Structure Control of Liquid Crystalline Block Copolymers in Liquid⁃Phase Self⁃assembly

doi:10.19894/j.issn.1000-0518.210363

Chinese Journal of Applied Chemistry ›› 2021, Vol. 38 ›› Issue (10): 1255-1267.DOI: 10.19894/j.issn.1000-0518.210363

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Structure Control of Liquid Crystalline Block Copolymers in Liquid⁃Phase Self⁃assembly

Ai-Hua CHEN¹^,²(), Cheng-Yun ZHANG¹, Zi-Chao DENG¹, Ya-Lan SUN¹

¹School of Materials Science and Engineering，Beihang University，Beijing 100191，China
²Beijing Advanced Innovation Centre for Biomedical;Engineering，Beihang University，Beijing 100191，China

Received:2021-07-26 Accepted:2021-08-23 Published:2021-10-01 Online:2021-10-15
Contact: Ai-Hua CHEN
About author:chenaihua@buaa.edu.cn
Supported by:
National Natural Science Foundation of China(51472018);Beijing Natural Science Foundation of China(2202024)

Abstract

Abstract:

Liquid crystallization can be used as an external driving force to be introduced into the block copolymer self-assembly system to control the anisotropic morphology of the aggregates. The main chain type liquid crystalline has strong rigidity， so the polymerization is difficult. But the flexible spacer of the side-chain liquid crystalline is adjustable， and is suitable for living polymerization， so the self-assembly behavior of the side chain type liquid crystalline block copolymer has received extensive attention. In this review， combined with the liquid-phase self-assembly method of block copolymer aggregates， we summarize the research on the structure control of the side-chain liquid crystalline block copolymer solution self-assembly from the aspects of liquid crystalline mesogenic types， liquid crystalline phases state and their functionalizations. Finally， this review summarizes the limitations of the research work related to the self-assembly of side-chain liquid crystalline block copolymers， and looks forward to its development trends.

Key words: Side-chain liquid crystalline block copolymer, Solution self-assembly, Polymerization-induced self-assembly, Morphology control

CLC Number:

O631

Ai-Hua CHEN, Cheng-Yun ZHANG, Zi-Chao DENG, Ya-Lan SUN. Structure Control of Liquid Crystalline Block Copolymers in Liquid⁃Phase Self⁃assembly[J]. Chinese Journal of Applied Chemistry, 2021, 38(10): 1255-1267.

Figures/Tables 13

Fig.1 Solution self-assembly of liquid crystalline block copolymers containing cholesterol groups［30］

Fig.2 Supramolecular assembly of fluorinated liquid crystalline block copolymer P2VP-b-PFMA［34］

Fig.3 Solution self-assembly of three-arm dendritic amphiphilic liquid crystalline block copolymer containing azobenzene mesogen［42］

Fig.4 （a） Schematic diagram of the self-assembly of Janus single-stranded nanoparticles under photocrosslinking；（b） Phase diagram of particle morphology under different light time and PPEGMA mass fraction conditions［43］

Fig.5 Self-assembly of mesogen-jacketed liquid crystalline block copolymer solution to prepare polymer particles with reversed bicontinuous structure［46］

Fig.6 Schematic diagram of light-controlled "self-engulf" of PEO-b-PMAAz snowman-shaped Janus nanoparticles［35］

Fig.7 Polymerization-induced self-assembly of cholesteric liquid crystalline block copolymers［52］

Fig.8 PISA combined with seed method to prepare PDMA-b-PBzMA-b-PFMA triblock liquid crystal polymer nanoparticles［53］

Fig.9 （a） Polymerization-induced hierarchical self-assembly of PMAA-b-PMAAz into anisotropic polymer particles；（b） Phase diagram of PMAA-b-PMAAz particle morphology［57］

Fig.10 Polymerization-induced hierarchical self-assembly of block copolymers containing diphenylethylene mesogens into nanowires［58］

Fig.11 High magnification TEM photos and SAXS curves of （a） PLMA-b-PMAStb，（b） PDMA-b-PMA11Bi and （c） PMAA-b-PMAAz system nanoparticles［59］

Table 1 Thermal properties of different liquid crystalline homopolymers［59］

样品 Sample	转变温度		转变焓
样品 Sample	T_S-Sm^b/℃	T_Sm-I^c/℃	ΔH_S-Sm^b/（J·g^-1）	ΔH_Sm-I^c/（J·g^-1）
PMAAz₅₇^［60］	69.5	117.7	6.0	15.9
PMA11Bi₉₁^a	116.7	148.8	7.4	16.8
PMAStb₃₁^［60］	151.1	165.8	13.1	18.2

