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RAFT polymerization-induced self-assembly of semifluorinated liquid-crystalline block copolymers

  • Yongqi Yang EMAIL logo , Zhilong Yuan , Youjun Yan , Daixin Zhang , Xin Luo EMAIL logo and Guangyao Liu EMAIL logo
Published/Copyright: September 15, 2022
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e-Polymers
From the journal e-Polymers Volume 22 Issue 1

Abstract

It is a major challenge to prepare commercially viable scale semifluorinated liquid-crystalline block copolymers (SEFL-BCPs) using solution processing techniques. The technology of selectively solvating one block in a suitable solvent to realize self-assembly provides a promising route for the preparation of core-corona block polymer materials with extensive potential applications. However, considerable limitations have been discovered after much practice. BCP assemblies often require a separate synthesis step and are performed at high dilution. Herein, a one-pot approach combining polymerization-induced and crystallization-driven self-assembly (PISA-CDSA) was used to obtain well-defined, precise compositions of SEFL-BCPs. It is first synthesized via reversible addition-fragmentation chain transfer ethanol dispersion polymerization between 1H,1H,2H,2H-heptadecafluorodecyl acrylate and poly(N,N-dimethylacrylamide) at a concentration up to 20% v/v. Various morphologies, including 1D fiber-like micelles, 2D lamellar structures, and fusion structures, were first observed via transmission electron microscopy. This scalable PISA-CDSA strategy is greatly expanding the morphology scope and applicability of the polymer liquid crystal materials science field.

Keywords: RAFT; polymerization-induced self-assembly; crystallization-driven self-assembly; semifluorinated liquid-crystalline; block copolymer nanoparticle

Fluorinated polymers are playing an increasingly important role in industries such as biotechnology, construction, energy devices, optics, and self-assemblies due to their excellent properties of self-retardant, self-cleaning, low surface energy, chemical stability, corrosion resistance, and high thermal stability (1,2). Hence, versatile synthesis technologies for various fluorinated materials with controllable structures and customizable functions are urgently desirable (3–5). Polymer technologies using crystallization as a tool to control the self-assembly of amphiphilic molecules in solution for the preparation of nonspherical nanoparticles and layered composite structures are receiving increasing attention. Among them, the crystallization-driven self-assembly (CDSA) technique proposed by Ian Manners is widely recognized and used (6,7). Despite the great success of synthesis technology, the preparation of uniformly sized 1D or 2D polymer nanostructures with functional and colloidal stability remains a major challenge. The poor breadth of monomer families, low solubility of fluoropolymers, or the need to use solvents, initiators, or fluorinated ligands have greatly limited the application of the protocol. Recently, important progress has been made via reversible addition-fragmentation chain transfer (RAFT) polymerization and iron-catalyzed atom transfer radical polymerization of semifluorinated methacrylate (8,9). Surprisingly, however, for monomers with high number of fluorocarbons, only oligomers were reported, which was due to the poor solubility of the fluoropolymers with high degrees of polymerization (DPs) (10). Therefore, it was hoped that a new paradigm could be developed to circumvent the limitations encountered in homogeneous polymerization.

Semifluorinated poly(meth)acrylate side groups with large number of fluorocarbons (usually ≥7) exhibit an ordered liquid-crystalline (LC) nature due to the more rigid and much bulkier F-alkyl chains (11). As such, the self-assembly of semifluorinated liquid-crystalline (SFLC) block copolymers (BCPs) have been widely studied (12,13). In conventional BCP self-assembly, a widely used strategy is to first dissolve two blocks of BCPs in a common solvent and then switch the solvent or temperature. Unfortunately, finding a common solvent for BCPs containing SFLC segments is very difficult. Even with the addition of fluorinated solvents, the SFLC blocks are still not completely dissolved, and there is still an unavoidable combination (14). In the self-assembly process of SFLC BCPs, the insolubility difficulty is greatly amplified owing to the rigid rod-like conformation of the fluorinated group and the presence of disparate blocks. Therefore, a low SFLC BCP concentration is a further limitation, making the scaling up of production very difficult. Polymerization-induced self-assembly (PISA) and living CDSA have been widely accepted as powerful and versatile strategies for the scale-up synthesis of BCP nanoobjects at high concentrations with controllable morphologies (7,15,16). We envision that RAFT-PISA and RAFT-CDSA will be versatile and facile strategies that can be used to synthesize BCPs containing SFLC core-forming blocks.

