Robust grafting of PEG-methacrylate brushes from polymeric coatings

A study is presented of the grafting of poly(ethylene glycol)methyl ether methacrylate (PEGMA) from polymeric macroinitiator films to form well-defined polymer brushes, using activators generated/regenerated by electron transfer (AGET/ARGET) atom transfer radical polymerization (ATRP). Polymer brush coatings can potentially be obtained on surfaces of virtually any shape and composition, because of the ease of conformal casting of the anchoring macroinitiator film. Polymer brush coatings are synthesized in a robust way, as ARGET and AGET ATRP require little to no deoxygenation and make use of stable catalysts. The monomer, catalyst, ligand and reducing agent concentrations, the amount and type of initiating moiety in the anchoring films, and the choice of solvents are optimized, resulting in control over the rate of reaction, and the molecular weight of poly(PEGMA). The best conditions are determined for the formation of a poly(PEGMA) brush with high grafting density, controlled thickness and “living” ends available for post-functionalization.     

Surface functionalization of nanodiamond particles via atom transfer radical polymerization

Ultradispersed diamond (UDD)/polymer brushes having excellent solution dispersibilities are prepared by atom transfer radical polymerization (ATRP) using the “grafting-from” synthesis strategy. ATRP initiators, covalently attached to oxidized surface carbon atoms of UDD aggregates using esterification chemistry, initiate polymerization of methacrylate monomers to form hydrophobic UDD/poly(iso-butyl methacrylate) and UDD/poly(tert-butyl methacrylate) polymer brushes. Acid hydrolysis of a UDD/poly(tert-butyl methacrylate) polymer brush affords a hydrophilic UDD/poly(methacrylic acid) polymer brush. Based on surface area measurements and GPC data, the calculated surface density of a representative UDD/polymer brush material is ca. five polymer chains/100 nm². A wide variety of UDD/polymer brush materials having controlled dispersibility and functional group reactivity are now potentially available using this synthesis strategy.     

Influence of poly(acrylic acid) grafting density on switchable protein adsorption/desorption of poly(2-methyl-2-oxazoline)/poly(acrylic acid) mixed brushes

Poly(dopamine) is employed as an anchor to obtain a series of poly(acrylic acid) (PAA) and poly(2-methyl-2-oxazoline) (PMOXA) mixed brush coatings by sequential grafting to methods with PAA chains longer than PMOXA chains. Then, the prepared mixed brush coatings are rigorously characterized. The results show that the grafting density of PAA in mixed brushes could be well adjusted by changing the concentration of PAA solution used for the preparation of mixed brush coatings and the amounts of lysozyme adsorbed on PMOXA/PAA mixed brushes increase with increasing the grafting density of PAA chains while the desorption amounts decrease significantly when the grafting density of PAA is higher than one-half of PMOXA chains. When the grafting density of PAA is about one-half of PMOXA chains, the mixed brush could absorb high amounts of lysozyme (898.4 ng cm⁻²), and then more than 90% of adsorbed proteins could be released sharply by changing pH and ionic strength (I). © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48135.     

A polyamide thin-film composite membrane modified by Michael addition grafting of hyperbranched poly(amine ester)

In this work polyamide thin-film composite membrane (TFC) surface modified via Michael addition grafting of a hydrophilic hyperbranched poly(amine ester). For this purpose, amine-rich polyamide layer formed by interfacial polymerization on a polyethersulfone support, and then acrylated hyperbranched poly(amine ester) (AC-HBPAE) was used as grafting moiety. The membrane surface was characterized by attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), atomic force microscopy (AFM) and water contact angle techniques. Field emission scanning electron microscopy (FE-SEM) was used to evaluate surface and cross-section morphology of samples. Filtration performances and bio-fouling resistance were also studied using a nanofiltration cell. Surface chemical composition and contact angle indicated the successful grafting of acrylated poly(amine ester) to the membrane surface. The results also indicated there is a solid relationship between acrylation percentage of hyperbranched polymer and membrane properties such as fouling resistance. A uniform and hydrophilic surface observed for TFC membrane modified with 5% acrylated hyperbranched poly(amine ester).     

Electropolymerized bilayer coatings of polyaniline and poly(N-methylaniline) on mild steel and their corrosion protection performance

Polyaniline (PANI) and poly(N-methylaniline) (PNMA) have been electrodeposited on mild steel from oxalic acid bath using cyclic voltammetric technique. Pretreatments like passivation and primer polymer coatings were required for effective coating. Differently stacked composite polymer layers on the metal surface by layer-by-layer approach have also been obtained and their properties have been compared with their corresponding copolymer coatings. FTIR study confirms the formation of electroactive polymer compounds on mild steel. Evaluation of these coatings in 3.5% NaCl solution by potentiodynamic polarization and electrochemical impedance spectroscopy reveals significant corrosion resistant behavior. Relatively higher corrosion protection is exhibited by copolymer coatings and composite-bilayer coatings than the corresponding homopolymer coatings. The composite metal–PANI–PNMA layer shows higher stability and better protection than the metal–PNMA–PANI layer.     

Homo- and mixed polymer brushes prepared by surface-grafting of asymmetric non-sticky/sticky diblock copolymers and their stimuli–responsive behaviors

We synthesize a non-sticky/sticky diblock copolymer, poly[styrene-b-3-(trimethoxysilyl)propylmethacrylate], to produce polymer brushes using the grafting-to technique. Uniform coatings of the polymer brushes are efficiently produced because of the multiple reactive groups offered by the sticky block, and the surface coverage and nanoscopic morphology of the brush layer are adjusted by varying the concentrations of the immersion polymer solutions and the immersion time of the substrate. The nanoscopic pattern of the polymer brushes is subsequently utilized to produce mixed polymer brushes. The resulting homo- or mixed polymer brushes change their nanoscopic morphology in response to external stimuli of temperature and solvent. The results indicate that grafting of the asymmetric non-sticky/sticky block copolymer is an efficient method for producing a surface of polymer brushes with nanoscopic chemical heterogeneity.     

Multiple hydrophilic polymer ultra-thin layers covalently anchored to polyethylene films

A novel procedure has been developed to covalently graft multiple hydrophilic polymer ultra-thin layers to functionalized polyethylene surface. Polyethylene films have been functionalized by two methods, chromic acid oxidation and maleic anhydride grafting, to produce surfaces containing reactive groups, carboxylic acid and anhydride, respectively. The reactive groups formed in the functionalization were used to anchor a poly(vinyl alcohol) (PVA) ultra-thin layer by thermal esterification. After anchoring PVA, a second ultra-thin layer, constituted of poly(acrylic acid) (PAA), was also anchored. The second layer was anchored by thermal esterification between PVA hydroxyl groups and PAA carboxylic acid groups. The procedure presented in this work allows the formation of an ultra-thin layer. The macromolecule anchoring reactions occur only at the interfaces, consequently, only the macromolecules in contact with the interface are anchored. The formation of the ultra-thin layer and the surface characteristics have been analyzed through XPS, ATR-FTIR, SEM, and AFM data.     

Investigation of design parameters in generating antifouling and lubricating surfaces using hydrophilic polymer brushes

Long-term stability of hydrophilic surface coatings that prevent fouling, cell adhesion and present a lubricious interface for biomaterials has been widely investigated in recent years. As an alternative to the gold standard poly(ethylene glycol) (PEG), poly(2-oxazoline)-based coatings are promising due to their higher stability against oxidative degradation in comparison to PEG. In this study, we compare the antifouling and tribological properties of PEG and poly(2-methyl-2-oxazoline) (PMOXA) brush structures as a function of structural design parameters such as grafting density, chain length, and the monomer solubility. Brush properties such as hydration (number of H₂O molecules per monomer), shear modulus, and serum adsorption as a function of design parameters were estimated using optical waveguide lightmode spectroscopy and quartz crystal microbalance/dissipation techniques. At high monomer surface densities, PMOXA showed approximately three times higher structurally associated H₂O molecules per monomer in comparison to PEG brushes, leading to stiffer PMOXA brushes. We found that the chain stiffening of PMOXA brushes lead to higher macroscopic coefficients of friction; however presented similar adsorbed serum mass (high antifouling properties) when compared to PEG brushes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47659.     

