Abstract
Cross-linked poly(methyl methacrylate) (PMMA) microspheres have been successfully prepared by using the asymmetric cross-linker allyl methacrylate (AMA) via dispersion polymerization. The influence of the AMA amount and polymerization process on the PMMA particle size and morphology has been studied thoroughly. It was found that micron-sized, cross-linked PMMA particles with narrow size distributions could be obtained by a semi-continuous process with the asymmetric cross-linker AMA. The obtained micron-sized, cross-linked PMMA particles could be further used as a light diffusion agent in a polycarbonate matrix, and their light diffusion properties were significantly enhanced by increasing the gel content in the cross-linked particles. Moreover, the influence of the polymerization process, cross-linker content in PMMA and PMMA content in the polycarbonate matrix on light diffusion was carefully investigated. The results showed that the PMMA particles containing 5.0 wt% AMA, obtained by semi-continuous polymerization, had a higher haze and gel content and exhibited a better light diffusion effect than did the other particles.
Similar content being viewed by others
References
Tanaka N, McCalley DV (2016) Core-shell, ultrasmall particles, monoliths, and other support materials in high-performance liquid chromatography. Anal Chem 88:279–298
Song Y, Fan JB, Li X, Liang X, Wang S (2019) pH-regulated heterostructure porous particles enable similarly sized protein separation. Adv Mater 31:1900391
Ma G (2012) Control of heterogeneous structure of porous polymer microspheres prepared from polymerization system and preformed polymer system. Colloid Polym Sci 291:53–70
Lin XF, Kankala RK, Tang N, Xu PY, Hao LZ, Yang DY, Wang SB, Zhang YS, Chen AZ (2018) Supercritical fluid-assisted porous microspheres for efficient delivery of insulin and inhalation therapy of diabetes. Adv Healthcare Mater 12:1800910
Yougen H, Tao Z, Pengli Z, Rong S (2011) Preparation of monodisperse polystyrene/silver composite microspheres and their catalytic properties. Colloid Polym Sci 290:401–409
Li X, Qin L, Zhang Y, Xu Z, Tian L, Guo X, Zhang G (2019) Self-assembly of Mn(II)-amidoximated PAN polymeric beads complex as reusable catalysts for efficient and stable heterogeneous electro-Fenton oxidation. ACS Appl Mater Interfaces 11:3925–3936
Guo S, Zhou S, Li H, You B (2015) Light diffusing films fabricated by strawberry-like PMMA/SiO2 composite microspheres for LED application. J Colloid Interface Sci 448:123–129
Hu J, Zhou Y, Wang M, Yang M, Yan G (2016) Optical diffusers based on the novel fillers of polysiloxane@boehmite core–shell microspheres. Mater Lett 165:107–110
Wang SL, Yue K, Liu LY, Yang WT (2013) Photoreactive, core-shell cross-linked/hollow microspheres prepared by delayed addition of cross-linker in dispersion polymerization for antifouling and immobilization of protein. J Colloid Interface Sci 389:126–133
Ru Y, Zhang X, Wang L, Dai L, Yang W, Qiao J (2015) Polymer composites with high haze and high transmittance. Polym Chem 6:6632–6636
Chen H, Yang F, Chen Q, Zheng J (2017) A novel design of multi-mechanoresponsive and mechanically strong hydrogels. Adv Mater 29:1606900
Adelnia H, Gavgani JN, Soheilmoghaddam M (2015) Fabrication of composite polymer particles by stabilizer-free seeded polymerization. Colloid Polym Sci 293:2445–2450
Zheng C, Zhou Y, Jiao Y, Zhang H (2018) Narrow or monodisperse, physically cross-linked, and “living” spherical polymer particles by one-stage RAFT precipitation polymerization. Macromolecules 52:143–156
Ni H, Liu J, Shi K, Wu M, Yang Y, Zhang L (2016) PMAA-based RAFT dispersion polymerization of MMA in ethanol: conductivity, block length and self-assembly. RSC Adv 6:58218–58225
Peng B, Imhof A (2015) Surface morphology control of cross-linked polymer particles via dispersion polymerization. Soft Matter 11:3589–3598
Tseng CM, Lu YY, El-Aasser MS, Vanderhoff JW (1986) Uniform polymer particles by dispersion polymerization in alcohol. J Polym Sci A Polym Chem 24:2995–3007
Shay JS, English RJ, Spontak RJ, Balik CM, Khan SA (2000) Dispersion polymerization of polystyrene latex stabilized with novel grafted poly(ethylene glycol) macromers in 1-propanol/water. Macromolecules 33:6664–6671
Peng B, van der Wee E, Imhof A, van Blaaderen A (2012) Synthesis of monodisperse, highly cross-linked, fluorescent PMMA particles by dispersion polymerization. Langmuir 28:6776–6785
Cho YS, Shin CH, Han S (2016) Dispersion polymerization of polystyrene particles using alcohol as reaction medium. Nanoscale Res Lett 11:46
Wang T, Sun Z, Liang F, Fan H, Xiang J, Chen Y (2019) Poly(methylmethacrylate) microspheres with matting characteristic prepared by dispersion polymerization. Int J Polym Anal Charact 24:731–740
Zhang B, Lu J, Liu X, Jin H, He G, Guo X (2018) Synthesis of controllable carboxylated polystyrene microspheres by two-step dispersion polymerization with hydrocarbon alcohols. Int J Polym Sci 2018:1–8
Mu J, Zhou Y, Bu X, Zhang T (2014) Preparation and characterization of micron-sized PMMA/SiO2 composite microspheres. J Inorg Organomet Polym Mater 24:776–779
Song J-S, Winnik MA (2005) Cross-linked, monodisperse, micron-sized polystyrene particles by two-stage dispersion polymerization. Macromolecules 38:8300–8307