In this communication, complete morphological transitions of SFLC BCPs are revealed (Scheme 1). RAFT ethanol dispersion PISA of poly(N,N-dimethylacrylamide)- poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate) (PDMA21-b-PHDFA x ) BCPs was conducted at 60°C using macromolecular chain transfer agent (macro-CTA) PDMA21 as a stabilizer block and 2,2′-azobis(2,4-dimethylvaleronitrile) (ABVN) as an initiator ([ABVN]/[PDMA21] = 0.3). Low dispersity macro-CTA PDMA21 was prepared via RAFT solution polymerization (50% w/v) of 2-ethylsulfanylthiocarbonylsulfanyl-propionic acid methyl ester and N,N-dimethylacrylamide (DMA) in dimethylformamide (DMF). An 84% monomer conversion was confirmed by 1H NMR after stopping polymerization at 2 h. The DP of DMA was calculated to be 21 by comparing the integral ratio of signals h (δ = 3.67 ppm) and e (δ = 2.76–3.26 ppm) (Figure 1a). A narrow molecular weight distribution of PDMA21 was analyzed by gel permeation chromatography (GPC), as shown in Figure 1b. Good control of the molecular weight distribution (Đ = 1.16) was indicated by the good agreement between the experimental molecular weight (M n = 2,123 g·mol−1) and theoretical molecular weight (M n = 2,306 g·mol−1).

Scheme 1 RAFT-PISA progress of SFLC BCPs via chain extension of PDMA21 macro-CTA.
Scheme 1

RAFT-PISA progress of SFLC BCPs via chain extension of PDMA21 macro-CTA.

Figure 1 1H NMR spectrum (a) and GPC trace (b) of PDMA21 macro-CTA.
Figure 1

1H NMR spectrum (a) and GPC trace (b) of PDMA21 macro-CTA.

Subsequently, in ethanol at 60°C, PDMA21 was chain-extended by RAFT dispersion polymerization of HDFA at 20% w/v solids content. The polymerization conditions and a summary of the results are shown in detail in Table S1. 1H NMR spectra were used to confirm the BCP structure by using a mixture of CDCl3/CF2CFCl2 (3:2, v/v) to efficiently dissociate SFLC block aggregates. Near-quantitative conversion (≥99%) of monomeric HDFA was completed within 24 h. The 1H NMR spectrum of PDMA21-b-PHDFA5 is shown as a representative example (Figure S1 in Supplementary material). The DP was calculated by comparing the integral ratio of signals e (δ = 4.36 ppm) and l (δ = 3.67 ppm). The experimental molecular weight (M n = 4,284 g·mol−1) of PDMA21-b-PHDFA5 determined by GPC showed good agreement with the theoretical molecular weight (M n = 4,896 g·mol−1) (Figure S2). However, the reason for polydispersity values greater than 1.3 may be related to the nature of the monomer (18).

By periodically withdrawing aliquots from the SFLC BCP solution, RAFT ethanol dispersion polymerization at a 20% w/v solids content with the target of PDMA21-PHDFA40 full conversion was studied (Figure 2). The RAFT dispersion polymerization followed the typical two-stage kinetics, with significant acceleration of the nucleation rate at ∼2 h, and 95% monomer conversion was observed after 6 h. A good pseudo-first-order kinetic plot was found after 2 h. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to characterize the SFLC block nanoobject size and morphology (Table S1 in Supplementary material and Figure 3). As shown in Figure 3, an unusual morphological transition was revealed, while the DP of the core-forming SFLC block increased from 10 to 45. An unusual directionally extended fibrous one-dimensional morphology with an average width of 20 nm and an average length of 660 nm was observed at DP = 10 (Figure S3). As the DP increased to 15, the fused fibers became thicker and longer, and the average width and length were 40 and 600 nm, respectively (Figure S4). Fusion of 1D fibers occurred upon further increasing the DP, resulting in the generation of 2D nanolayers at DP = 20–35 with an average width of 100–960 nm and an average length of 790–1,700 nm (Figures S5–S7). A nontraditional multilayer fusion lamellar structure was observed at DP = 40 with an average diameter of 40 nm and an average length of 790 nm. A new morphology with a porous fusion structure (average diameter of 80 nm) appeared after a further increase in the DP (Figure 3h, Figures S8 and S9). The anisotropic morphology produced by PISA was caused by the LC nature of the core-forming block, which was proven by differential scanning calorimetry (DSC) measurements (Figure 4).

Figure 2 (a) Polymerization kinetics of dispersion polymerization of HDFA mediated by PDMA21 at a 20% solids content in ethanol at 60°C and (b) plot of the pseudo-first-order kinetics of the polymerization. ABVN/PDMA21/HDFA = 0.3:1:40.
Figure 2

(a) Polymerization kinetics of dispersion polymerization of HDFA mediated by PDMA21 at a 20% solids content in ethanol at 60°C and (b) plot of the pseudo-first-order kinetics of the polymerization. ABVN/PDMA21/HDFA = 0.3:1:40.