Fig.12 （a） PDMAEMA-b-PMMAz polymerization-induced self-assembly diagram；（b） Nanowire structure are obtained in linear PDMAEMA system；（c） “Necklace-like” nanofibers composed of square particles are obtained after charged；（d） “Holbrick-like” particles are obtained after cross-linking［61］

References 61

1	JACOB N I. Intermolecular and surface forces［M］. Amsterdam： Elsevier， 2011.
2	MAI Y， EISENBERG A. Self-assembly of block copolymers［J］. Chem Soc Rev， 2012， 41（18）： 5969.
3	TOY R， PEIRIS P M， GHAGHADA K B， et al. Shaping cancer nanomedicine： the effect of particle shape on the in vivo journey of nanoparticles［J］. Nanomedicine， 2014， 9（1）： 121-134.
4	GENG Y， DALHAIMER P， CAI S， et al. Shape effects of filaments versus spherical particles in flow and drug delivery［J］. Nat Nanotechnol， 2007， 2（4）： 249-255.
5	LI X， IOCOZZIA J， CHEN Y， et al. From precision synthesis of block copolymers to properties and applications of nanoparticles［J］. Angew Chem Int Ed， 2018， 57（8）： 2046-2070.
6	ALBIGÈS R， KLEIN P， ROI S， et al. Water-based acrylic coatings reinforced by PISA-derived fibers［J］. Polym Chem， 2017， 8（34）： 4992-4995.
7	ZHANG L， EISENBERG A. Multiple morphologies of “crew-cut” aggregates of polystyrene-b-poly（acrylic acid） block copolymers［J］. Science， 1995， 268（5218）： 1728-1731.
8	MAI Y， EISENBERG A. Self-assembly of block copolymers［J］. Chem Soc Rev， 2012， 41（18）： 5969.
9	ZHANG L， EISENBERG A. Multiple morphologies and characteristics of “crew-cut” micelle-like aggregates of polystyrene-b-poly（acrylic acid） diblock copolymers in aqueous solutions［J］. J Am Chem Soc， 1996， 118（13）： 3168-3181.
10	CAMERON N S， CORBIERRE M K， EISENBERG A. Asymmetric amphiphilic block copolymers in solution： a morphological wonderland［J］. Canadian J Chem， 1999， 77（8）： 1311-1326.
11	ZHANG L F， EISENBERG A. Formation of crew-cut aggregates of various morphologies from amphiphilic block copolymers in solution［J］. Polym Adv Technol， 1998， 9（10/11）： 677-699.
12	KIM H， KANG B， CHOI J， et al. Morphological behavior of A₂B block copolymers in thin films［J］. Macromolecules， 2018， 51（3）： 1181-1188.
13	HOEBEN F J M， JONKHEIJM P， MEIJER E W， et al. About supramolecular assemblies of π-conjugated systems［J］. Chem Rev， 2005， 105（4）： 1491-1546.
14	WARREN N J， ARMES S P. Polymerization-induced self-assembly of block copolymer nano-objects via RAFT aqueous dispersion polymerization［J］. J Am Chem Soc， 2014， 136（29）： 10174-10185.
15	CANNING S L， SMITH G N， ARMES S P. A critical appraisal of RAFT-mediated polymerization-induced self-assembly［J］. Macromolecules， 2016， 49（6）： 1985-2001.
16	CHEN S， SHI P， ZHANG W. In situ synthesis of block copolymer nano-assemblies by polymerization-induced self-assembly under heterogeneous condition［J］. Chinese J Polym Sci， 2017， 35（4）： 455-479.
17	DERRY M J， FIELDING L A， ARMES S P. Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization［J］. Prog Polym Sci， 2016， 52： 1-18.
18	MELLOT G， BEAUNIER P， GUIGNER J， et al. Beyond simple AB diblock copolymers： application of bifunctional and trifunctional RAFT agents to PISA in water［J］. Macromol Rapid Commun， 2019， 40（2）： 1800315.
19	ZHANG L， EISENBERG A. Thermodynamic vs kinetic aspects in the formation and morphological transitions of crew-cut aggregates produced by self-assembly of polystyrene-b-poly（acrylic acid） block copolymers in dilute solution［J］. Macromolecules， 1999， 32（7）： 2239-2249.
20	ZHANG L， EISENBERG A. Morphogenic effect of added ions on crew-cut aggregates of polystyrene-b-poly（acrylic acid） block copolymers in solutions［J］. Macromolecules， 1996， 29（27）： 8805-8815.
21	MAI Y， ZHOU Y， YAN D. Synthesis and size-controllable self-assembly of a novel amphiphilic hyperbranched multiarm copolyether［J］. Macromolecules， 2005， 38（21）： 8679-8686.
