Preparation and properties of crosslinked network coatings based on perfluoropolyether/poly(dimethyl siloxane)/acrylic polyols for marine fouling–release applications

α,ω‐Triethoxysilane terminated poly(dimethyl siloxane) (PDMS) oligomer, α,ω‐triethoxysilane terminated perfluoropolyether (PFPE) oligomer, and acrylic polyols were first synthesized via an addition reaction and free‐radical polymerization. Then, crosslinked network coatings based on PFPE/PDMS/acrylic polyols for marine fouling‐release applications were prepared by a condensation reaction. The structure of the crosslinked network coating was characterized by Fourier transform infrared spectroscopy. The chemical composition of the coating surface was characterized by X‐ray photoelectron spectroscopy. The thermal properties, surface energy, mechanical properties, adhesion, and antiseawater immersion performance of the coatings were systematically studied. The antibiofouling properties of the crosslinked network coating were evaluated by laboratory biofouling assays with the bacteria Escherichia coli and the fouling diatom Navicula. The results from the preliminary study suggested that this crosslinked network coating had good adhesion and promising antifouling properties that were comparable to a silicone standard. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41860.     

Evolution of the film properties of 3-methacryloxypropyl trimethoxysilane containing waterborne acrylic coatings during storage

The use of alkoxysilane monomers is one of the most attractive methods to obtain one-pot self-crosslinkable latexes for coating applications. The copolymerization kinetics shows that the alkoxysilane monomer is effectively incorporated into the copolymer. However, the hydrolysis and condensation reactions that give the latex the self-crosslinking ability can also prematurely happen. As a result, the microstructure of the latex, and consequently of the dried polymer film, will change during the storage. Herein, the evolution of key film properties, such as, water uptake and tensile strength as a function of the storage time of latexes with different alkoxysilane monomer loadings is presented. As storage time increases, there is an improvement on the mechanical properties, obtaining a harder polymer as the result of the development of the hydrolysis and condensation reactions during the first 4 weeks. However, for more extended storage periods (17 weeks) there is a significant decrease in the mechanical performance, because the crosslinking in the latex has developed enough to hinder the film formation.     

Evaluation of mechanical properties and hydrophobicity of room-temperature,moisture-curable polysilazane coatings

Polysilazane coatings have a broad need in real-life applications, which require low processing or working temperature. In this work, five commercially available polysilazanes have been spin-coated on polycarbonate substrates and cured in ambient environment and temperature to obtain transparent, crack-free, and dense films. The degree of crosslinking is found to have a significant impact on the hardness and Young's modulus of the polysilazane films but has a minor influence on the film thickness and hydrophobicity. Among all five polysilazane coatings, the inorganic perhydropolysilazane-based coating exhibits the largest hardness (2.05 ± 0.01 GPa) and Young's modulus (10.76 ± 0.03 GPa) after 7 days of curing, while the polyorganosilazane-derived films exhibit higher hydrophobicity. The molecular structure of polysilazanes plays a key role in mechanical properties and hydrophobicity of the associated films, as well as the adhesion of coatings to substrates, providing an intuitive and reliable way for selecting a suitable polysilazane coating material for a specific application.     

Controlled preparation and properties of acrylic acid epoxy-acrylate composite emulsion for self-crosslinking coatings

A stable epoxy-acrylate composite latex was successfully prepared through emulsion polymerization of modified epoxy acrylic (EPAC) oligomer with acrylate monomer. The EPAC oligomer was obtained using active acrylic acid (AA) to react with epoxy resin. And by regulating the reaction degree of the active hydrogen of AA and epoxide group, there is the acquisition of terminal double bond that gives EPAC reactivity, together with the partial retention of the epoxide group that enables self-crosslinking during film formation. The structural conformation of the oligomer was ascertained by Fourier transform infrared (FTIR) spectroscopy. The factors influencing the stability of the epoxy-acrylate composite latex were investigated. The epoxy-acrylate composite latex was the most stable when methyl acrylic acid was 1.5 wt% and modified EPAC oligomer was 15 wt% of the total monomer weight. The morphology and property of the composite latex films were characterized by scanning electron microscopy, transmission electron microscopy (TEM), and temperature-modulated differential scanning calorimetry (TOPEM-DSC). The results confirm that there is successful emulsion copolymerization between modified EPAC oligomer and acrylate monomer. TEM show that the particles of epoxy-acrylate composite have a core-shell structure, and there is no free epoxy resin. The FTIR and TOPEM-DSC results reveal that the copolymer emulsion possesses self-crosslinking ability. During film formation, self-crosslinking reaction occurs between epoxide groups with carboxyl groups, giving exothermal phenomena. The thermal stability as well as the corrosion resistance of the films was analyzed. The results show outstanding thermal stability as well as corrosion resistance attributable to the crosslinking reticulation structure. It is envisaged that the epoxy-acrylate composite latex has great potential in the development of high-performance aqueous coatings.     