Figure 3 Representative TEM micrographs of BCP nanoparticles synthesized using PDMA21 as a macro-CTA in 20% w/v EtOH solution at 60°: (a) fibrous morphology, (b) fused fibrous morphology, (c) fused lamellar morphology, (d–f) gradually fused layered structure, (g) multilayer fusion lamellar structure, and (h) porous fusion structure. (a) x = 10, (b) x = 15, (c) x = 20, (d) x = 25, (e) x = 30, (f) x = 35, (g) x = 40, and (h) x = 45.
Figure 3

Representative TEM micrographs of BCP nanoparticles synthesized using PDMA21 as a macro-CTA in 20% w/v EtOH solution at 60°: (a) fibrous morphology, (b) fused fibrous morphology, (c) fused lamellar morphology, (d–f) gradually fused layered structure, (g) multilayer fusion lamellar structure, and (h) porous fusion structure. (a) x = 10, (b) x = 15, (c) x = 20, (d) x = 25, (e) x = 30, (f) x = 35, (g) x = 40, and (h) x = 45.

Figure 4 DSC traces for PDMA21-b-PHDFA40 fluorinated block copolymer nanoobjects (a) and PHDFA40 (b) homopolymer. The red and black lines refer to the cooling half-cycle and heating half-cycle, respectively.
Figure 4

DSC traces for PDMA21-b-PHDFA40 fluorinated block copolymer nanoobjects (a) and PHDFA40 (b) homopolymer. The red and black lines refer to the cooling half-cycle and heating half-cycle, respectively.

As proven by Lv et al., the temperature of polymerization (T p) plays a decisive role in the morphological evolution process. The main reason is that the core-forming block mobility is influenced by T p (19). When the glass transition temperature (T g) was higher than or close to the T p, the fluidity of the SFLC BCPs was delayed, which was beneficial for promoting the transformation of one-dimensional vesicles into tubular structures. In our PISA work, the polymerization temperature of all PISA formulations was 60°C, which is lower than the commonly used polymerization temperature. DSC measurement was used to check if the T p we used was close to the isotropic phase transition temperature of the SFLC BCPs.

As shown in Figure 4, an isotropic phase transition temperature of 60°C for PDMA21-b-PHDFA40 was revealed, suggesting that the T p we used was close to the literature report (19). The T g values of PDMA21 (Figure S10), PDMA21-b-PHDFA (Figure 4a), and PHDFA (Figure 4b) were determined by DSC to be 65°C, 79°C, and 74°C, respectively. The single T g shown by the BCP implies that the two blocks may be miscible rather than phase-segregated in the bulk. The ethanol dispersion of BCP nanoparticles was also tested by DSC, but no meaningful information was observed because of the evaporation of ethanol in the measurement process. However, the facile morphological transitions of SFLC BCPs in ethanol indicate that the SFLC BCPs were to some extent solvated, leading to T g values lower than T p (20). The isotropic transition temperature of PHDFA40 (63°C) and the melting point of PDMA21 (65°C) were also consistent with the literature values, which further demonstrates the LC nature of SFLC BCPs synthesized in RAFT-PISA (18,21).

In summary, RAFT-PISA and RAFT-CDSA dispersion polymerization has been certified to be a versatile and well-established platform for the preparation of SFLC BCPs. The insolubility of PHDFA, which is a great challenge in conventional solution polymerization, can be fully utilized in RAFT dispersion polymerization to directly furnish SFLC BCPs through a PISA and CDSA platform. The LC nature of the core-forming block leads to the general formation of interesting nonspherical anisotropic fusion morphologies. We speculate that the synthesis of other fluorinated BCPs can also be realized by the RAFT platform through the judicious choice of solvents. We strongly believe that the RAFT-PISA and RAFT-CDSA protocol can be extended to the synthesis of other fluorine-containing BCPs through a rational choice of solvent. This will not only expand the preparation of different types of fluorinated BCPs but also lead to the discovery of new morphologies of polymer nanoparticles. The type of macro-CTA, solids content, temperature, and other factors also affect the morphological transformation of block polymers, and related research is currently being conducted.