22	HONG H， MAI Y， ZHOU Y， et al. Self-assembly of large multimolecular micelles from hyperbranched star copolymers［J］. Macromol Rapid Commun， 2007， 28（5）： 591-596.
23	D'AGOSTO F， RIEGER J， LANSALOT M. RAFT-mediated polymerization-induced self-assembly［J］. Angew Chem Int Ed， 2020， 59（22）： 8368-8392.
24	MELLOT G， GUIGNER J， JESTIN J， et al. Bisurea-functionalized RAFT agent： a straightforward and versatile tool toward the preparation of supramolecular cylindrical nanostructures in water［J］. Macromolecules， 2018， 51（24）： 10214-10222.
25	MELLOT G， GUIGNER J M， BOUTEILLER L， et al. Templated PISA： driving polymerization-induced self-assembly towards fibre morphology［J］. Angew Chem Int Ed， 2019， 58（10）： 3173-3177.
26	GUERRE M， SEMSARILAR M， GODIARD F， et al. Polymerization-induced self-assembly of PVAc-b-PVDF block copolymers via RAFT dispersion polymerization of vinylidene fluoride in dimethyl carbonate［J］. Polym Chem， 2017， 8（9）： 1477-1487.
27	TRITSCHLER U， PEARCE S， GWYTHER J， et al. 50th anniversary perspective： functional nanoparticles from the solution self-assembly of block copolymers［J］. Macromolecules， 2017， 50（9）： 3439-3463.
28	BOISSÉ S， RIEGER J， DI-CICCO A， et al. Synthesis via RAFT of amphiphilic block copolymers with liquid-crystalline hydrophobic block and their self-assembly in water［J］. Macromolecules， 2009， 42（22）： 8688-8696.
29	周其凤，王新久. 液晶高分子［M］. 北京：科学出版社， 1994.
	ZHOU Q F， WANG X J. Liquid crystal polymers［M］. Beijing： Science Press， 1994.
30	PIÑOL R， JIA L， GUBELLINI F， et al. Self-assembly of PEG-b-liquid crystal polymer： the role of smectic order in the formation of nanofibers［J］. Macromolecules， 2007， 40（16）： 5625-5627.
31	JIA L， CAO A， LÉVY D， et al. Smectic polymer vesicles［J］. Soft Matter， 2009， 5（18）： 3446.
32	XING X， SHIN H， BOWICK M J， et al. Morphology of nematic and smectic vesicles［J］. Proc Natl Acad Sci， 2012， 109（14）： 5202-5206.
33	LI X， JIN B， GAO Y， et al. Monodisperse cylindrical micelles of controlled length with a liquid-crystalline perfluorinated core by 1D “self-seeding”［J］. Angew Chem Int Ed， 2016， 55（38）： 11392-11396.
34	JIN B， SANO K， AYA S， et al. One-pot universal initiation-growth methods from a liquid crystalline block copolymer［J］. Nat Commun， 2019， 10（1）： 2397.
35	TONG X， WANG G， SOLDERA A， et al. How can azobenzene block copolymer vesicles be dissociated and reformed by light？［J］. J Phys Chem B， 2005， 109（43）： 20281-20287.
36	HAN D， TONG X， ZHAO Y， et al. Block copolymers comprising π-conjugated and liquid crystalline subunits： induction of macroscopic nanodomain orientation［J］. Angew Chem Int Ed， 2010， 49（48）： 9162-9165.
37	ZHAO Y， TREMBLAY L， ZHAO Y. Doubly photoresponsive and water-soluble block copolymers： synthesis and thermosensitivity［J］. J Polym Sci， Part A： Polym Chem， 2010， 48（18）： 4055-4066.
38	FU S， ZHANG H， ZHAO Y. Optically and thermally activated shape memory supramolecular liquid crystalline polymers［J］. J Mater Chem C， 2016， 4（22）： 4946-4953.
39	FAN W， TONG X， LI G， et al. Photoresponsive liquid crystalline polymer single-chain nanoparticles［J］. Polym Chem， 2017， 8（22）： 3523-3529.
40	QU T， ZHAO Y， LI Z， et al. Micropore extrusion-induced alignment transition from perpendicular to parallel of cylindrical domains in block copolymers［J］. Nanoscale， 2016， 8（6）： 3268-3273.
41	ZHENG X， LI Z， ZHAO Y， et al. Polydimethylsiloxane-assisted alignment transition from perpendicular to parallel of cylindrical microdomains in block copolymer films［J］. RSC Adv， 2016， 6（96）： 93298-93302.
42	WANG P， CAO S， ZHAO Y， et al. Spherical compound micelles with lamellar stripes self-assembled from star liquid crystalline diblock copolymers in solution［J］. Macromol Chem Phys， 2017， 218（19）： 1700148.
