Abstract
The development of metal-free photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) in Pickering emulsion by cellulose nanocrystals (CNCs) has successfully investigated. In the presence of ethyl 2-bromoisobutyrate (initiator) and triethylamine (additives), Eosin Y (photocatalyst) can effectively achieve the controllable polymerization of methyl methacrylate utilize CNCs as stabilizer. The polymerization in Pickering emulsion has relatively higher stability. The polymerizations of MMA showed typical “living”/controlled characteristics with controlled molecular weights (150,100–219,100 g/mol) and low Mw/Mn (1.10–1.25). CNCs can not only be recycled, but also can be applicable as one of the most robust “green” emulsifier for PET-ATRP in Pickering emulsion.
Graphic abstract
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Abdalkarim SYH, Yu HY, Wang DC, Yao JM (2017) Electrospun poly(3-hydroxybutyrate-co-3-hydroxy-valerate)/cellulose reinforced nanofibrous membranes with ZnO nanocrystals for antibacterial wound dressings. Cellulose 24:2925–2938. https://doi.org/10.1007/s10570-017-1303-0
An S, Abdiryim T, Ding Y, Nurulla I (2008) A comparative study of the microemulsion and interfacial polymerization for polyindole. Mater Lett 62:935–938. https://doi.org/10.1016/j.matlet.2007.07.014
Bai LJ, Zhang LF, Cheng ZP, Zhu XL (2012) Activators generated by electron transfer for atom transfer radical polymerization: recent advances in catalyst and polymer chemistry. Polym Chem 3:2685–2697. https://doi.org/10.1039/c2py20286g
Bai L, Huan SQ, Xiang WC, Rojas OJ (2018a) Pickering emulsions by combining cellulose nanofibrils and nanocrystals: phase behavior and depletion stabilization. Green Chem 20:1571–1582. https://doi.org/10.1039/c8gc00134k
Bai LJ et al (2018b) RAFT-mediated Pickering emulsion polymerization with cellulose nanocrystals grafted with random copolymer as stabilizer. RSC Adv 8:28660–28667. https://doi.org/10.1039/c8ra03816c
Bai LJ, Jiang XY, Sun ZX, Ma AY (2019) Self-healing nanocomposite hydrogels based on modified cellulose nanocrystals by surface-initiated photoinduced electron transfer ATRP. Cellulose. https://doi.org/10.1007/s10570-019-02449-2
Bian C, Zhou YN, Guo JK, Luo ZH (2018) Aqueous metal-free atom transfer radical polymerization: experiments and model-based approach for mechanistic understanding. Macromolecules 51:2367–2376. https://doi.org/10.1021/acs.macromol.8b00348
Briggs NM, Weston JS, Li B, Venkataramani D, Aichele CP, Harwell JH, Crossley SP (2015) Multiwalled carbon nanotubes at the interface of pickering emulsions. Langmuir 31:13077–13084. https://doi.org/10.1021/acs.langmuir.5b03189
Cheng M, Qin ZY, Chen YY, Liu JM, Ren ZC (2017) Facile one-step extraction and oxidative carboxylation of cellulose nanocrystals through hydrothermal reaction by using mixed inorganic acids. Cellulose 24:3243–3254. https://doi.org/10.1007/s10570-017-1339-1
Chevalier Y, Bolzinger MA (2013) Emulsions stabilized with solid nanoparticles: pickering emulsions. Coll Surf Physicochem Eng Asp 439:23–34. https://doi.org/10.1016/j.colsurfa.2013.02.054
Chmielarz P et al (2017) Electrochemically mediated atom transfer radical polymerization (eATRP). Prog Polym Sci 69:47–78. https://doi.org/10.1016/j.progpolymsci.2017.02.005