Synthesis,characterization, and electropolymerization of Mannich bases: Influence of substituents on protective ability of organic coatings

Aminoalkyl phenol derivatives were prepared and tested for electrooxidation in alkaline hydroalcoholic electrolytes. We estimated the relative insulating character of thin (<0.3 μm) organic coatings on several metal electrodes (Fe, Cu, and Ni), through both voltammetric and potentiostatic runs. Unsaturated allyl and but‐3‐enyl groups confer the most effective passivation phenomenon, while N‐methyl‐substituted Mannich bases do not provide the good protective properties expected. This result was explained through the relative easiness of the nitrogen oxidation of these monomers, leading to parasite reactions (methoxylation of the growing polymer chains) and additional termination reactions, thereby limiting the molecular weight of the polymer. FTIRAS results showed that products of the anodic oxidative coupling process consist (especially for the nature of monomer) of a poly(oxy‐1,4‐phenylene)‐type structure. Amino and unsaturated substituted groups remain unchanged during electropolymerization, making the resulting coatings attractive to use as reactive primer layers. The thickness of the coatings was found to reach 2–5 μm in free‐water solutions. This behavior, particular to Mannich bases, was explained by the hydrophilic character of the growing polymer chains due to the presence of amino groups. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 1054–1067, 2000     

Creation of dense polymer brush layers by the controlled deposition of an amphiphilic responsive comb polymer

We introduce a copolymer with a comb topology that has been engineered to assemble in a brush configuration at an air-water interface. The molecule comprises a 6.1 kDa poly(methyl methacrylate) backbone with a statistical amount of poly[2-(dimethyl amino)ethyl methacrylate] polybase side chains averaging 2.43 per backbone. Brush layers deposited with the hydrophobic PMMA backbone adsorbed to hydrophobized silicon are stable in water even when stored at pH values less than 2.0 for over 24 h. The use of a Langmuir trough allows a simple controlled deposition of the layers at a variety of grafting densities. Depth profiling of brush layers was performed using neutron reflectometry and reveals a significant shifting of the responsiveness of the layer upon changing the grafting density. The degree of swelling of the layers at a pH value of 4 (below the pK_b) decreases as grafting density increases. Lowering the pH of the subphase during deposition causes the side chains to become charged and more hydrophilic extending to a brush-like configuration while at neutral pH the side chains lie in a “pancake” conformation at the interface.     

Preparation of Ni-g-polymer core–shell nanoparticles by surface-initiated atom transfer radical polymerization

Surface-initiated atom transfer radical polymerization (si-ATRP) technique was successfully employed to modify Ni nanoparticles with polymer shells. ATRP initiators were covalently bonded onto Ni nanoparticle surfaces by a combination of ligand exchange and condensation reactions. Various kinds of polymers including poly(methyl methacrylate) (PMMA) and poly(n-isopropylacrylamide) (PNIPAM) were grafted from the immobilized initiators. The grated polymer shells gave Ni nanoparticles exceptionally good dispersion and stability in solvents. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA) and transmission electron spectroscopy (TEM) were employed to confirm the grafting and to characterize the nanoparticle core–shell structure. Gel permeation chromatography (GPC) studies of cleaved polymer chains revealed that the grafting polymerization was well controlled. The magnetic properties of Ni-g-polymer nanoparticles were also studied.     

