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| Preparation and characterization of conducting polymer-coated thermally expandable microspheres |
| Shu-Ying Chena, Zhi-Cheng Suna, Lu-Hai Lia, Yong-Hao Xiaoa, Yan-Min Yub |
a Beijing Engineering Research Center of Printed Electronics, School of Printing and Packaging Engineering, Beijing Institute of Graphic Communication, Beijing 102600, China;
b College of Environmental & Energy Engineering, Beijing University of Technology, Beijing 100124, China |
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Abstract The thermally expandable microspheres (TEMs) were prepared via suspension polymerization with acrylonitrile (AN), methyl methacrylate (MMA) and methyl acrylate (MA) as monomers and n-hexane as the blowing agent. Meanwhile, a novel type of functional and conductive thermal expandable microsphere was obtained through strongly covering the surface of microsphere by conductive polymers with the mass loading of 1.5%. The optimal conditions to prepare high foaming ratio and equally distributed microcapsules were investigated with AN-MMA-MA in the proportion of 70%/20%/10% (m/m/m), and 25 wt% of n-hexane in oil phase. The further investigation results showed that the unexpanded TEMs were about 30 μm in diameter and the maximum expansion ratio was nearly 125 times of original volume. The polypyrrole (PPy) was smoothly coated on the surface of the TEMs and the expansion property of PPy-coated TEMs was almost the same as the uncoated TEMs. Moreover, the structure and expanding performance of TEMs and PPy-coated TEMs were characterized by scanning electron microscopy (SEM), laser particle size analyzer and dilatometer (DIL).
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Received: 02 September 2016
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| Fund:The authors are thankful to the National Natural Science Foundation of China (Nos. 21206171,21376010), the Project of Natural Science Foundation of Beijing (No. 2152012), the Young Elite Teacher Project (No. 27170115004/027), the Project of 2011 Collaborative Innovation for Green Printing and Publishing Technology and the Project of Beijing Municipal Commission of Education (No. km201410005007) for the financial supports. |
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Corresponding Authors:
Zhi-Cheng Sun, Yan-Min Yu
E-mail: sunzhicheng@bigc.edu.cn;ymyu@bjut.edu.cn
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[80_TD$DIF]S.Y. Chen, Z.C. Sun, L.H. Li, Preparation and characterization of thermally expandable microspheres, Mater. Sci. Forum 852(2016) 596-600 Trans Tech Publications.
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M. Safajou-Jahankhanemlou, F. Abbasi, M. Salami-Kalajahi, Synthesis and characterization of thermally expandable PMMA-based microcapsules with different cross-linking density, Colloid Polym. Sci. 294(2016) 1055-1064.
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M.D. Banea, L.F.M. da Silva, R.J.C. Carbas, R.D.S.G. Campilho, Mechanical and thermal characterization of a structural polyurethane adhesive modified with thermally expandable particles, Int. J. Adhes. Adhes. 54(2014) 191-199.
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S.Y. Yu, Y.C. Li, T. Xiong, et al., A ladder conjugated polymer transducer for solidcontact Cu2+-selective electrodes, Chin. Chem. Lett. 25(2014) 364-366.
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X.Y. Hu, Q.X. Liu, D. Ma, et al., One-step synthesis of MnO2 doped poly (anilineco-o-aminophenol) and the capacitive behaviors of the conducting copolymer, Chin. Chem. Lett. 26(2015) 1367-1370.
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| [26] |
Y.Y. Yao, L. Zhang, Z.F. Wang, J.K. Xu, Y.P. Wen, Electrochemical determination of quercetin by self-assembled platinum nanoparticles/poly (hydroxymethylated-3,4-ethylenedioxylthiophene) nanocomposite modified glassy carbon electrode, Chin. Chem. Lett. 25(2014) 505-510.
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M.R. Huang, Y.B. Ding, X.G. Li, et al., Synthesis of semiconducting polymer microparticles as solid ionophore with abundant complexing sites for long-life Pb(II) sensors, ACS Appl. Mater. Interfaces 6(2014) 22096-22107.
|
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M.R. Huang, H.J. Lu, X.G. Li, Synthesis and strong heavy-metal ion sorption of copolymer microparticles from phenylenediamine and its sulfonate, J. Mater. Chem. 22(2012) 17685-17699.
|
| [29] |
X.G. Li, H. Feng, M.R. Huang, G.L. Gu, M.G. Moloney, Ultrasensitive Pb(II) potentiometric sensor based on copolyaniline nanoparticles in a plasticizerfree membrane with a long lifetime, Anal. Chem. 84(2011) 134-140.
