Synthesis of raspberry-like polymer/SiO2 hybrid colloidal spheres grafted by block-copolymer poly(MPC-b-MPS) for underwater superoleophobic anti-biofouling coatings

doi:10.1016/j.jcis.2018.03.054

Journal of Colloid and Interface Science

Volume 522, 15 July 2018, Pages 20-28

https://doi.org/10.1016/j.jcis.2018.03.054 Get rights and content

Abstract

Raspberry-like polymer/inorganic compound hybrid colloidal spheres have attracted tremendous interest owing to their many potential applications, but most of them are concentrated on synthesis methods, controlling structures and morphologies. Herein, we synthesize raspberry-like poly(ethyl methacrylate)/SiO₂ colloidal spheres and further graft a hydrophilic diblock copolymer on the SiO₂ nanoparticles. The obtained copolymer-grafted hybrid sphere-based coatings are robust and display excellent underwater superoleophobic and anti-biofouling performances as well as self-repairing ability.

Graphical abstract

Coatings with excellent underwater superoleophobic and anti-biofouling performances as well as self-repairing ability have been fabricated through the grafting of hydrophilic block copolymer on the raspberry-like polymer/SiO₂ hybrid colloidal spheres.

Introduction

Polymer/inorganic compound hybrid colloidal spheres are one of the most exciting research fields in the past two decades because they combine the advantages of both the ductility, good processability of polymers and the rigidity, heat resistance of inorganic materials, as well as their stimuli-responsiveness, photoelectric properties, etc., and thus display tremendous potentials in functional coatings, composite materials, biomedical materials, photoelectric materials, etc [1], [2], [3], [4], [5], [6].

Various morphologies such as typical core-shell, raspberrylike, multi-core-shell with different polymeric and inorganic components have been synthesized by our group and others based on heterophase polymerization techniques in (mini)emulsion, suspension and dispersion polymerizations [7], [8], [9], [10], [11], [12], [13], [14], [15], [16]. Nevertheless, a large majority focuses the controlling on structures and morphologies of hybrid colloidal spheres with only several involving properties and applications [17], [18], [19], [20]. Recently, we have successfully synthesized UV-responsive, and pH-/T- dual-responsive raspberry-like hybrid colloidal spheres by Pickering emulsion polymerization using titania and silica nanoparticles as the Pickering agents, in which the former showed self-healing superhydrophobicity and self-cleaning ability when used in waterborne coatings, while the latter displayed sequential release of two payloads in two storerooms selectively and independently triggered by temperature or pH [21], [22]. We also fabricated a self-repairing underwater superoleophobic and anti-biofouling coating through the self-assembly of hydrophilic polymeric chain modified raspberry-like microgel spheres. The obtained surface material not only has excellent underwater superoleophobicity but also owns very good subaqueous anti-biofouling property [23].

Since PMPC comprises well-known anti-biofouling phosphoryl choline groups [24], [25], introduction of MPC will significantly reduce the coating’s protein adsorption when used in aqueous environment [26], [27], [28]. In this study, we synthesize raspberry-like poly(ethyl methacrylate) (PEMA)/SiO₂ hybrid colloidal spheres and further graft hydrophilic diblock copolymer poly(2-methacryloyloxyethyl phosphorylcholine-b-3-(trimethoxysilyl)propyl methacrylate) (poly(MPC-b-MPS)) on the SiO₂ nanoparticles of hybrid spheres through the reaction of silanol groups of SiO₂ and the methoxyl groups of MPS. The obtained coating demonstrates very good underwater superoleophobic and anti-biofouling performances as well as self-repairing ability.

Section snippets

Materials

2-Methacryloyloxyethyl phosphorylcholine (MPC, AR, 96%) was purchased from Nanjing Joy-nature institute of science and technology and used as received. 3-(Trimethoxysilyl)propyl methacrylate (MPS, AR, 97%) was purchased from Aladdin Chemical Reagent Co., Ltd. and passed through a neutral alumina column to eliminate inhibitor prior to use. Ethyl α-bromoisobutyrate (EBiB, AR, 98%), ethyl methacrylate (EMA, AR, 99%), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA, AR, 99%), 2,2′-bipyridyl

Syntheses and analyses of hybrid colloidal spheres

Six different molecular weights of poly(MPC) (p1, p2, p3, p4, p5 and p6) and their corresponding diblock copolymers poly(MPC-b-MPS) (cp1, cp2, cp3, cp4, cp5 and cp6) were synthesized. As shown in Table 1 and Fig. 1a, for poly(MPC)_x-Br, the number-average molecular weight (M_n) measured by GPC increases from 3260, 5660, 7570, 10,320, 15,670 to 26,800 g mol⁻¹ through increasing the (MPC/EBiB) ratios for p1, p2, p3, p4, p5 to p6, with the corresponding polymerization degree of MPC calculated as 11,

Conclusions

In summary, we have demonstrated raspberry-like polymer/SiO₂ hybrid colloidal spheres grafted by diblock copolymer poly(2-methacryloyloxyethyl phosphorylcholine-b-3-(trimethoxysilyl)propyl methacrylate) brushes. The polymer cores and the copolymer brushes can ensure the spheres to form dense and robust coating films without using additional binders compared to the previously reported methods. All these grafted hybrid colloidal sphere-based coatings exhibit excellent superoleophobic, quick

Acknowledgment

Financial supports of this research from National Key Research and Development Program of China (2017YFA0204600) and the National Natural Science Foundation of China (51721002, 51673045) are appreciated.

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Regular ArticleSynthesis of raspberry-like polymer/SiO2 hybrid colloidal spheres grafted by block-copolymer poly(MPC-b-MPS) for underwater superoleophobic anti-biofouling coatings

Abstract

Graphical abstract

Introduction

Section snippets

Materials

Syntheses and analyses of hybrid colloidal spheres

Conclusions

Acknowledgment

Adv. Colloid Interface Sci.

Adv. Colloid Interface Sci.

Colloids Surf. B: Biointerfaces

Pickering-type stabilized nanoparticles by heterophase polymerization

Chem. Soc. Rev.

Colloidal capsules: nano- and microcapsules with colloidal particle shells

Chem. Soc. Rev.

Recent progress on silica coating of nanoparticles and related nanomaterials

Adv. Mater.

Polymer/silica nanocomposites: preparation, characterization, properties, and applications

Chem. Rev.

Synthesis of nano/microstructures at fluid interfaces

Angew. Chem. Int. Ed.

Colloidal nanocomposite particles: quo vadis?

J. Mater. Chem.

Use of silica particles for the formation of organic−inorganic particles by surfactant-free emulsion polymerization

Langmuir

Synthesis of daisy-shaped and multipod-like silica/polystyrene nanocomposites

Nano Lett.

Stimuli-responsive pickering emulsions: recent advances and potential applications

Soft Matter

An aqueous emulsion route to synthesize mesoporous carbon vesicles and their nanocomposites

Adv. Mater.

A novel preparation method of raspberry-like PMMA/SiO2 hybrid microspheres

Macromolecules

Synthesis of raspberry-like PMMA/SiO2 nanocomposite particles via a surfactant-free method

Macromolecules

Regular Article
Synthesis of raspberry-like polymer/SiO₂ hybrid colloidal spheres grafted by block-copolymer poly(MPC-b-MPS) for underwater superoleophobic anti-biofouling coatings

Synthesis of raspberry-like PMMA/SiO₂ nanocomposite particles via a surfactant-free method