43	WEN W， HUANG T， GUAN S， et al. Self-assembly of single chain janus nanoparticles with tunable liquid crystalline properties from stilbene-containing block copolymers［J］. Macromolecules， 2019， 52（8）： 2956-2964.
44	ZHOU Q F， LI H M， FENG X D. Synthesis of liquid-crystalline polyacrylates with laterally substituted mesogens［J］. Macromolecules， 1987， 20（1）： 233-234.
45	CAI H， JIANG G， CHEN C， et al. New Morphologies and phase transitions of rod-coil dendritic-linear block copolymers depending on dendron generation and preparation procedure［J］. Macromolecules， 2014， 47（1）： 146-151.
46	LYU X， XIAO A， ZHANG W， et al. Head-tail asymmetry as the determining factor in the formation of polymer cubosomes or hexasomes in a rod-coil amphiphilic block copolymer［J］. Angew Chem Int Ed， 2018， 57（32）： 10132-10136.
47	HOU X， GUAN S， QU T， et al. Light-triggered reversible self-engulfing of Janus nanoparticles［J］. ACS Macro Lett， 2018， 7（12）： 1475-1479.
48	刘世勇. 大分子自组装新编［M］. 北京：科学出版社， 2018.
	LIU S Y. Emerging trends in macromolecular self-assembly［M］. Beijing： Science Press， 2018.
49	AN Z， SHI Q， TANG W， et al. Facile RAFT precipitation polymerization for the microwave-assisted synthesis of well-defined， double hydrophilic block copolymers and nanostructured hydrogels［J］. J Am Chem Soc， 2007， 129（46）： 14493-14499.
50	ZHANG W， HONG C， PAN C. Polymerization-induced self-assembly of functionalized block copolymer nanoparticles and their application in drug delivery［J］. Macromol Rapid Commun， 2019， 40（2）： 1800279.
51	LOWE A B. RAFT alcoholic dispersion polymerization with polymerization-induced self-assembly［J］. Polymer， 2016， 106： 161-181.
52	ZHANG X， BOISSÉ S， BUI C， et al. Amphiphilic liquid-crystal block copolymer nanofibers via RAFT-mediated dispersion polymerization［J］. Soft Matter， 2012， 8（4）： 1130-1141.
53	HUO M， ZHANG Y， ZENG M， et al. Morphology evolution of polymeric assemblies regulated with fluoro-containing mesogen in polymerization-induced self-assembly［J］. Macromolecules， 2017， 50（20）： 8192- 8201.
54	HUO M， LI D， SONG G， et al. Semi-fluorinated methacrylates： a class of versatile monomers for polymerization-induced self-assembly［J］. Macromol Rapid Commun， 2018， 39（7）： 1700840.
55	HUO M， SONG G， ZHANG J， et al. Nonspherical liquid crystalline assemblies with programmable shape transformation［J］. ACS Macro Lett， 2018， 7（8）： 956-961.
56	SHEN L， GUO H， ZHENG J， et al. RAFT polymerization-induced self-assembly as a strategy for versatile synthesis of semifluorinated liquid-crystalline block copolymer nanoobjects［J］. ACS Macro Lett， 2018， 7（3）： 287-292.
57	GUAN S， ZHANG C， WEN W， et al. Formation of anisotropic liquid crystalline nanoparticles via polymerization-induced hierarchical self-assembly［J］. ACS Macro Lett， 2018， 7（3）： 358-363.
58	GUAN S， WEN W， YANG Z， et al. Liquid crystalline nanowires by polymerization induced hierarchical self-assembly［J］. Macromolecules， 2019， 53（1）： 465-472.
59	GUAN S， CHEN A. Influence of spacer lengths on the morphology of biphenyl-containing liquid crystalline block copolymer nanoparticles via polymerization-induced self-assembly［J］. Macromolecules， 2020， 53（15）： 6235-6245.
60	ASAOKA S， UEKUSA T， TOKIMORI H， et al. Normally oriented cylindrical nanostructures in amphiphilic PEO-LC diblock copolymers films［J］. Macromolecules， 2011， 44（19）： 7645-7658.
61	WEN W， CHEN A. Influence of single chain nanoparticle stabilizers on polymerization induced hierarchical self-assembly［J］. Polym Chem， 2021， 12（18）： 2743-2751.

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Structure Control of Liquid Crystalline Block Copolymers in Liquid⁃Phase Self⁃assembly

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