesogen-jacketed liquid crystalline polymers and elastomers bearing polynorbornene backbone. J Mater Chem C 1:1482–1490
Ye C, Zhang HL, Huang Y, Chen EQ, Lu YL, Shen DY, Wan XH, Shen ZH, Cheng SZD, Zhou QF (2004) Molecular weight dependence of phase structures and transitions of mesogen-jacketed liquid crystalline polymers based on 2-vinylterephthalic acids. Macromolecules 37:7188–7196
Yin XY, Ye C, Ma X, Chen EQ, Qi XY, Duan XF, Wan XH, Cheng SZD, Zhou QF (2003) Manipulating supramolecular self-assembly via tailoring pendant group size of linear vinyl polymers. J Am Chem Soc 125:6854–6855
Yu ZN, Wan XH, Tu HL, Chen XF, Zhou QF (2003a) A novel thermotropic behavior of a mesogen-jacketed liquid crystal polymer. Acta Polym Sin:430–433
Yu ZN, Wan XH, Zhang HL, Chen XF, Zhou QF (2003b) A free radical initiated optically active vinyl polymer with memory of chirality after removal of the inducing stereogenic center. Chem Commun:974–975
Yu ZQ, Lam JWY, Zhao KQ, Zhu CZ, Yang S, Lin JS, Li BS, Liu JH, Chen EQ, Tang BZ (2013) Mesogen jacketed liquid crystalline polyacetylene containing triphenylene discogen: synthesis and phase structure. Polym Chem 4:996–1005
Zhang D, Liu YX, Wan XH, Zhou QF (1999) Synthesis of a new side-chain type liquid crystal polymer poly[dicyclohexyl vinylterephthalate]. Macromolecules 32:4494–4496
Zhang H, Yu Z, Wan X, Zhou QF, Woo EM (2002) Effects of molecular weight on liquid-crystalline behavior of a mesogen-jacketed liquid crystal polymer synthesized by atom transfer radical polymerization. Polymer 43:2357–2361
Zhang LY, Chen S, Zhao H, Shen ZH, Chen XF, Fan XH, Zhou QF (2010) Synthesis and properties of a series of mesogen-jacketed liquid crystalline polymers with polysiloxane backbones. Macromolecules 43:6024–6032
Zhang Q-K, Tian H-J, Li C-F, Zhu Y-F, Liang Y, Shen Z, Fan X-H (2014) Synthesis and phase behavior of a new 2-vinylbiphenyl-based mesogen-jacketed liquid crystalline polymer with high glass transition temperature and low threshold molecular weight. Polym Chem 5:4526–4533
Zhao YF, Fan XH, Wan XH, Chen XF, Yi Y, Wang LS, Dong X, Zhou QF (2006) Unusual phase behavior of a mesogen-jacketed liquid crystalline polymer synthesized by atom transfer radical polymerization. Macromolecules 39:948–956
Zhou QF, Li HM, Feng XD (1987) Synthesis of liquid-crystalline polyacrylates with laterally substituted mesogens. Macromolecules 20:233–234
Zhou QF, Zhu XL, Wen ZQ (1989) Liquid-crystalline side-chain polymers without flexible spacer. Macromolecules 22:491–493
Zhou QF, Wan XH, Zhu XL, Zhang F, Feng XD (1993) Restudy of the old poly-2,5-di(benzoyloxy)styrene as a new liquid-crystal polymer. Mol Cryst Liq Cryst 231:107–117
Zhu YF, Guan XL, Shen ZH, Fan XH, Zhou QF (2012) Competition and promotion between two different liquid-crystalline building blocks: Mesogen-jacketed liquid-crystalline polymers and triphenylene discotic liquid crystals. Macromolecules 45:3346–3355
Zhu YF, Tian HJ, Wu HW, Hao DZ, Zhou Y, Shen ZH, Zou DC, Sun PC, Fan XH, Zhou QF (2014a) Ordered nanostructures at two different length scales mediated by temperature: a triphenylene-containing mesogen-jacketed liquid crystalline polymer with a long spacer. J Polym Sci Part A Polym Chem 52:295–304
Zhu YF, Zhang ZY, Zhang QK, Hou PP, Hao DZ, Qiao YY, Shen ZH, Fan XH, Zhou QF (2014b) Mesogen-jacketed liquid crystalline polymers with a polynorbornene main chain: green synthesis and phase behaviors. Macromolecules 47:2803–2810
Zhu YF, Liu W, Zhang MY, Zhou Y, Zhang YD, Hou PP, Pan Y, Shen ZH, Fan XH, Zhou QF (2015) POSS-containing jacketed polymer: hybrid inclusion complex with hierarchically ordered structures at sub-10 nm and angstrom length scales. Macromolecules 48:2358–2366
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2019 Springer-Verlag GmbH Germany, part of Springer Nature
About this entry
Cite this entry
Shen, Z. (2019). Mesogen-Jacketed Liquid Crystalline Polymers: Molecular Design and Synthesis. In: Palsule, S. (eds) Polymers and Polymeric Composites: A Reference Series. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-37179-0_48-1
Download citation
DOI: https://doi.org/10.1007/978-3-642-37179-0_48-1
Received:
Accepted:
Published:
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-37179-0
Online ISBN: 978-3-642-37179-0
eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics