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RAFT polymerization-induced self-assembly of poly(ionic liquids) in ethanol

  • Yongqi Yang , Xiawei Li EMAIL logo , Youjun Yan , Rongkai Pan , Jun Liu , Meng Lian , Xin Luo EMAIL logo and Guangyao Liu EMAIL logo
Published/Copyright: September 20, 2022
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e-Polymers
From the journal e-Polymers Volume 22 Issue 1

Abstract

Poly(ionic liquids) (PILs) exhibit better durability, processability, and mechanical stability than ionic liquids. PIL self-assembly in green solvents is a well-established strategy for preparing polyelectrolytes. Reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly (PISA) has proven to be the most controllable method for synthesizing polyelectrolytes. However, there have been few reports on preparing high-order morphology PILs by RAFT-PISA. A new type of ionic monomer, 1-butyl-3-(4-vinylbenzyl)imidazolium hexafluorophosphate ([BVBIm][PF6]), was prepared from substitution reaction and ion exchange reaction of 1-butylimidazole and 4-vinylbenzyl chloride. Herein, various morphologies, including spheres, worms, and vesicles, were easily obtained via RAFT ethanolic dispersion polymerization using poly(N,N-dimethylacrylamide) (PDMA43) as the macromolecular chain transfer agent and [BVBIm][PF6] as the monomer. Dispersion polymerization kinetic experiments, dynamic light scattering, transmission electron microscopy, and differential scanning calorimetry were used to investigate the PDMA43-b-P([BVBIm][PF6]) x block nanoparticles. This efficient RAFT-PISA method for preparing functionalized PIL nano-objects with controlled morphologies represents significant progress in this field.

Graphical abstract

Keywords: RAFT; polymerization-induced self-assembly; poly(ionic liquids); dispersion polymerization; morphologies

Ionic liquids usually refer to organic salts that are liquid at temperatures below 100°C (1). Due to their thermal stability, negligible vapor pressure, electrochemical stability, and excellent solubilizing ability, they have been used as green solvents in organic synthesis and chemical processing (2). As special polyelectrolytes, poly(ionic liquids) (PILs) have attracted sustained attention in recent years due to their unique physicochemical properties (3). PILs are polymers containing ionic liquid units in either the side chain or backbone (4). PILs combine the excellent mechanical properties and processability of polymers and the special properties of ionic liquids. They have important applications in catalysis, emulsion, energy devices, and CO2 adsorption and as precursors of carbon materials (5,6).

The rapid development of reversible deactivation radical polymerization techniques has remarkably benefited the preparation of well-defined PILs with predictable molecular weight, tunable architecture, and low polydispersity index (7,8). To date, several block copolymers containing at least one PIL block have been prepared, and their self-assembly has been studied (9). Despite the great success in the preparation of various nanostructured PILs, the traditional self-assembly suffers from low solid content (less than 1% w/v) and multiple steps, which limit the commercialization process of PILs and their future applications (10).

Recently, polymerization-induced self-assembly (PISA) has gained increasing attention because it is a versatile and efficient approach for precise control over the molecular weight and morphology of block copolymer nano-objects at high solid contents (11–13). Block copolymers with increasing molecular weight are produced by chain extension of solvophilic stabilizer blocks. When the critical chain length is reached, the block copolymer can self-assemble in situ to produce a rich library of morphologies. Various influencing factors, including the block ratio, polymer structure, solvophilic nucleation block, solid content, block incompatibility, and homopolymer/block copolymer ratio, were clarified to affect the block morphology (14). Although numerous tailormade polymer nanoparticles have been prepared in water, alcohol, and other solvents, the PISA method with ionic liquid monomers to prepare PIL nanoparticles is still extremely challenging and remains mostly unexplored. This may be due to the difficulty of monomer polymerization caused by electrostatic repulsion, which usually leads to a low molecular weight and a broad distribution (15). To our knowledge, no more than six examples of PIL (used as both stabilizers and core-forming blocks) nanoparticles produced by PISA have been recently reported. Various morphologies realized via reversible addition-fragmentation chain transfer (RAFT) polymerization of P[1-[2-acryloylethyl]-3-methyl(or benzyl)imidazolium bromide] (as a PIL macromolecular chain transfer agent [macro-CTA]) and 2-vinylpyridine in water were reported by Bernard et al. (16). Subsequently, thermoresponsive poly[1-(4-vinylbenzyl)-3-methylimidozolium tetrafluoroborate] trithiocarbonate was synthesized by RAFT polymerization of polystyrene in water/methanol (17). Double PIL block copolymers based on cobalt-mediated radical PISA of N-vinyl-3-alkylimidazolium salts were reported by Detrembleur and coworkers (18). Later, RAFT/MADIX aqueous PISA of 3-n-dodecyl-1-vinylimidazolium bromide was investigated (19). However, a full range of morphologies (spheres, worms, and vesicles) had not been reported until our PIL block copolymer nano-objects synthesized via RAFT-PISA of 1-butyl-3-(4-vinylbenzyl) imidazolium tetrafluoroborate were investigated (20).

Herein, we report complete morphological transitions of PIL nano-objects based on the new ionic monomer 1-butyl-3-(4-vinylbenzyl) imidazole hexafluorophosphate ([BVBIm][PF6]) via RAFT-mediated dispersion polymerization in ethanol at 70℃. The block polymers were obtained by systematically changing the solid contents and number-averaged degree of polymerization (DP) of the PIL. As shown in Scheme 1, the imidazole ionic monomer [BVBIm][PF6] was selected because of its moderate solubility in ethanol.

Scheme 1 RAFT ethanolic dispersion polymerization process for poly(N,N-dimethylacrylamide)-poly(1-butyl-3-(4-vinylbenzyl)imidazolium hexafluorophosphate), PDMA43-b-P([BVBIm][PF6]) x , nano-objects.
Scheme 1

RAFT ethanolic dispersion polymerization process for poly(N,N-dimethylacrylamide)-poly(1-butyl-3-(4-vinylbenzyl)imidazolium hexafluorophosphate), PDMA43-b-P([BVBIm][PF6]) x , nano-objects.

The macro-CTA poly(N,N-dimethylacrylamide) (PDMA43) (Đ = 1.05) was synthesized based on a reported procedure (20), as confirmed by 1H NMR and gel permeation chromatography results (Figures S1 and S2 in Supplementary material). The new ionic monomer [BVBIm][PF6] was synthesized by a two-step reaction. First, 1-butyl-3-(4-vinylbenzyl) imidazolium chloride was obtained via a reaction between 4-vinylbenzyl chloride and 1-butylimidazole. Then, an anionic double decomposition reaction was carried out with KPF6 in water to obtain [BVBIm][PF6]. 1H, 13C, and 19F NMR spectroscopy were used to confirm the purity of the ionic monomer (Figure S3). The block polymer PDMA43-b-P([BVBIm][PF6]) x was also confirmed by 1H NMR (Figure S4).

RAFT dispersion polymerization of [BVBIm][PF6] mediated by the macro-CTA PDMA43 and initiator 2,2′-azobis(2-methylpropionitrile) ([AIBN]/[PDMA43] = 0.5) was conducted from 12% w/v to 25% w/v solid contents in ethanol at 70°C (Scheme 1). The experiments were conducted at 20% w/v solid contents by periodically withdrawing aliquots during the RAFT dispersion polymerization of the target PDMA43-b-P([BVBIm][PF6])60 at full conversion. The polymerization solution rapidly became translucent at 0.5 h, and 95% monomer conversion was eventually reached at 8 h (Figure 1). A pseudo-first-order kinetic curve of [BVBIm][PF6] conventional radical polymerization was obtained. An analysis of the samples extracted during polymerization by transmission electron microscopy (TEM) showed that spherical particles and worm-like particles with similar diameters (average diameter 20 nm) were mainly formed at 2 h (30% conversion) and 3 h (53% conversion), and worm-fused lamellar structures (average diameter of 50 nm) and vesicle structures (average diameter of 180 nm, film thickness of 20 nm) were formed at 4 h (70% conversion) and 7 h (92% conversion), respectively (Figure S5). This morphological transformation order agrees with that of block copolymers reported in the literature (20).

Figure 1 Dispersion polymerization kinetics for the target PDMA43-b-P([BVBIm][PF6])60 at 25% w/v solid contents and 70°C: (a) monomer conversion vs polymerization time (insets: TEM micrographs for the nano-objects observed at the indicated conversions; scale bar: 0.5 µm) and (b) pseudo-first-order kinetic plot.
Figure 1

Dispersion polymerization kinetics for the target PDMA43-b-P([BVBIm][PF6])60 at 25% w/v solid contents and 70°C: (a) monomer conversion vs polymerization time (insets: TEM micrographs for the nano-objects observed at the indicated conversions; scale bar: 0.5 µm) and (b) pseudo-first-order kinetic plot.

The dispersion polymerization morphological transitions were studied in detail by systematically changing the solid content (12–25% w/v) and the target PIL block DP. Generally, high monomer conversions (>90%) were achieved within 24 h (Table S1 in Supplementary material). Representative TEM micrographs of the nano-objects produced via RAFT polymerization at a solid content of 25% w/v are shown in Figure 2.

Figure 2 TEM micrographs for PDMA43-b-P([BVBIm][PF6]) x nano-objects synthesized at 25% w/v solids and 70°C: (a) x = 28, (b) x = 34, (c) x = 39, (d) x = 43, (e) x = 48, and (f) x = 54.
Figure 2

TEM micrographs for PDMA43-b-P([BVBIm][PF6]) x nano-objects synthesized at 25% w/v solids and 70°C: (a) x = 28, (b) x = 34, (c) x = 39, (d) x = 43, (e) x = 48, and (f) x = 54.

Block copolymer nanospheres with a diameter of 61.3 nm were synthesized at a PIL DP of 28. After fusion, worms with similar diameters but a polydisperse length of more than 200 nm were formed. Then, these worms fused to form lamellar structures in the middle of the “jellyfish,” and their morphology further changed, forming a lamellar-encapsulated vesicle structure. Then, the wrapped lamellae further fused to form polydisperse vesicles with a diameter of more than 400 nm (Figure 2e and f). The morphological transition sequence of PIL block copolymers and intermediate morphology observed in this article suggest that a full range of morphologies consistent with the results reported by An et al. (20) can be derived. A similar morphological transition process was observed by reducing the solid contents and changing the PIL DP (Figures S6–S9), and a thorough morphology diagram is shown in Figure 3. Although both spheres and vesicles occupied a relatively large composition space, fully worm morphologies were basically not observed, and these morphologies coexisted with spherical and lamellar structures.

Figure 3 Morphology diagram with representative TEM micrographs for PDMA43-b-P([BVBIm][PF6]) x nano-objects (scale bar 200 nm) synthesized via ethanolic RAFT dispersion polymerization at 70°C.
Figure 3

Morphology diagram with representative TEM micrographs for PDMA43-b-P([BVBIm][PF6]) x nano-objects (scale bar 200 nm) synthesized via ethanolic RAFT dispersion polymerization at 70°C.

The glass transition temperature (T g) values of P([BVBIm][PF6])50, PDMA43, and PDMA43-b-P([BVBIm][PF6])50 were determined via differential scanning calorimetry (DSC) (Figure S10). While the T g of P([BVBIm][PF6]) x was 86°C, that of PDMA43 was 105°C, and the block copolymer showed only one T g of 98°C, all values satisfy the Fox equation. This may be due to the close T g values of PDMA43 and the PIL homopolymer. DSC tests of the ethanol dispersions of block copolymer nanoparticles were also performed, but no valuable information was gained because of the evaporation of ethanol during measurement. However, the morphological transition of P([BVBIm][PF6]) x in ethanol strongly indicates that the PIL blocks were solvated to a certain extent, and their T g was lower than the polymerization temperature (70°C), which had also been demonstrated in previous literature (20). The high solubility (>100% w/v) of [BVBIm][PF6] in ethanol also indirectly proved that it was well plasticized by ethanol during the PIL block core formation process. Therefore, the T g under dispersion polymerization conditions can be inferred to be lower than that determined by DSC.

In conclusion, various morphologies were observed during RAFT-PISA of PDMA43-b-P([BVBIm][PF6]) x , including spheres, worms, and vesicles. Since the research on PIL block copolymer nano-objects has attracted continuous attention, the results of this study not only help in understanding the morphological transitions of PIL core block copolymer nanoparticles but also supply an efficient route with various application values to prepare innovative materials. The structure of ionic liquid monomers can be easily tuned through anion exchange and alkyl substitution. The effect of the ionic liquid structure on the PISA morphology is being studied in detail.

1 Experimental

1.1 Materials and methods

N,N-Dimethylacrylamide (≥99%) was purchased from J&K Scientific. 4-Vinylbenzyl chloride (≥90%) and 1-butylimidazole (≥98%) were purchased from TCI. AIBN (≥99%) was purchased from Sigma-Aldrich (recrystallized from ethanol). Anhydrous diethyl ether (≥99.7%) was purchased from Sinopharm Chemical Reagent Co., Ltd. N,N′-dimethylformamide ≥99.5%) was purchased from Beijing Jinming Biotechnology Co., Ltd. Al2O3 (Greagent, AR, neutral, 200–300 mesh) and ethanol (Adamas, EtOH, ≥99.8%) was purchased from Shanghai Titan Co., Ltd. An Al2O3 column was used to remove the inhibitor in monomers. 2-Ethylsulfanylthiocarbonylsulfanylpropionic acid methyl ester (CTA) was synthesized based on a previously reported method (21).

The PDMA43-b-P([BVBIm][PF6]) x nanomaterials obtained via RAFT dispersion polymerization in ethanol were synthesized by varying the target DP of the PIL block in the range of 30–70 and systematically investigated at 12–25% w/v solid contents (Table S1). The synthesis procedure of PDMA43-b-P([BVBIm][PF6])50 is given as a representative example. PDMA43 (0.0424 g, 0.0095 mmol), 1-butyl-3-(4-vinylbenzyl) imidazolium hexafluorophosphate ([BVBIm][PF6], 0.1826 g, 0.47 mmol), and 2 mL ethanol (to dissolve all the reagents) were weighed into a 20 mL glass vial. After purging the reaction mixture with nitrogen in an ice/water bath for 25 min under a stirring speed of 600 rpm, the vial was placed into an oil bath at 70°C for 24 h. Then, 0.78 mg AIBN dissolved in 100 μL ethanol (AIBN/PDMA43 = 0.5) was added via a syringe. 1H NMR spectroscopy in DMSO-d6 was used to determine the monomer conversion and block copolymer composition, and dynamic light scattering and TEM were used to analyze the size and morphology.

Acknowledgments

We thank the Natural Science Foundation of Shandong Province (ZR2020QB084), China for financial support and Professor Zesheng An for his help in the research work.

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

  2. Author contributions: Yongqi Yang, Xiawei Li, Youjun Yan, Rongkai Pan, and Jun Liu: writing – original draft, writing – review and editing; Yongqi Yang, Meng Lian, Xin Luo, and Guangyao Liu: writing – original draft, designed the project and performed the data analysis. All authors discussed the results. All authors have read and agreed to the published version of the manuscript.

  3. Conflict of interest: Authors state no conflict of interest.

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

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Received: 2022-07-05
Revised: 2022-08-02
Accepted: 2022-08-08
Published Online: 2022-09-20

© 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-2022-0069
Keywords for this article
RAFT; polymerization-induced self-assembly; poly(ionic liquids); dispersion polymerization; morphologies
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  4. Hyper-crosslinked polymers with controlled multiscale porosity for effective removal of benzene from cigarette smoke
  5. The HDPE composites reinforced with waste hybrid PET/cotton fibers modified with the synthesized modifier
  6. Effect of polyurethane/polyvinyl alcohol coating on mechanical properties of polyester harness cord
  7. Fabrication of flexible conductive silk fibroin/polythiophene membrane and its properties
  8. Development, characterization, and in vitro evaluation of adhesive fibrous mat for mucosal propranolol delivery
  9. Fused deposition modeling of polypropylene-aluminium silicate dihydrate microcomposites
  10. Preparation of highly water-resistant wood adhesives using ECH as a crosslinking agent
  11. Chitosan-based antioxidant films incorporated with root extract of Aralia continentalis Kitagawa for active food packaging applications
  12. Molecular dynamics simulation of nonisothermal crystallization of a single polyethylene chain and short polyethylene chains based on OPLS force field
  13. Synthesis and properties of polyurethane acrylate oligomer based on polycaprolactone diol
  14. Preparation and electroactuation of water-based polyurethane-based polyaniline conductive composites
  15. Rapeseed oil gallate-amide-urethane coating material: Synthesis and evaluation of coating properties
  16. Synthesis and properties of tetrazole-containing polyelectrolytes based on chitosan, starch, and arabinogalactan
  17. Preparation and properties of natural rubber composite with CoFe2O4-immobilized biomass carbon
  18. A lightweight polyurethane-carbon microsphere composite foam for electromagnetic shielding
  19. Effects of chitosan and Tween 80 addition on the properties of nanofiber mat through the electrospinning
  20. Effects of grafting and long-chain branching structures on rheological behavior, crystallization properties, foaming performance, and mechanical properties of polyamide 6
  21. Study on the interfacial interaction between ammonium perchlorate and hydroxyl-terminated polybutadiene in solid propellants by molecular dynamics simulation
  22. Study on the self-assembly of aromatic antimicrobial peptides based on different PAF26 peptide sequences
  23. Effects of high polyamic acid content and curing process on properties of epoxy resins
  24. Experiment and analysis of mechanical properties of carbon fiber composite laminates under impact compression
  25. A machine learning investigation of low-density polylactide batch foams
  26. A comparison study of hyaluronic acid hydrogel exquisite micropatterns with photolithography and light-cured inkjet printing methods
  27. Multifunctional nanoparticles for targeted delivery of apoptin plasmid in cancer treatment
  28. Thermal stability, mechanical, and optical properties of novel RTV silicone rubbers using octa(dimethylethoxysiloxy)-POSS as a cross-linker
  29. Preparation and applications of hydrophilic quaternary ammonium salt type polymeric antistatic agents
  30. Coefficient of thermal expansion and mechanical properties of modified fiber-reinforced boron phenolic composites
  31. Synergistic effects of PEG middle-blocks and talcum on crystallizability and thermomechanical properties of flexible PLLA-b-PEG-b-PLLA bioplastic
  32. A poly(amidoxime)-modified MOF macroporous membrane for high-efficient uranium extraction from seawater
  33. Simultaneously enhance the fire safety and mechanical properties of PLA by incorporating a cyclophosphazene-based flame retardant
  34. Fabrication of two multifunctional phosphorus–nitrogen flame retardants toward improving the fire safety of epoxy resin
  35. The role of natural rubber endogenous proteins in promoting the formation of vulcanization networks
  36. The impact of viscoelastic nanofluids on the oil droplet remobilization in porous media: An experimental approach
  37. A wood-mimetic porous MXene/gelatin hydrogel for electric field/sunlight bi-enhanced uranium adsorption
  38. Fabrication of functional polyester fibers by sputter deposition with stainless steel
  39. Facile synthesis of core–shell structured magnetic Fe3O4@SiO2@Au molecularly imprinted polymers for high effective extraction and determination of 4-methylmethcathinone in human urine samples
  40. Interfacial structure and properties of isotactic polybutene-1/polyethylene blends
  41. Toward long-live ceramic on ceramic hip joints: In vitro investigation of squeaking of coated hip joint with layer-by-layer reinforced PVA coatings
  42. Effect of post-compaction heating on characteristics of microcrystalline cellulose compacts
  43. Polyurethane-based retanning agents with antimicrobial properties
  44. Preparation of polyamide 12 powder for additive manufacturing applications via thermally induced phase separation
  45. Polyvinyl alcohol/gum Arabic hydrogel preparation and cytotoxicity for wound healing improvement
  46. Synthesis and properties of PI composite films using carbon quantum dots as fillers
  47. Effect of phenyltrimethoxysilane coupling agent (A153) on simultaneously improving mechanical, electrical, and processing properties of ultra-high-filled polypropylene composites
  48. High-temperature behavior of silicone rubber composite with boron oxide/calcium silicate
  49. Lipid nanodiscs of poly(styrene-alt-maleic acid) to enhance plant antioxidant extraction
  50. Study on composting and seawater degradation properties of diethylene glycol-modified poly(butylene succinate) copolyesters
  51. A ternary hybrid nucleating agent for isotropic polypropylene: Preparation, characterization, and application
  52. Facile synthesis of a triazine-based porous organic polymer containing thiophene units for effective loading and releasing of temozolomide
  53. Preparation and performance of retention and drainage aid made of cationic spherical polyelectrolyte brushes
  54. Preparation and properties of nano-TiO2-modified photosensitive materials for 3D printing
  55. Mechanical properties and thermal analysis of graphene nanoplatelets reinforced polyimine composites
  56. Preparation and in vitro biocompatibility of PBAT and chitosan composites for novel biodegradable cardiac occluders
  57. Fabrication of biodegradable nanofibers via melt extrusion of immiscible blends
  58. Epoxy/melamine polyphosphate modified silicon carbide composites: Thermal conductivity and flame retardancy analyses
  59. Effect of dispersibility of graphene nanoplatelets on the properties of natural rubber latex composites using sodium dodecyl sulfate
  60. Preparation of PEEK-NH2/graphene network structured nanocomposites with high electrical conductivity
  61. Preparation and evaluation of high-performance modified alkyd resins based on 1,3,5-tris-(2-hydroxyethyl)cyanuric acid and study of their anticorrosive properties for surface coating applications
  62. A novel defect generation model based on two-stage GAN
  63. Thermally conductive h-BN/EHTPB/epoxy composites with enhanced toughness for on-board traction transformers
  64. Conformations and dynamic behaviors of confined wormlike chains in a pressure-driven flow
  65. Mechanical properties of epoxy resin toughened with cornstarch
  66. Optoelectronic investigation and spectroscopic characteristics of polyamide-66 polymer
  67. Novel bridged polysilsesquioxane aerogels with great mechanical properties and hydrophobicity
  68. Zeolitic imidazolate frameworks dispersed in waterborne epoxy resin to improve the anticorrosion performance of the coatings
  69. Fabrication of silver ions aramid fibers and polyethylene composites with excellent antibacterial and mechanical properties
  70. Thermal stability and optical properties of radiation-induced grafting of methyl methacrylate onto low-density polyethylene in a solvent system containing pyridine
  71. Preparation and permeation recognition mechanism of Cr(vi) ion-imprinted composite membranes
  72. Oxidized hyaluronic acid/adipic acid dihydrazide hydrogel as cell microcarriers for tissue regeneration applications
  73. Study of the phase-transition behavior of (AB)3 type star polystyrene-block-poly(n-butylacrylate) copolymers by the combination of rheology and SAXS
  74. A new insight into the reaction mechanism in preparation of poly(phenylene sulfide)
  75. Modified kaolin hydrogel for Cu2+ adsorption
  76. Thyme/garlic essential oils loaded chitosan–alginate nanocomposite: Characterization and antibacterial activities
  77. Thermal and mechanical properties of poly(lactic acid)/poly(butylene adipate-co-terephthalate)/calcium carbonate composite with single continuous morphology
  78. Review Articles
  79. The use of chitosan as a skin-regeneration agent in burns injuries: A review
  80. State of the art of geopolymers: A review
  81. Mechanical, thermal, and tribological characterization of bio-polymeric composites: A comprehensive review
  82. The influence of ionic liquid pretreatment on the physicomechanical properties of polymer biocomposites: A mini-review
  83. Influence of filler material on properties of fiber-reinforced polymer composites: A review
  84. Rapid Communications
  85. Pressure-induced flow processing behind the superior mechanical properties and heat-resistance performance of poly(butylene succinate)
  86. RAFT polymerization-induced self-assembly of semifluorinated liquid-crystalline block copolymers
  87. RAFT polymerization-induced self-assembly of poly(ionic liquids) in ethanol
  88. Topical Issue: Recent advances in smart polymers and their composites: Fundamentals and applications (Guest Editors: Shaohua Jiang and Chunxin Ma)
  89. Fabrication of PANI-modified PVDF nanofibrous yarn for pH sensor
  90. Shape memory polymer/graphene nanocomposites: State-of-the-art
  91. Recent advances in dynamic covalent bond-based shape memory polymers
  92. Construction of esterase-responsive hyperbranched polyprodrug micelles and their antitumor activity in vitro
  93. Regenerable bacterial killing–releasing ultrathin smart hydrogel surfaces modified with zwitterionic polymer brushes
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