Ciftci M, Tasdelen MA, Li WW, Matyjaszewski K, Yagci Y (2013) Photoinitiated ATRP in inverse microemulsion. Macromolecules 46:9537–9543. https://doi.org/10.1021/ma402058a
Cordero R, Jawaid A, Hsiao MS, Lequeux Z, Vaia RA, Ober CK (2018) Mini monomer encapsulated emulsion polymerization of PMMA using aqueous ARGET ATRP. ACS Macro Lett 7:459–463. https://doi.org/10.1021/acsmacrolett.8b00038
Discekici EH et al (2017) Light-mediated atom transfer radical polymerization of semi-fluorinated (Meth)acrylates: facile access to functional materials. J Am Chem Soc 139:5939–5945. https://doi.org/10.1021/jacs.7b01694
Dong HC, Matyjaszewski K (2010) Thermally responsive P(M(EO)(2)MA-co-OEOMA) copolymers via AGET ATRP in miniemulsion. Macromolecules 43:4623–4628. https://doi.org/10.1021/ma100570s
Glasing J, Jessop PG, Champagne P, Cunningham MF (2018) Graft-modified cellulose nanocrystals as CO2-switchable pickering emulsifiers. Polym Chem 9:3864–3872. https://doi.org/10.1039/c8py00417j
Haafiz MKM, Hassan A, Zakaria Z, Inuwa IM (2014) Isolation and characterization of cellulose nanowhiskers from oil palm biomass microcrystalline cellulose. Carbohydr Polym 103:119–125. https://doi.org/10.1016/j.carbpol.2013.11.055
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500. https://doi.org/10.1021/cr900339w
He YQ et al (2013) Factors that affect pickering emulsions stabilized by graphene oxide. ACS Appl Mater Interfaces 5:4843–4855. https://doi.org/10.1021/am400582n
Hu Z, Berry RM, Pelton R, Cranston ED (2017) One-pot water-based hydrophobic surface modification of cellulose nanocrystals using plant polyphenols. ACS Sustain Chem Eng 5:5018–5026. https://doi.org/10.1021/acssuschemeng.7b00415
Ikem VO, Menner A, Horozov TS, Bismarck A (2010) Highly permeable macroporous polymers synthesized from pickering medium and high internal phase emulsion templates. Adv Mate 22:3588–3592. https://doi.org/10.1002/adma.201000729
Jenkins AD, Jones RG, Moad G (2010) Terminology for reversible-deactivation radical polymerization previously called “controlled” radical or “living” radical polymerization (IUPAC Recommendations 2010). Pure Appl Chem 82:483–491. https://doi.org/10.1351/pac-rep-08-04-03
Kalashnikova I, Bizot H, Cathala B, Capron I (2011) New pickering emulsions stabilized by bacterial cellulose nanocrystals. Langmuir 27:7471–7479. https://doi.org/10.1021/la200971f
Kalashnikova I, Bizot H, Cathala B, Capron I (2012) Modulation of cellulose nanocrystals amphiphilic properties to stabilize oil/water interface. Biomacromol 13:267–275. https://doi.org/10.1021/bm201599j
Kwak Y, Magenau AJD, Matyjaszewski K (2011) ARGET ATRP of methyl acrylate with inexpensive ligands and ppm concentrations of catalyst. Macromolecules 44:811–819. https://doi.org/10.1021/ma102665c
Laitinen O, Ojala J, Sirvio JA, Liimatainen H (2017) Sustainable stabilization of oil in water emulsions by cellulose nanocrystals synthesized from deep eutectic solvents. Cellulose 24:1679–1689. https://doi.org/10.1007/s10570-017-1226-9
Li J, Hitchcock AP, Stover HDH (2010) Pickering emulsion templated interfacial atom transfer radical polymerization for microencapsulation. Langmuir 26:17926–17935. https://doi.org/10.1021/la102867v
Li L, Tao H, Wu BL, Zhu G, Li K, Lin N (2018) Triazole end-grafting on cellulose nanocrystals for water-redispersion improvement and reactive enhancement to nanocomposites. ACS Sustain Chem Eng 6:14888–14900. https://doi.org/10.1021/acssuschemeng.8b03407
