Implementation qrcode in Java PROPERTIES
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Scheme 12.7 Preparation of azo BCs by supramolecular self-assembly between a BC and a low molecular weight azo compound. Source: Reproduced from Sidorenko et al., 2003.
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12.2.4. Special Reactions
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Some special reaction with a particularly designed route can be used to synthesize azo BCs. For instance, a series of poly(vinyl ether)-based azo LCBCs were synthesized by using living cationic polymerization and free-radical polymerization techniques (Serhatli and Serhatli, 1998). As shown in Scheme 12.8, 4.4uazobis(4-cyano pentanol) (ACP) was used to couple quantitatively two wellde ned polymers of LC living poly(vinyl ether), initiated by the methyl tri uoromethane sulfonate/tetrahydrothiophene system. Then the ACP in the main chain was thermally decomposed to produce polymeric radical, which was used to initiate the polymerization of MMA or styrene to obtain PMMA-based or PS-based azo BCs (AB or ABA types).
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12.3. PROPERTIES 12.3.1. Basic Properties
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Azo BCs are multifunctional polymeric materials, which combine the photochemical properties of azo polymers and the microphase separation of functional BCs. On the one hand, the azo block and the other segments cannot be miscible, unlike statistically random copolymers in which the azo moieties are dispersed homogeneously over the whole bulk lms. On the other hand, the azo BCs cannot form macroscopically phase-separated structures like polymer blends (Bates and Fredrichson, 1999). The azo moiety may play the roles of both mesogen and photosensitive chromophore, when it is attached to the polymer main chain by a longer soft spacer. Both the photoisomerization and the phase transition of the LC to the isotropic phase are involved in the process of microphase separation because of
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CH3 CH3 CH2 CH OCH2CH2CH2 C N N C CH2CH2CH2O CH CH2 CN CN O O R1 R1 ABA triblock copolymer
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AB diblock copolymer
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Scheme 12.8 Preparation of azo BCs by using living cationic polymerization and free-radical polymerization techniques. Source: Reproduced from Serhatli and Serhatli, 1998.
the immiscibility between the azo blocks and non-azo blocks. As shown in Fig. 12.2, all the processes in the microphase separation at different temperatures might be in uenced by the azo photoisomerization, andthe microphase-separated nanostructures in azo BC lms could have effect on the photochemical behavior of azo blocks and vice versa (Cui et al., 2003). The photochemical control and supramolecular self-assembly make the azo BCs in solid state superior to that of azo homopolymers or azo random copolymers. On the one hand, the azo BCs inherit most of the excellent properties of azo homopolymers (Ichimura, 2000), such as trans cis photoisomerization, photoselective alignment with azo transition moments almost perpendicular to the polarization direction of the actinic light, and photochemical phase transition, since the trans-azo can be a mesogen because its molecular shape is rodlike, whereas the cis-azo never shows any LC phase because of its bent shape. All the illustrations of the photosensitive performances are shown in Fig. 12.3 (Yu et al., 2005a).
Supramolecular self-assembly in azo BC films Azo BC in isotropic melt Order disorder transition Microphase separation Temperature T > TLC Rubbery or LC T > Tg Vis, trans Glassy, crystal, or LC Glassy or LC UV Rubbery or LC T > Tg T > Tm
Azo block in majority phases
cis Azo block in minority phases
Figure 12.2. Microphase separation and azo photoisomerization in bulk lms of well-de ned azo BCs. TLC is LC isotropic phase transition temperature.
Photoisomerization UV
9A 5.5 A
Vis, cis
Photoselective alignment
Transition moment
A k cos2
Linearly polarized light (LPL) Photochemical phase transition Order LC phase
UV Vis, Isotropic phase
Figure 12.3. Properties of azo BCs inherited from azo homopolymers. A is the absorption of azo chromophores, y represents the angle between the polarization direction of the linearly polarized light and the transition moment of an azo moiety.
On the other hand, the well-de ned azo BCs show excellent features different from azo random copolymers. Recently, the performance of molecular cooperative motion (MCM) between azo moieties and other photoinert groups has been studied in azo triblock copolymers with speci cally designed structures (Yu et al., 2007). Triggered by a linearly polarized laser beam at 488 nm, the azo chromophores became aligned by the Weigert effect, then the photoinert groups were oriented together with the azo moieties under the function of MCM, although they do not absorb the actinic light (Wu et al., 1998a,b). When the azo and the photoinert mesogens form the majority phase (continuous matrix), the photocontrol orientation can be transferred to the microphase-separated nanodomains inside the LC matrix owing to SMCM (see Fig. 12.4; Yu et al., 2005c). Interestingly, the photoinduced MCM can be con ned in nanoscaled regions by microphase separation when the azo and the other mesogenic blocks are situated in the minority phases (separated phases) (Yu et al., 2007a). No obvious in uence on the substrate was detected since the photoinduced alignment occurred in the intermittent phases, and the phototriggered oriented motion was disrupted by the glassy substrates of PMMA or PS. Thanks to the nanoscaled MCM, the scattering of visible light can be avoided by con ning the mesogenic domain to the nanoscale, which improves the optical properties of azo BC lms. Accordingly, thick lms (B200 mm) with high transparency and low absorption based on the microphase separation of wellde ned azo BCs have been obtained, enabling them to record Bragg-type gratings for volume storage. Figure 12.5 gives the possible scheme of Bragg diffraction based on transparent thick lms (B200 mm) of the well-de ned azo triblock copolymer. Furthermore, the stability of the photoinduced orientation in lms was greatly improved by decreasing the photosensitive azo content in BC composition.
Molecular cooperative motion (MCM)
Supramolecular cooperative motion (SMCM)
Figure 12.4. Photoinduced cooperative motion in bulk lms of azo BCs. Azo in the minority phase (left) and azo in the majority phase (right). Source: Reproduced from Yu et al., 2005c; 2007a. See color insert.