|
| [30] |
X.G. Li, R. Liu, M.R. Huang, Facile synthesis and highly reactive silver ion adsorption of novel microparticles of sulfodiphenylamine and diaminonaphthalene copolymers, Chem. Mater. 17(2005) 5411-5419.
|
| [31] |
X.G. Li, X.L. Ma, J. Sun, M.R. Huang, Powerful reactive sorption of silver(I) and mercury(II) onto poly(o-phenylenediamine) microparticles, Langmuir 25(2009) 1675-1684.
|
| [32] |
X.G. Li, Y.Z. Liao, M.R. Huang, V. Strong, R.B. Kaner, Ultra-sensitive chemosensors for Fe(III) and explosives based on highly fluorescent oligofluoranthene, Chem. Sci. 4(2013) 1970-1978.
|
| [33] |
A. Schmid, L.R. Sutton, S.P. Armes, P.S. Bain, G. Manfrè, Synthesis and evaluation of polypyrrole-coated thermally-expandable microspheres:an improved approach to reversible adhesion, Soft Matter 5(2009) 407-412.
|
| [34] |
H.E. Cingil, J.A. Balmer, S.P. Armes, P.S. Bain, Conducting polymer-coated thermally expandable microspheres, Polym. Chem. 1(2010) 1323-1331.
|
| [35] |
G. Vamvounis, M. Jonsson, E. Malmström, A. Hult, Synthesis and properties of poly (3-n-dodecylthiophene) modified thermally expandable microspheres, Eur. Polym. J. 49(2013) 1503-1509.
|
| [36] |
X.G. Li, Q.F. Lü, M.R. Huang, Self-stabilized nanoparticles of intrinsically conducting copolymers from 5-sulfonic-2-anisidine, Small 4(2008) 1201-1209.
|
| [37] |
X.G. Li, F. Wei, M.R. Huang, Y.B. Xie, Facile synthesis and intrinsic conductivity of novel pyrrole copolymer nanoparticles with inherent self-stability, J. Phys. Chem. B 111(2007) 5829-5836.
|
| [38] |
X.G. Li, Z.Z. Hou, M.R. Huang, M.G. Moloney, Efficient synthesis of intrinsically conducting polypyrrole nanoparticles containing hydroxy sulfoaniline as key self-stabilized units, J. Phys. Chem. C 113(2009) 21586-21595.
|
| [39] |
X.G. Li, A. Li, M.R. Huang, Efficient and scalable synthesis of pure polypyrrole nanoparticles applicable for advanced nanocomposites and carbon nanoparticles, J. Phys. Chem. C 114(2010) 19244-19255.
|
| [40] |
M. Jonsson, O. Nordin, E. Malmström, C. Hammer, Suspension polymerization of thermally expandable core/shell particles, Polymer 47(2006) 3315-3324.
|
| [41] |
Z.S. Hou, Y.R. Xia, W.Q. Qu, C.Y. Kan, Preparation and properties of thermoplastic expandable microspheres with P(VDC-AN-MMA) shell by suspension polymerization, Int. J. Polym. Mater. Polym. Biomater. 64(2015) 427-431.
|
| [42] |
J.G. Kim, J.U. Ha, S.K. Jeoung, et al., Halloysite nanotubes as a stabilizer:fabrication of thermally expandable microcapsules via Pickering suspension polymerization, Colloid Polym. Sci. 293(2015) 3595-3602.
|
| [1] |
S. Gouin, Microencapsulation:industrial appraisal of existing technologies and trends, Trends Food Sci. Technol. 15(2004) 330-347.
|
| [2] |
S. Benita, Microencapsulation:Methods and Industrial Applications, 2nd ed., CRC Press, Boca Raton, 2005.
|
| [3] |
S.D. Morehouse Jr., Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same, U.S. Patent 3615972.
|
| [4] |
J.L. Garner, P.A. Tiffany, Method for expanding microspheres and expandable composition, U.S. Patent 4179546.
|
| [5] |
G.E. Melber, W.A. Oswald, L.E. Wolinski, Composition and process for drying and expanding microspheres, U.S. Patent 4722943.
|
| [6] |
H.S. Wu, F.M. Sun, V.L. Dimonie, A. Klein, Expandable hollow particles, U.S. Patent 583526.
