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Surface Modification and Functionalization of Polymers

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (31 August 2019) | Viewed by 47683

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Special Issue Editors

Dr. Qiang Wei

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Guest Editor

Department of Cellular Biophysics, Max Planck Institute for Medical Research, 70569 Stuttgart, Germany
Interests: surface modification; biointerphase; cell biology
Special Issues, Collections and Topics in MDPI journals

Prof. Linxian Li

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Guest Editor

Ming Wai Lau Centre for Reparative Medicine, Karolinska Institutet, Hong Kong
Interests: surface functionalization; biointerfaces; combinatorial materials

Prof. Hui Zhao

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Guest Editor

Institute of Fundamental and Frontier Sciences, University of Electronic Science and Technology of China, Chengdu 610051, China
Interests: controlled polymerization; confined chemistry; responsive polymers

Special Issue Information

Dear Colleagues,

Polymers, a large class of materials, are particularly important in our daily life. The application of polymers is involved in but not limited to the fields of biomaterials and biomedical devices, energy materials, environmental materials, optical materials, engineering materials, etc. Polymers used for these purposes are mostly selected based on their bulk mechanical properties rather than on the suitability of their surface properties. However, the interfacial properties of polymer materials, including both chemical composition and physical morphology, greatly affect their efficiency in applications. In some cases, polymer materials even fail in practical applications without surface functionalization. For example, the adsorption of blood proteins on the unmodified surfaces of implant devices initiates a cascade of biological responses.

Considering the high requirements of the surface modification and functionalization of polymers, we urgently need to better understand the interfacial behaviors between polymer materials and their application environment. Moreover, the development of novel approaches to modify polymer surfaces with desired surface characters is required to meet the growing demand of the applications.

Therefore, the editors are pleased to launch this Special Issue and invite researchers to contribute their reviews and original papers in the field of the surface modification and functionalization of polymers. Potential topics cover but are not restricted to the following:

Surface modification technologies of polymer materials;
Functional polymers with designed interfacial properties;
Surface patterning technologies on polymer materials;
Technologies for controlling surface morphology;
Stimuli-responsive surfaces;
Superhydrophilic, superhydrophilic, and slippery surfaces;
Interfacial interactions between polymer materials and their application environment;
Characterization of the surfaces and interfaces of functional polymers.

Dr. Qiang Wei
Prof. Linxian Li
Prof. Hui Zhao
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Polymer
Surface modification
Surface function
Coating
Interfacial property
Biointerfaces
Surface patterning
Surface morphology
Surface chemistry

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Published Papers (9 papers)

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Research

13 pages, 2558 KB

Open AccessArticle

Surface Treatment Effects on the Mechanical Properties of Silica Carbon Black Reinforced Natural Rubber/Butadiene Rubber Composites

by Miaomiao Qian, Weimin Huang, Jinfeng Wang, Xiaofeng Wang, Weiping Liu and Yanchao Zhu

Polymers 2019, 11(11), 1763; https://doi.org/10.3390/polym11111763 - 27 Oct 2019

Cited by 28 | Viewed by 5970

Abstract

For the first time, phenolic formaldehyde resin (PF)-treated silica carbon black (SiCB) were prepared with different treatment conditions and their effect as fillers on the mechanical properties of filler filled natural rubber/butadiene rubber (NR/BR) composites were investigated in detail. The PF coating layer on the SiCB derived from rusk husk not only promoted the dispersion of the fillers but also improved the interfacial interactions between fillers and the rubber matrix. As a result, both the cross-link density and mechanical properties of the obtained composites were effectively enhanced. The filler SiCB with 3 wt % PF surface treatment greatly improved the tensile strength of NR/BR composites and reached 7.1 MPa, which increased by 73.7% compared with that of SiCB-filled NR/BR composites. The improved interfacial interactions promoted higher energy dissipation, leading to simultaneously enhancing the glass transition temperature of the obtained composites. Due to the easy processing and low cost of filler as well as the effectively enhanced mechanical properties of composites, the PF-coating methodology has a great potential for practical applications in SiCB reinforced high-performance composites. A commercial filler, carbon black (N774), was also used in this study and evaluated under the same conditions for comparison. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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16 pages, 4488 KB