Experimental

2-Ethylsulfanylthiocarbonylsulfanylpropionic acid methyl ester (CTA) was based on a procedure reported previously in the literature (17). CF2ClCFCl2 (99.5%) was purchased from Shanghai Macklin Biochemical. 1H,1H,2H,2H-HDFA (97%) and N,N-DMA (99%) were purchased from J&K Scientific. ABVN (99%) was purchased from Sigma-Aldrich. N,N-DMF (99.5%), Al2O3 (99.99%, gamma-phase, 10 nm), ethanol (EtOH, 99.5%), and CDCl3 (99.8%) were purchased from Shanghai Titan Co., Ltd. The monomers were passed through a column of Al2O3 to remove the inhibitor before use.

The synthesis procedure of the macro-CTA poly(dimethylacrylamide) (PDMA21) was based on a previously reported procedure (17). The poly(dimethylacrylamide)-poly(1H,1H,2H,2H-heptadecafluorodecyl acrylate) (PDMA21-PHDFA x ) block copolymer was systematically investigated at 20% solids by varying the target DP of the block polymer in the range 10–45 (Table S1). The synthesis of PDMA21-b-P(HDFA)40 is given as a representative procedure. PDMA21 (0.1223 g, 5.30 × 10−2 mmol) and HDFA (1.0990 g, 2.12 mmol) were weighed into a 20 mL glass vial. Then, 5 mL ethanol was added to dissolve all the reagents to form a homogeneous solution. After the reaction mixture was purged with nitrogen for 20 min in an ice/water bath, the vial was placed into an oil bath at 60°C with a stirring speed of 500 rpm. Then, a certain amount of ABVN (ABVN/PDMA21 = 0.3) dissolved in 100 μL ethanol was added via a syringe. After 24 h of polymerization under nitrogen, the monomer conversion and block copolymer composition were determined by 1H NMR spectroscopy in CDCl3, and the size and morphology were analyzed by DLS and TEM.

Acknowledgments

Financial support from the Natural Science Foundation of Shandong Province, grant number ZR2020QB084, is gratefully acknowledged. We thank Professor Zesheng An of Jilin University for his support and help with the work.

  1. Funding information: Natural Science Foundation of Shandong Province, grant number ZR2020QB084.

  2. Author contributions: Yongqi Yang, Zhilong Yuan, Youjun Yan, and Daixin Zhang performed the experiments. Yongqi Yang, Xin Luo, and Guangyao Liu designed the project and performed the data analysis. Yongqi Yang wrote the article. All authors discussed the results. All authors have read and agreed to the published version of the manuscript.

  3. Conflict of interest: The authors declare no conflict of interest.

  4. Data availability statement: All data generated or analyzed during this study are included in this published article.

References

(1) Peng Z, Song J, Gao Y, Liu J, Lee C, Chen G, et al. A fluorinated polymer sponge with superhydrophobicity for high-performance biomechanical energy harvesting. Nano Energy. 2021;85:106021. 10.1016/j.nanoen.2021.106021.Search in Google Scholar

(2) Soulestin T, Ladmiral V, Dos Santos FD, Ameduri B. Vinylidene fluoride-and trifluoroethylene-containing fluorinated electroactive copolymers. How does chemistry impact properties? Prog Polym Sci. 2017;72:16–60. 10.1016/j.progpolymsci.2017.04.004.Search in Google Scholar

(3) Wang CG, Chong AML, Goto A. One reagent with two functions: simultaneous living radical polymerization and chain-end substitution for tailoring polymer dispersity. ACS Macro Lett. 2021;10(5):584–90. 10.1021/acsmacrolett.1c00179.Search in Google Scholar PubMed

(4) Dadashi-Silab S, Kim K, Lorandi F, Szczepaniak G, Kramer S, Peteanu L, et al. Red-light-induced, copper-catalyzed atom transfer radical polymerization. ACS Macro Lett. 2022;11(3):376–81. 10.1021/acsmacrolett.2c00080.Search in Google Scholar PubMed

(5) Lv F, An Z, Wu P. Efficient access to inverse bicontinuous mesophases via polymerization-induced cooperative assembly. CCS Chem. 2020;3(8):2211–22. 10.31635/ccschem.020.202000407.Search in Google Scholar

(6) Tao D, Wang Z, Huang X, Tian M, Lu G, Manners I, et al. Continuous and segmented semiconducting fiber‐like nanostructures with spatially selective functionalization by living crystallization‐driven self‐assembly. Angew Chem Int Ed. 2020;132(21):8309–16.10.1002/ange.202000327Search in Google Scholar

(7) Tao D, Feng C, Cui Y, Yang X, Manners I, Winnik MA, et al. Monodisperse fiber-like micelles of controlled length and composition with an oligo (p-phenylenevinylene) core via “living” crystallization-driven self-assembly. J Am Chem Soc. 2017;139(21):7136–9. 10.1021/jacs.7b02208.Search in Google Scholar PubMed