|
| [7] |
L.O. Svedberg, G. Hovland, T. Holmlund, Method and expansion device for preparing expanded thermoplastic microspheres, U.S. Patent 7192989.
|
| [8] |
L.O. Svedberg, P. Ajdén, Method and a device for preparation of expanded microspheres, WIPO Patent Application WO/2014/198532.
|
| [9] |
[80_TD$DIF]S.Y. Chen, Z.C. Sun, L.H. Li, Preparation and characterization of thermally expandable microspheres, Mater. Sci. Forum 852(2016) 596-600 Trans Tech Publications.
|
| [10] |
Z.S. Hou, C.Y. Kan, Preparation and properties of thermoexpandable polymeric microspheres, Chin. Chem. Lett. 25(2014) 1279-1281.
|
| [11] |
M. Jonsson, O. Nordin, A.L. Kron, E. Malmström, Thermally expandable microspheres with excellent expansion characteristics at high temperature, J. Appl. Polym. Sci. 117(2010) 384-392.
|
| [12] |
M. Fujino, T. Taniguchi, Y. Kawaguchi, M. Ohshima, Mathematical models and numerical simulations of a thermally expandable microballoon for plastic foaming, Chem. Eng. Sci. 104(2013) 220-227.
|
| [13] |
M. Safajou-Jahankhanemlou, F. Abbasi, M. Salami-Kalajahi, Synthesis and characterization of thermally expandable PMMA-based microcapsules with different cross-linking density, Colloid Polym. Sci. 294(2016) 1055-1064.
|
| [14] |
M. Jonsson, O. Nordin, A.L. Kron, E. Malmström, Influence of crosslinking on the characteristics of thermally expandable microspheres expanding at high temperature, J. Appl. Polym. Sci. 118(2010) 1219-1229.
|
| [15] |
M. Jonsson, O. Nordin, E. Malmström, Increased onset temperature ofexpansion in thermally expandable microspheres through combination of crosslinking agents, J. Appl. Polym. Sci. 121(2011) 369-375.
|
| [16] |
R. Urbas, U.S. Elesini, Color differences and perceptive properties of prints made with microcapsules, J. Graph. Eng. Des. 6(2015) 15.
|
| [17] |
J.W. Jeong, J.G. Mccall, G. Shin, et al., Wireless optofluidic systems for programmable in vivo pharmacology and optogenetics, Cell 162(2015) 662-674.
|
| [18] |
M.D. Banea, L.F.M. da Silva, R.J.C. Carbas, R.D.S.G. Campilho, Mechanical and thermal characterization of a structural polyurethane adhesive modified with thermally expandable particles, Int. J. Adhes. Adhes. 54(2014) 191-199.
|
| [19] |
M.D. Banea, L.F.M. da Silva, R.J.C. Carbas, Debonding on command of adhesive joints for the automotive industry, Int. J. Adhes. Adhes. 59(2015) 14-20.
|
| [20] |
J. Loomis, P. Xu, B. Panchapakesan, Stimuli-responsive transformation in carbon nanotube/expanding microsphere-polymer composites, Nanotechnology 24(2013) 185703.
|
| [21] |
L.J. Wang, X. Yang, J. Zhang, C. Zhang, L. He, The compressive properties of expandable microspheres/epoxy foams, Compos.Part B-Eng. 56(2014) 724-732.
|
| [22] |
M. Jonsson, D. Nyström, O. Nordin, E. Malmström, Surface modification of thermally expandable microspheres by grafting poly (glycidyl methacrylate) using ARGET ATRP, Eur. Polym. J. 45(2009) 2374-2382.
|
| [23] |
Y.C. Lu, J. Broughton, P. Winfield, Surface modification of thermally expandable microspheres for enhanced performance of disbondable adhesive, Int. J. Adhes. Adhes. 66(2016) 33-40.
|
| [24] |
S.Y. Yu, Y.C. Li, T. Xiong, et al., A ladder conjugated polymer transducer for solidcontact Cu2+-selective electrodes, Chin. Chem. Lett. 25(2014) 364-366.
|
| [25] |
X.Y. Hu, Q.X. Liu, D. Ma, et al., One-step synthesis of MnO2 doped poly (anilineco-o-aminophenol) and the capacitive behaviors of the conducting copolymer, Chin. Chem. Lett. 26(2015) 1367-1370.