Liu F, Tang CH (2013) Soy protein nanoparticle aggregates as pickering stabilizers for oil-in-water emulsions. J Agric Food Chem 61:8888–8898. https://doi.org/10.1021/jf401859y
Liu XD, Zhang LF, Cheng ZP, Zhu XL (2016) Metal-free photoinduced electron transfer-atom transfer radical polymerization (PET-ATRP) via a visible light organic photocatalyst. Polym Chem 7:689–700. https://doi.org/10.1039/c5py01765c
Liu BF et al (2018) A green pickering emulsion stabilized by cellulose nanocrystals via RAFT polymerization. Cellulose 25:77–85. https://doi.org/10.1007/s10570-017-1559-4
Liu SM, Bai LJ, Wang WX, Chen H (2019) Fabrication of microcapsules by the combination of biomass porous carbon and polydopamine for dual self-healing hydrogels. J Agric Food Chem 67:1061–1071. https://doi.org/10.1021/acs.jafc.8b06241
Lorandi F, Wang Y, Fantin M, Matyjaszewski K (2018) Ab initio emulsion atom-transfer radical polymerization. Angew Chem Inter Ed 57:8270–8274. https://doi.org/10.1002/anie.201804647
Lu P, Hsieh YL (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82:329–336. https://doi.org/10.1016/j.carbpol.2010.04.073
Ma AY, Wang N, Bai LJ, Chen H, Wang WX (2018) Surface-initiated metal-free photoinduced ATRP of 4-vinylpyridine from SiO2 via visible light photocatalysis for self-healing hydrogels. Ind Eng Chem Res 57:17417–17429. https://doi.org/10.1021/acs.iecr.8b05020
Manga MS, Cayre OJ, Biggs S, Hunter TN (2018) Influence of pH-responsive monomer content on the behavior of Di-block copolymers in solution and as stabilizers of pickering latex particle emulsifiers. Front Chem 6:301. https://doi.org/10.3389/fchem.2018.00301
Matyjaszewski K (2012) Atom transfer radical polymerization (ATRP): current status and future perspectives. Macromolecules 45:4015–4039. https://doi.org/10.1021/ma3001719
Matyjaszewski K, Tsarevsky NV (2014) Macromolecular engineering by atom transfer radical polymerization. J Am Chem Soc 136:6513–6533. https://doi.org/10.1021/ja408069v
Pan XC, Lathwal S, Mack S, Yan JJ, Das SR, Matyjaszewski K (2017) Automated synthesis of well-defined polymers and biohybrids by atom transfer radical polymerization using a DNA synthesizer. Angew Chem Inter Ed 56:2740–2743. https://doi.org/10.1002/anie.201611567
Pearson RM, Lim CH, McCarthy BG, Musgrave CB, Miyake GM (2016) Organocatalyzed atom transfer radical polymerization using N-aryl phenoxazines as photoredox catalysts. J Am Chem Soc 138:11399–11407. https://doi.org/10.1021/jacs.6b08068
Rao ZL, Liu SM, Wu RY, Bai LJ, Wang WX (2019) Fabrication of dual network self-healing alginate/guar gum hydrogels based on polydopamine-type microcapsules from mesoporous silica nanoparticles. Int J Biol Macromol 129:916–926. https://doi.org/10.1016/j.ijbiomac.2019.02.089
Ryan MD, Pearson RM, French TA, Miyake GM (2017) Impact of light intensity on control in photoinduced organocatalyzed atom transfer radical polymerization. Macromolecules 50:4616–4622. https://doi.org/10.1021/acs.macromol.7b00502
Song ML, Yu HY, Chen LM, Zhu JY, Wang YY (2019) Multibranch strategy to decorate carboxyl groups on cellulose nanocrystals to prepare adsorbent/flocculants and Pickering emulsions. ACS Sustain Chem Eng 7:6969–6980. https://doi.org/10.1021/acssuschemeng.8b06671