Open AccessArticle

The Impact of Laser Radiation on Polypropylene Molded Pieces Depending on Their Surface Conditions

by Piotr Czyżewski, Dariusz Sykutera, Marek Bieliński and Adam Troszyński

Polymers 2019, 11(10), 1660; https://doi.org/10.3390/polym11101660 - 11 Oct 2019

Cited by 7 | Viewed by 3149

Abstract

The article presents an analysis of the impact of a laser beam interaction (Nd: YVO₄) with selected operational parameters on the quality of graphical marks obtained on the surfaces of polypropylene-molded pieces with different surface textures (variable parameters of the surface layer). Polypropylene test specimens were produced by injection using the original injection mold, which allowed for the obtainment of products with variable surface finish parameters determined by the surface condition of the forming cavity. The presented relationship between the parameters of laser performance, the texture of a molded piece surface, the molded piece’s color, and types of masterbatches supporting the marking process allows for the assessment of the efficiency of graphic symbol application by laser marking. The original evaluation criteria for the conducted process were adopted. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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14 pages, 3489 KB

Open AccessArticle

Enhanced Two-Photon Fluorescence and Fluorescence Imaging of Novel Probe for Calcium Ion by Self-Assembly with Conjugated Polymer

by Yue-liang Zhai, Qiu-bo Wang, Hao Yu, Xiao-yuan Ji and Xian Zhang

Polymers 2019, 11(10), 1643; https://doi.org/10.3390/polym11101643 - 10 Oct 2019

Cited by 6 | Viewed by 3338

Abstract

The calcium ion (Ca²⁺) isa highly versatile intracellular signal messenger regulating many different cellular functions. It is important to design probes with good fluorescence and two-photon (TP) active cross-sections (Φδ) to explore the concentration distribution of Ca²⁺. In this manuscript, a novel TP fluorescence calcium probe (BAPTAVP) with positive charges, based on the classical Ca²⁺ indicator of BAPTA (1,2-bis(2-aminophenoxy)-ethane-N,N,N’,N’-tetra acetic acid), and a conjugated polymer (PCBMB) with negative charges were designed and synthesized. The results from transmission electron microscopy (TEM), atomic force microscopy (AFM), dynamic light scattering (DLS), and the zeta potential (ZP) showed that nanoparticles were obtained by the self-assembly of PCBMB and BAPTAVP. Moreover, the fluorescence properties of BAPTAVP were effectively improved by fluorescence resonance energy transfer (FRET) with PCBMB and attenuating the intramolecular charge transfer (ICT) after the addition of Ca²⁺. The quantum yield and Φδ of PCBMB-BAPTAVP increased by about four and six times in comparison to those of BAPTAVP, respectively. The TP fluorescence imaging experiments indicated that the PCBMB-BAPTAVP system could effectively detect Ca²⁺ in living cells with high sensitivity. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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12 pages, 6622 KB

Open AccessArticle

Isotactic-Polypropylene/Atactic-Polystyrene Miktoarm Star Copolymers: Synthesis and Aggregation Morphology

by Yuanjie Wang, Xinzhi Liu, Liying Liu and Hui Niu

Polymers 2019, 11(10), 1574; https://doi.org/10.3390/polym11101574 - 27 Sep 2019

Cited by 4 | Viewed by 4547

Abstract

In this work, a series of isotactic-polypropylene/atactic-polystyrene (iPP/aPS) miktoarm star copolymers, P_xS_y, was synthesized via an arm-first approach. Varied star macromolecule architectures were fabricated by designing the arm length and the arm numbers (x and y). These miktoarm stars were able to form micelles in selective solvent (N,N′-dimethylformamide (DMF)), in which the insoluble iPP arms formed the core and the soluble aPS arms formed the shell. The miktoarm polymers aggregated to micro-nanoscale binary structures (MNBSes) in the casting process, and their morphologies, including the MNBS shape and size, were greatly influenced by the P_xS_y architectures. The MNBSes endowed the material surface with superhydrophobic performance with a water contact angle of 157.0° and a sliding angle of 1.5°. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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21 pages, 3279 KB