(8) Huo M, Li D, Song G, Zhang J, Wu D, Wei Y, et al. Semi‐fluorinated methacrylates: a class of versatile monomers for polymerization‐induced self‐assembly. Macromol Rapid Commun. 2018;39(7):1700840. 10.1002/marc.201700840.Search in Google Scholar PubMed

(9) Dadashi-Silab S, Matyjaszewski K. Iron-catalyzed atom transfer radical polymerization of semifluorinated methacrylates. ACS Macro Lett. 2019;8(9):1110–4. 10.1021/acsmacrolett.9b00579.Search in Google Scholar PubMed

(10) Ma Q, Wang W, Zhang L, Cao H. RAFT polymerization of semifluorinated monomers mediated by a NIR fluorinated‐photocatalyst. Macromol Rapid Commun. 2022;43:2200122. 10.1002/marc.202200122.Search in Google Scholar PubMed

(11) Dolui S, Kumar D, Banerjee S, Ameduri B. Well-defined fluorinated copolymers: current status and future perspectives. Acc Chem Res. 2021;2(4):242–51. 10.1021/accountsmr.1c00015.Search in Google Scholar

(12) Guerre M, Lopez G, Améduri B, Semsarilar M, Ladmiral V. Solution self-assembly of fluorinated polymers, an overview. Polym Chem. 2021;12(27):3852–77. 10.1039/D1PY00221J.Search in Google Scholar

(13) Guan S, Chen A. Influence of spacer lengths on the morphology of biphenyl-containing liquid crystalline block copolymer nanoparticles via polymerization-induced self-assembly. Macromolecules. 2020;53(15):6235–45. 10.1021/acs.macromol.0c00959.Search in Google Scholar

(14) Gao Y, Li X, Hong L, Liu G. Mesogen-driven formation of triblock copolymer cylindrical micelles. Macromolecules. 2012;45:1321–30. 10.1021/ma202084m.Search in Google Scholar

(15) Busatto N, Keddie JL, Roth PJ. Sphere-to-worm morphological transitions and size changes through thiol–para-fluoro core modification of PISA-made nano-objects. Polym Chem. 2020;11(3):704–11. 10.1039/C9PY01585J.Search in Google Scholar

(16) Corrigan N, Jung K, Moad G, Hawker CJ. Reversible-deactivation radical polymerization (controlled/living radical polymerization): from discovery to materials design and applications. Prog Polym Sci. 2020;111:101311. 10.1016/j.progpolymsci.2020.101311.Search in Google Scholar

(17) Zhou W, Qu Q, Xu Y, Ze A. Aqueous polymerization-induced self-assembly for the synthesis of ketone-functionalized nano-objects with low polydispersity. ACS Macro Lett. 2015;4(5):495–9. 10.1021/acsmacrolett.5b00225.Search in Google Scholar PubMed

(18) Shen L, Guo H, Zheng J, Wang X, Yang Y, An Z. RAFT polymerization-induced self-assembly as a strategy for versatile synthesis of semifluorinated liquid-crystalline block copolymer nanoobjects. ACS Macro Lett. 2018;7(3):287–92. 10.1021/acsmacrolett.8b00070.Search in Google Scholar PubMed

(19) Lv F, An Z, Wu P. What determines the formation of block copolymer nanotubes. Macromolecules. 2020;53:367–73. 10.1021/acs.macromol.9b01868.Search in Google Scholar

(20) Yang Y, Zheng J, Man S, Sun X, An Z. Synthesis of poly(ionic liquid)-based nano-objects with morphological transitions via RAFT polymerization-induced self-assembly in ethanol. Polym Chem. 2018;9(7):824–7. 10.1039/C8PY00040A.Search in Google Scholar

(21) Nojima S, Higaki Y, Ishige R, Kabayama H, Ohta N, Masunaga H, et al. Crystallization-induced structure fluctuation of crystallized microdomain structurecomposed of strongly segregated crystalline-crystalline deblock copolymers. Polymer. 2016;102:256–65. 10.1016/j.polymer.2016.09.024.Search in Google Scholar
Received: 2022-05-30
Revised: 2022-07-26
Accepted: 2022-08-15
Published Online: 2022-09-15

© 2022 Yongqi Yang et al., published by De Gruyter

This work is licensed under the Creative Commons Attribution 4.0 International License.

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https://doi.org/10.1515/epoly-2022-0072
Keywords for this article
RAFT; polymerization-induced self-assembly; crystallization-driven self-assembly; semifluorinated liquid-crystalline; block copolymer nanoparticle
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