Teixeira RFA, McKenzie HS, Boyd AA, Bon SAF (2011) Pickering emulsion polymerization using laponite clay as stabilizer to prepare armored “soft” polymer latexes. Macromolecules 44:7415–7422. https://doi.org/10.1021/ma201691u
Theriot JC, Lim CH, Yang H, Ryan MD, Musgrave CB, Miyake GM (2016) Organocatalyzed atom transfer radical polymerization driven by visible light. Science 352:1082–1086. https://doi.org/10.1126/science.aaf3935
Treat NJ et al (2014) Metal-free atom transfer radical polymerization. J Am Chem Soc 136:16096–16101. https://doi.org/10.1021/ja510389m
Wei YP, Jia YY, Wang WJ, Li BG, Zhu SP (2014) Surfactant-ligand design for ab initio emulsion atom transfer radical polymerization. Macromolecules 47:7701–7706. https://doi.org/10.1021/ma501905d
Wei YP, Liu PW, Wang WJ, Li BG, Zhu SP (2015) Well-controlled and stable emulsion ATRP of MMA with low surfactant concentration using surfactant-ligand design as the copper capture agent. Polym Chem 6:2837–2843. https://doi.org/10.1039/c5py00012b
Werner A, Schmitt V, Sebe G, Heroguez V (2017) Synthesis of surfactant-free micro- and nanolatexes from pickering emulsions stabilized by acetylated cellulose nanocrystals. Polym Chem 8:6064–6072. https://doi.org/10.1039/c7py01203a
Ye SN, Yu HY, Wang DC (2018) Green acid-free one-stephydrothermal ammoniumpersulfate oxidation of viscose fiber wastes to obtaincarboxylated spherical cellulose nanocrystals for oil/water pickering emulsion. Cellulose 25:5139–5155. https://doi.org/10.1007/s10570-018-1917-x
Yu HY, Qin ZY, Liang BL, Liu N, Zhou Z, Chen L (2013) Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1:3938–3944. https://doi.org/10.1039/c3ta01150j
Yu HY, Abdalkarim SYH, Zhang H, Wang C, Tam KC (2019) Simple process to produce high-yield cellulose nanocrystals using recyclable citric/hydrochloric acids. ACS Sustain Chem Eng 7:4912–4923. https://doi.org/10.1021/acssuschemeng.8b05526
Zhang YC et al (2017) Cellulose nanofibril-reinforced biodegradable polymer composites obtained via a pickering emulsion approach. Cellulose 24:3313–3322. https://doi.org/10.1007/s10570-017-1324-8
Zhang WP, Li LY, Ou WH, Song LL, Zhang QJ (2018) Hydrophobic modification of hemp powders for their application in the stabilization of pickering emulsions. Cellulose 25:4107–4120. https://doi.org/10.1007/s10570-018-1848-6
Zhu Y, Luo XG, Wu X, Li W, Li B, Lu A, Liu SL (2017) Cellulose gel dispersions: fascinating green particles for the stabilization of oil/water pickering emulsion. Cellulose 24:207–217. https://doi.org/10.1007/s10570-016-1093-9
Acknowledgments
The research was financially supported by the National Natural Science Foundation of China (Nos. 51773086 and 51573075), the Key Program for Basic Research of Natural Science Foundation of Shandong Province (No. ZR2018ZC0946) and the Project of Shandong Province Higher Educational Science (Nos. J16LC20 and J18KA080).
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflicts of interest
There are no conflicts to declare.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Wang, G., Xi, M., Bai, L. et al. Pickering emulsion of metal-free photoinduced electron transfer-ATRP stabilized by cellulose nanocrystals. Cellulose 26, 5947–5957 (2019). https://doi.org/10.1007/s10570-019-02528-4
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-019-02528-4