Open AccessArticle

Preparation of Methacrylate-Based Polymers Modified with Chiral Resorcinarenes and Their Evaluation as Sorbents in Norepinephrine Microextraction

by Alver Castillo-Aguirre and Mauricio Maldonado

Polymers 2019, 11(9), 1428; https://doi.org/10.3390/polym11091428 - 30 Aug 2019

Cited by 16 | Viewed by 3464

Abstract

Aminomethylation reactions between chiral amino compounds (S)-(-)-1-phenylethylamine and l-proline with tetranonylresorcinarene and tetra-(4-hydroxyphenyl)resorcinarene in presence of formaldehyde were studied. The reaction between l-proline and resorcinarenes generated regioselectively chiral tetra-Mannich bases, due to the molecular incorporation of the fragment of the chiral amino acid. On the other hand, tetranonylresorcinarene and (S)-(-)-1-phenylethylamine formed regio- and diasteroselectively chiral tetrabenzoxazines, both by chiral auxiliary functionalization and by the transformation of the molecular structure that confers inherent chirality. The products obtained were characterized using IR, ¹H-NMR, ¹³C-NMR, COSY, HMQC, and HMBC techniques. The reaction of (S)-(-)-1-phenylethylamine with tetra-(4-hydroxyphenyl)resorcinarene did not proceed under the experimental conditions. Once the chiral aminomethylated tetra-(4-hydroxyphenyl)resorcinarene was obtained, the chemical modification of poly(GMA–co–EDMA) was studied, and the results showed an efficient incorporation of the aminomethylated compound. For the physical modification, chiral aminomethylated tetranonylresorcinarenes were employed, finding that the incorporation of modified resorcinarenes occurs, but with less efficiency than that observed using chemical modification. The modified polymers were characterized via FT-IR, scanning electron microscopy imaging, and elemental analysis. Finally, polymers modified with chiral resorcinarenes were used as sorbents in norepinephrine microextraction; for practical purposes, artificial urine was prepared and used. To perform the microextraction, the decision was made to use the modern rotating-disk sorptive extraction technique (RDSE), because of its analytical attributes as a green, or eco-friendly, technique. According to the results, the method preliminarily validated for the determination of norepinephrine in artificial urine shows that the modified polymer with chiral derivative of tetra-(4-hydroxyphenyl)resorcinarene worked effectively as a new sorbent phase for the quantitative microextraction of norepinephrine, exhibiting high stability and homogeneity of composition and structure within the working range. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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12 pages, 1683 KB

Open AccessArticle

Pyrene-Functionalized Polyacetylenes: Synthesis and Photoluminescence Property

by Tanxiao Shen, Nan Jiang, Xiao’a Zhang, Lirong He, Xian Hua Lang, Jing Zhi Sun and Hui Zhao

Polymers 2019, 11(8), 1366; https://doi.org/10.3390/polym11081366 - 19 Aug 2019

Cited by 4 | Viewed by 5845

Abstract

Four pyrene-functionalized polyacetylenes were designed and prepared through a typical post-polymerization modification route, which is the highly efficient reaction between activated ester and primary anime groups. The chemical structures of the resultant polymers were characterized with multiple spectroscopic techniques and the data indicated the successful functionalization of the polyacetylenes. The introduction of the pyrene moieties into the polymer structure allowed us to investigate the interactions between the polymer backbone and side chains. For the mono-substituted polyacetylenes, both the monomer and excimer emission features of the pyrene groups could be recorded, while for the di-substituted polyacetylenes, the fluorescence from the pyrene excimer vanished and the fluorescence intensity from the pyrene monomer decreased, the fluorescence from the polymer chain predominated the emission features. The concomitant energy transfer from the pyrene monomer and excimer to poly(diphenylacetylene) backbone was associated with the underlying mechanism. In addition to the substitution modes, the linkage between the poly(diphenylacetylene) backbone and the pyrene moiety also played a significant role in the determination of the emission species. A long alkyl spacer was beneficial to the pyrene monomer emission while a short one may be helpful to the formation of the excimer and intramolecular energy transfer. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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13 pages, 1736 KB

Open AccessArticle

Aminomethylated Calix[4]resorcinarenes as Modifying Agents for Glycidyl Methacrylate (GMA) Rigid Copolymers Surface

by Betty Astrid Velásquez-Silva, Alver Castillo-Aguirre, Zuly Jenny Rivera-Monroy and Mauricio Maldonado