Approach to Obtain Electrospun Hydrophilic Fibers and Prevent Fiber Necking

Solution electrospinning of a blend containing a hydrophobic polymer with a hydrophilic functional polymer as an additive is a simple and straight‐forward route to obtain functional and hydrophilic fibers accompanied by the mechanical properties of the hydrophobic polymer. However, this process of thermodynamically unfavored surface segregation of the hydrophilic additive is not well understood. To understand the process the dependencies of the surface hydrophilization on type of hydrophilic polymers, the solvent, and the process, using poly(caprolactone) (PCL) as the matrix polymer is explored. The results show that hydrophilic fibers can be obtained using different additive hydrophilic polymers. The combination of polymer blends which show this effect can be predicted using the Flory–Huggins interaction parameter. In addition mechanical and micromechanical properties of PCL fibers blended with NCO‐terminated star‐shaped poly(ethylene glycol) (sPEG‐NCO) as additive are investigated. In this context blending with sPEG‐NCO turns out to be a powerful tool to prevent fiber necking rendering this method an interesting candidate for tissue engineering application, where it is mandatory to retain the surface properties under mechanical stress.     

Sub-20 nm Bilayer Hydrophilic Poly(Vinyl Pyrrolidone) Coatings for Antifouling Nanofiltration Membranes

Fouling is a major concern in membrane technology. Neutral hydrophilic coatings alleviate fouling on membrane surfaces by passively resisting the adsorption of foulants without altering the properties of membranes. Coatings, however, often result in a trade-off of reduced water flux. Ultrathin hydrophilic coatings could minimize the influence on water flux, but its fabrication is challenging via traditional methods. Here, fabrication of sub-20 nm bilayer hydrophilic coating is reported that is grafted onto nanofiltration (NF) membranes via a one-step initiated chemical vapor deposition (iCVD) method. The iCVD coating is conducted by conformally depositing a crosslinked poly(vinyl pyrrolidone-co-ethylene glycol dimethacrylate) bottom layer on pretreated NF membrane, followed by in situ grafting of poly(vinyl pyrrolidone) homopolymer to further improve surface hydrophilicity. Both thickness and crosslinking degree of the bottom coating are systematically tailored to reduce its side effects on permeation rate and salt rejection. The modified NF membranes exhibit 99% lower microbial adhesion compared to the pristine membrane, with minor impact on permeation and salt rejection performance. The coating is also stable against continuous ultrasonication. The reported method is thus expected to shed light on facile novel ways of reducing membrane fouling in desalination and industrial wastewater treatment.     

Polymer brush coatings for combating marine biofouling

A variety of functional polymer brushes and coatings have been developed for combating marine biofouling and biocorrosion with much less environmental impact than traditional biocides. This review summarizes recent developments in marine antifouling polymer brushes and coatings that are tethered to material surfaces and do not actively release biocides. Polymer brush coatings have been designed to inhibit molecular fouling, microfouling and macrofouling through incorporation or inclusion of multiple functionalities. Hydrophilic polymers, such as poly(ethylene glycol), hydrogels, zwitterionic polymers and polysaccharides, resist attachment of marine organisms effectively due to extensive hydration. Fouling release polymer coatings, based on fluoropolymers and poly(dimethylsiloxane) elastomers, minimize adhesion between marine organisms and material surfaces, leading to easy removal of biofoulants. Polycationic coatings are effective in reducing marine biofouling partly because of their good bactericidal properties. Recent advances in controlled radical polymerization and click chemistry have also allowed better molecular design and engineering of multifunctional brush coatings for improved antifouling efficacies.     

聚合物刷子的合成进展

聚合物在材料表面物理吸附或化学接枝所形成的刷子状单分子层被称为聚合物刷子,本文介绍了聚合物刷子的概念、分类以及合成方法。     

Motion of nano-objects on polymer brushes

In this paper we review a new method to move nano-objects on a polymer surface that is made from diblock-copolymer and mixed brushes. Such brush systems consist of polymer chains covalently attached to a surface with high grafting density. If the two polymeric components the brush consists of are incompatible with each other, it shows microphase separation into nanopatterns of well defined size. Such a system possesses the unique property of changing the surface topography in response to different external conditions. Motion of nano objects adsorbed on the brush is induced by having the external conditions and thus the brush topography vary over time. This is shown by studying the distribution of silica nanoparticles adsorbed on several types of brushes while changing the external conditions. We identify parameters required for motion of nano objects, and discuss potential applications of the proposed technique for nano engineering.     