Cui H, Chen H, Qu RJ, Wang CH, Ji CN, Sun CM, Zhou WY, Yu MM (2008) Synthesis of monodisperse crosslinked polystyrene microspheres via dispersion copolymerization with the crosslinker-postaddition method. J Appl Polym Sci 107:3909–3916
Song J-S, Fdr T, Winnik MA (2004) Two-stage dispersion polymerization toward monodisperse, controlled micrometer-sized copolymer particles. J Am Chem Soc 126:6562–6563
Lee K-C, Lee S-Y (2007) Preparation of highly cross-linked, monodisperse poly(methyl methacrylate) microspheres by dispersion polymerization; part I. batch processes. Macromol Res 15:244–255
Zhang BH, Lv XQ, Zhu AQ, Zheng JW, Yang YQ, An ZS (2018) Morphological stabilization of block copolymer worms using asymmetric cross-linkers during polymerization-induced self-assembly. Macromolecules 51:2776–2784
Hu J, Zhou Y, Zhang T (2014) The novel optical diffusers based on the fillers of boehmite hollow microspheres. Mater Lett 136:114–117
Zhu J, Liu Y, Shen S, Wu J (2017) Fabrication of engineered particle-doped light diffuser with a soft transparent mold of UV-curable polymer. Opt Mater 73:234–240
Tang Y, Liang G, Song C, Li Z, Yu S, Ding X (2018) Enhancement of angular color uniformity of remote-phosphor-converted light-emitting diodes by electrospun-nanofiber diffusing films. Mater Lett 227:104–107
Zhong X, Zhou Y, He M, Tong Y, Fan L, Cai Z (2017) Synthesis of organosiloxane-coated SiO2/CeO2 with multilayered hierarchical structure and its application in optical diffusers. J Mater Sci 52:12806–12817
Kim JW, Lee CH, Jun JB, Suh KD (2001) Monodisperse micron-sized crosslinked polystyrene particles. VII. Importance of monomer-diffusible surface characteristics of growing particles. Colloid Surface A 194:57–64
Ho AK, Iin I, Gurr PA, Mills MF, Qiao GG (2005) Synthesis and characterization of star-like microgels by one-pot free radical polymerization. Polymer 46:6727–6735
Lee K-C, Lee S-Y (2008) Preparation of highly cross-linked, monodisperse poly(methyl methacrylate) microspheres by dispersion polymerization; part II. Semi-continuous processes. Macromol Res 16:293–302
Lee K-C, Wi H-A (2010) Highly crosslinked micron-sized, monodispersed polystyrene particles by batch dispersion polymerization, part 1: batch, delayed addition, and seeded batch processes. J Appl Polym Sci 115:297–307
Yang W, Ming W, Hu J, Lu X, Fu S (1998) Morphological investigations of crosslinked polystyrene microspheres by seeded polymerization. Colloid Polym Sci 276:655–661
Song J-S, Chagal L, Winnik MA (2006) Monodisperse micrometer-size carboxyl-functionalized polystyrene particles obtained by two-stage dispersion polymerization. Macromolecules 39:5729–5737
Lee K-C, Wi H-A (2010) Highly crosslinked micron-sized, monodispersed polystyrene particles by semicontinuous dispersion polymerization. II. Semicontinuous, delayed addition and seeded semicontinuous processes. J Appl Polym Sci 115:3092–3102
Zhao D, Shi X, Liu T, Lu X, Qiu G, Shea KJ (2016) Synthesis of surfactant-free hydroxypropyl methylcellulose nanogels for controlled release of insulin. Carbohydr Polym 151:1006–1011
Zhao Z, Qiu J, Xiong Y, Liu X, Shen J, Guo S (2017) In-situ preparation of core-shell-like scatterers and their effects on optical and mechanical properties of PC-matrix light diffusing materials. Mater Design 115:355–363
Irie Y, Yuasa S, Imoto H, Naka K (2017) Synthesis of bifunctional terminal octasilicate-core dendrimer containing fluorocarbon and hydrocarbon chains. J Polym Sci Pol Chem 55:912–918
Hu J, Zhou Y, Sheng X (2015) Hydrothermal synthesis of ZnO@polysiloxane microspheres and their application in preparing optical diffusers. RSC Adv 5:17064–17069
Suthabanditpong W, Tani M, Takai C, Fuji M, Buntem R, Shirai T (2016) Facile fabrication of light diffuser films based on hollow silica nanoparticles as fillers. Adv Powder Technol 27:454–460
Funding
This work was supported by the National Natural Science Foundation of China (Grant Nos. 51873041, 51933002 and 51473037) and the National Key R&D Program of China (Grant No. 2016YFC1100300).
Author information
Authors and Affiliations
Contributions
Xuechun Zhang and Wuli Yang conceived and designed the research. Material preparation, data collection and analysis were performed by Xuechun Zhang. Measurement of light diffusion property was performed by Xuechun Zhang, Yongbin Cao and Qin Jiang. Preparation of light diffusers was performed by Xuechun Zhang and Yuanying Zhang. The first draft of the manuscript was written by Xuechun Zhang, and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript.
Corresponding author
Ethics declarations
Conflict of interest
The authors declare that they have no conflict of interest.
Additional information
Publisher’s note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Electronic supplementary material
ESM 1
(DOCX 169 kb)
Rights and permissions
About this article
Cite this article
Zhang, X., Cao, Y., Jiang, Q. et al. Preparation of cross-linked poly(methyl methacrylate) microspheres using an asymmetric cross-linker via dispersion polymerization and its application in light diffusers. Colloid Polym Sci 298, 495–504 (2020). https://doi.org/10.1007/s00396-020-04622-7
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s00396-020-04622-7