Polymers 2019, 11(7), 1147; https://doi.org/10.3390/polym11071147 - 4 Jul 2019

Cited by 21 | Viewed by 4519

Abstract

Functionalization of tetrapropylcalix[4]resorcinarene, tetrapentylcalix[4]resorcinarene, tetranonylcalix[4]resorcinarene, and tetra-(4-hydroxyphenyl)calix[4]resorcinarene by means of aminomethylation reactions with the amino acids β-alanine and l-proline in the presence of aqueous formaldehyde was carried out. When β-alanine was used, the reaction products were tetrabenzoxazines. The reaction with tetra-(4-hydroxyphenyl)calix[4]resorcinarene did not proceed under the experimental conditions; therefore, l-proline was used, and the corresponding tetra-Mannich base was regio- and diasteroselectively formed. The products were characterized via FT-IR, ¹H NMR, ¹³C NMR, and elemental analysis. With these aminomethylated-calix[4]resorcinarenes, the chemical surface modification of the copolymers poly(GMA–co–EDMA) and poly(BMA–co–EDMA–co–MMA) in a basic medium was studied. The results were quite satisfactory, obtaining the corresponding copolymers functionalized by nucleophilic substitution reaction and ring-opening between the carboxyl group of the upper rim of aliphatic calix[4]resorcinarenes and the hydroxyl group of the lower rim in the aromatic calix[4]resorcinarene and the epoxy group of the glycidyl methacrylate residue of each copolymer. The modified copolymers were characterized via FT-IR, scanning electron microscopy imaging, and elemental analysis. Finally, the modified copolymer surfaces exhibited interaction with peptides, showing their potential application in chromatographic separation techniques such as high-performance liquid chromatography. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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33 pages, 6233 KB

Open AccessArticle

Surface Modification by Polyzwitterions of the Sulfabetaine-Type, and Their Resistance to Biofouling

by Eric Schönemann, André Laschewsky, Erik Wischerhoff, Julian Koc and Axel Rosenhahn

Polymers 2019, 11(6), 1014; https://doi.org/10.3390/polym11061014 - 8 Jun 2019

Cited by 27 | Viewed by 6935

Abstract

Films of zwitterionic polymers are increasingly explored for conferring fouling resistance to materials. Yet, the structural diversity of polyzwitterions is rather limited so far, and clear structure-property relationships are missing. Therefore, we synthesized a series of new polyzwitterions combining ammonium and sulfate groups in their betaine moieties, so-called poly(sulfabetaine)s. Their chemical structures were varied systematically, the monomers carrying methacrylate, methacrylamide, or styrene moieties as polymerizable groups. High molar mass homopolymers were obtained by free radical polymerization. Although their solubilities in most solvents were very low, brine and lower fluorinated alcohols were effective solvents in most cases. A set of sulfabetaine copolymers containing about 1 mol % (based on the repeat units) of reactive benzophenone methacrylate was prepared, spin-coated onto solid substrates, and photo-cured. The resistance of these films against the nonspecific adsorption by two model proteins (bovine serum albumin—BSA, fibrinogen) was explored, and directly compared with a set of references. The various polyzwitterions reduced protein adsorption strongly compared to films of poly(n‑butyl methacrylate) that were used as a negative control. The poly(sulfabetaine)s showed generally even somewhat higher anti-fouling activity than their poly(sulfobetaine) analogues, though detailed efficacies depended on the individual polymer–protein pairs. Best samples approach the excellent performance of a poly(oligo(ethylene oxide) methacrylate) reference. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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14 pages, 3106 KB

Open AccessArticle

Synthesis of an Aqueous Self-Matting Acrylic Resin with Low Gloss and High Transparency via Controlling Surface Morphology

by Qiwen Yong and Caizhen Liang

Polymers 2019, 11(2), 322; https://doi.org/10.3390/polym11020322 - 13 Feb 2019

Cited by 37 | Viewed by 8796

Abstract

This paper reports on a novel, film-forming acrylic polymer resin that exhibits low-gloss surface and high transparency via controlling film morphology at sub-micron roughness levels. Such microstructure is controlled by means of the copolymerization process increasing the allyl methacrylate (AMA) crosslinker content from 0 to 0.4 wt %. This acrylic resin makes it possible to avoid high loadings of matting agents, while also having good abrasion resistance and soft-touch feeling. Gloss levels of as low as 4 units at 60° incident angle and light transmittance of up to 85% have been achieved. The chemical structure of the aqueous acrylic resin was characterized by ATR-FTIR and NMR spectroscopy. The film morphology and surface roughness were measured by SEM and AFM analysis. The emulsion particle morphology and glass transition temperature were obtained by TEM and DSC, respectively. The effects of the crosslinker content on the light transmittance, glass transition temperature, and thermal degradation stability were also discussed in detail. The characterization results conclude that an acrylic polymer with interesting optical properties and high thermal stability can be obtained, which is desirable for leather applications. Full article

(This article belongs to the Special Issue Surface Modification and Functionalization of Polymers)

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