Hydrophilic surface modification of poly(vinyl chloride) film and tubing using physisorbed free radical grafting technique

The grafting of hydrophilic monomers from the surface of PVC films and complex geometries, such as tubing, was executed by a novel two-step process: physisorption of a hydrophobic free radical initiator onto a polymer surface followed by radical polymerization with hydrophilic monomers. The key step is creating a hydrophobic/hydrophilic diffusional barrier that promotes radical generation upon heating at the polymer surface. Transmission infrared spectroscopy, X-ray photoelectron spectroscopy, surface wettability and capillary rise, gravimetric analysis, UV-vis spectroscopy and gel permeation chromatography were utilized to prove successful covalent grafting of poly(hydroxyethylmethacrylate), poly(dimethylacrylamide), poly(hydroxyethylacrylate), poly(dimethylaminoethylmethacrylate), poly(acrylic acid), and poly(4-vinyl pyridine).     

刷状聚乙二醇两亲性共聚物的合成及其对载药的影响研究进展

刷状聚乙二醇（PEG）两亲性共聚物具有独特的性能和良好的应用前景,日益受到人们的重视。本文综述了刷状PEG两亲性共聚物的两种合成策略,即大分子单体法和主链-侧链偶联法,它们主要通过离子聚合、自由基聚合、开环聚合及各种耦合反应等实现。举例分析了这些方法的优缺点,并侧重于聚酯等生物可降解材料形成的刷状PEG共聚物。比较了直链PEG和刷状PEG共聚物胶束表面形态,简要分析了刷状PEG结构对纳米颗粒药物输送性能的影响,指出刷状PEG结构能延长体内循环时间从而提高药物疗效,但有效的合成方法及其胶束的体内外性能还需要更深入的探索。     

Characterizing and improving performance properties of thin solid films produced by weatherable water-borne colloidal suspensions on bronze substrates

While the development and application for transparent protective coatings for metals continues and broadens, the use of these coatings on high-value outdoor bronze objects, such as statues and architectural elements, requires extensive testing before use. Recent efforts in coatings technology have produced high-performance water-borne latex dispersions containing polyacrylics and poly(vinylidene fluoride) (PVDF) targeting extended coating lifetimes and improved UV resistance. Our studies show that a two-layer polymer film with a solvent based primer (Paraloid™ B-44) and a high performance water-borne topcoat (Kynar Aquatec™ RC-10206) exhibits high impedance as measured by electrochemical impedance spectroscopy. Upon annealing, those films further increased in impedance, suggesting improved corrosion protection compared to unannealed films. When soaking in water, films that contained high loading levels of coalescing agent (Dipropylene glycol monomethyl ether, DPM) in the topcoat formulation resulted in a visible whitening of the basecoat and a decrease in coating resistance. Characterization of the whitened layer by FT-IR indicated the presence of coalescent in the basecoat, suggesting that coalescent migrated from the topcoat into the primer basecoat. Annealing studies were performed to reduce uptake and reverse or inhibit water whitening.     

Enhancement of graft density and chain length of hydrophilic polymer brush for effective marine antifouling

2‐Hydroxyethyl methacrylate polymer brushes with various grafting densities and chain lengths were prepared through surface‐initiated atom transfer radical polymerization. X‐ray photoelectron spectra, ellipsometry measurement, contact angle measurement, and atom force microscope were used to characterize the prepared polymer brush. The biofouling assays of polymer brush were investigated by adhesion of Dunaliella tertiolecta, Navcular sp., and Bovine Serum Albumin protein and by static marine immersion field test. Besides, hydroxyl and sulfonate‐terminated self‐assembled monolayers, anionic charged 3‐sulfopropyl methacrylate potassium salt polymer brush were prepared for comparison. Results suggest that the settlement of microorganisms can be largely reduced by polymer with enough polymer chain length and grafting density. More importantly, static immersion field tests indicate that hydrophilic polymer film with enough hydration layer thickness is necessary for long‐term marine antifouling application. This comprehensive investigation is of great importance to understanding their influence on the adhesion of marine microorganism. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46232.