|
| [26] |
Y.Y. Yao, L. Zhang, Z.F. Wang, J.K. Xu, Y.P. Wen, Electrochemical determination of quercetin by self-assembled platinum nanoparticles/poly (hydroxymethylated-3,4-ethylenedioxylthiophene) nanocomposite modified glassy carbon electrode, Chin. Chem. Lett. 25(2014) 505-510.
|
| [27] |
M.R. Huang, Y.B. Ding, X.G. Li, et al., Synthesis of semiconducting polymer microparticles as solid ionophore with abundant complexing sites for long-life Pb(II) sensors, ACS Appl. Mater. Interfaces 6(2014) 22096-22107.
|
| [28] |
M.R. Huang, H.J. Lu, X.G. Li, Synthesis and strong heavy-metal ion sorption of copolymer microparticles from phenylenediamine and its sulfonate, J. Mater. Chem. 22(2012) 17685-17699.
|
| [29] |
X.G. Li, H. Feng, M.R. Huang, G.L. Gu, M.G. Moloney, Ultrasensitive Pb(II) potentiometric sensor based on copolyaniline nanoparticles in a plasticizerfree membrane with a long lifetime, Anal. Chem. 84(2011) 134-140.
|
| [30] |
X.G. Li, R. Liu, M.R. Huang, Facile synthesis and highly reactive silver ion adsorption of novel microparticles of sulfodiphenylamine and diaminonaphthalene copolymers, Chem. Mater. 17(2005) 5411-5419.
|
| [31] |
X.G. Li, X.L. Ma, J. Sun, M.R. Huang, Powerful reactive sorption of silver(I) and mercury(II) onto poly(o-phenylenediamine) microparticles, Langmuir 25(2009) 1675-1684.
|
| [32] |
X.G. Li, Y.Z. Liao, M.R. Huang, V. Strong, R.B. Kaner, Ultra-sensitive chemosensors for Fe(III) and explosives based on highly fluorescent oligofluoranthene, Chem. Sci. 4(2013) 1970-1978.
|
| [33] |
A. Schmid, L.R. Sutton, S.P. Armes, P.S. Bain, G. Manfrè, Synthesis and evaluation of polypyrrole-coated thermally-expandable microspheres:an improved approach to reversible adhesion, Soft Matter 5(2009) 407-412.
|
| [34] |
H.E. Cingil, J.A. Balmer, S.P. Armes, P.S. Bain, Conducting polymer-coated thermally expandable microspheres, Polym. Chem. 1(2010) 1323-1331.
|
| [35] |
G. Vamvounis, M. Jonsson, E. Malmström, A. Hult, Synthesis and properties of poly (3-n-dodecylthiophene) modified thermally expandable microspheres, Eur. Polym. J. 49(2013) 1503-1509.
|
| [36] |
X.G. Li, Q.F. Lü, M.R. Huang, Self-stabilized nanoparticles of intrinsically conducting copolymers from 5-sulfonic-2-anisidine, Small 4(2008) 1201-1209.
|
| [37] |
X.G. Li, F. Wei, M.R. Huang, Y.B. Xie, Facile synthesis and intrinsic conductivity of novel pyrrole copolymer nanoparticles with inherent self-stability, J. Phys. Chem. B 111(2007) 5829-5836.
|
| [38] |
X.G. Li, Z.Z. Hou, M.R. Huang, M.G. Moloney, Efficient synthesis of intrinsically conducting polypyrrole nanoparticles containing hydroxy sulfoaniline as key self-stabilized units, J. Phys. Chem. C 113(2009) 21586-21595.
|
| [39] |
X.G. Li, A. Li, M.R. Huang, Efficient and scalable synthesis of pure polypyrrole nanoparticles applicable for advanced nanocomposites and carbon nanoparticles, J. Phys. Chem. C 114(2010) 19244-19255.
|
| [40] |
M. Jonsson, O. Nordin, E. Malmström, C. Hammer, Suspension polymerization of thermally expandable core/shell particles, Polymer 47(2006) 3315-3324.
|
| [41] |
Z.S. Hou, Y.R. Xia, W.Q. Qu, C.Y. Kan, Preparation and properties of thermoplastic expandable microspheres with P(VDC-AN-MMA) shell by suspension polymerization, Int. J. Polym. Mater. Polym. Biomater. 64(2015) 427-431.
|
| [42] |
J.G. Kim, J.U. Ha, S.K. Jeoung, et al., Halloysite nanotubes as a stabilizer:fabrication of thermally expandable microcapsules via Pickering suspension polymerization, Colloid Polym. Sci. 293(2015) 3595-3602.
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