Rational design of vapor-deposited self-crosslinking polymer for transparent flexible oxygen barrier coatings

Transparent flexible barrier coatings consisting of a copolymer of 2-isocyanatoethyl methacrylate and 4-aminostyrene were fabricated using a facile vapor-based initiated chemical vapor deposition (iCVD) method. The isocyanate and amino groups were well reserved during deposition and reacted on the substrate surface, inducing self-crosslinking. The resultant coating showed a fairly smooth pinhole-free surface with more than 99% light transmittance across the visible range. With a proper compositional ratio, the synthesized coating demonstrated oxygen permeability 26 and 8 times lower than commercial PET and PVDF barrier films, respectively. The achieved barrier performance is attributed to the designed molecular structure, where interchain crosslinks are produced between a combination of both rigid and flexible side chains. Such combination enabled efficient packing of space while avoiding loose structures with low permeation resistance. The crosslinked network with rather flexible urea linkages also imparted excellent mechanical strength and high flexibility to the coating. Furthermore, the reported method is compatible with current industrial manufacturing process, thus expecting great potential in flexible electronics encapsulation.     

Copolymers of glycerol and propylene glycol diglycidyl ethers with aromatic dithiols

Monomers derived from renewable recourses have the potential to become the biobased alternatives for petroleum derived chemicals in the production of polymers. Glycerol, the byproduct of biodiesel refining, and propylene glycol derived from glycerol are promising candidates which can be used in the synthesis of polymers as they are or after chemical modification. The new copolymers of glycerol and propylene glycol diglycidyl ethers with aromatic dithiols were synthesized and investigated in this study. Their chemical structures were confirmed by IR, ¹H‐NMR spectroscopy, and gel permeation chromatography. The dependencies of the mechanical, thermal properties, swelling in the different solvents, biodegradability, and bioresistance of synthesized copolymers on their chemical structures were studied. The properties of some synthesized copolymer films were found to be comparable with those of commodity polymer films. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 4367–4374, 2013     

Highly efficient antifouling property based on self‐generating hydrogel layer of polyacrylamide coatings

Pursuit of robust antifouling coatings is a persistent objective for marine materials. We present here the experimental realization of a series of polyacrylamide‐based resins with a self‐generating hydrogel layer, arising from the polymerization of acrylamide (AM), butyl acrylate, methacrylic acid, and AM derivatives. The mechanical strength and thermal stability are markedly enhanced due to the change of the structure of modified resins. The preliminary results indicate that resultant resins with crosslinking structure show satisfactory abrasion resistance and swelling properties. The results of antifouling panel testing in shallow submergence for three months reveal that the addition of AM derivatives leads to generation of a thin soft and dynamic layer of hydrogel, which enhances antifouling properties. The formation of hydrogel and self‐generating property make it promising in various antifouling applications. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 44111.     

The effect of nonionic monomer HAM on properties of cationic surfactant‐free acrylic/alkyd hybrid emulsion

A series of cationic acrylic/alkyd resin (CPAAR) hybrid emulsions was successfully prepared through surfactant‐free emulsion polymerization, using methacryloxyethyltrimethyl ammonium chloride, methyl methacrylate, butyl acrylate and alkyd resin as reaction monomers. And nonionic N‐hydroxymethyl acrylamide (HAM) of different content was simultaneously incorporated into the CPAAR backbone. The structure of CPAAR copolymer was characterized by Fourier transform infared spectrometer, and then the effect of HAM content on properties of CPAAR emulsions was studied by particle size analyzer, transmission electron microscopy and rheometer. In addition, thermal properties, water absorption and contact angle of CPAAR latex films were also investigated. The results showed that the CPAAR emulsions prepared with 4.9 wt % HAM displayed smallest average particle size of 92.2 nm. As HAM content increased from 0 to 19.6 wt %, the initial viscosity of the emulsions increased from 22.48 to 53 mPa.s. At the same time, the emulsions transferred from Newtonian fluid to pseudoplastic fluid, and a transition from viscous liquid to elastic liquid was also detected. Meanwhile, the degradation temperature at 5% weight loss increased by 30.59°C. In addition, with increasing HAM content from 0 to 4.9 wt %, the water absorption and surface free energy of films increased by 4.42% and 5.02 mJ m^?2, respectively. However, the water absorption and surface free energy kept almost invariable with further increase in HAM content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41406.     

Crystallization,structure, and enhanced mechanical property of ethylene-octene elastomer crosslinked with dicumyl peroxide

Crosslinking of polyolefin elastomer (POE, ENGAGE™ 8480) with Dicumyl Peroxide (DCP) can have effects on its crystallization dynamics, crystal structure, and properties. The POE crosslinked uniformly has significantly lower crystalline ability than the one with only amorphous phase crosslinked, which, in turn, has weaker crystalline ability than neat POE. The crystallinity and melting point depend on how the POE is crosslinked. The neat POE and POE crosslinked in amorphous phase only, are investigated with DSC and in-situ tensile/synchrotron radiation (WAXD/SAXS). In situ tensile/synchrotron X-ray during a uniaxial stretching process indicates that severe crystal fragmentation is observed at a strain around 45%, and with further increase in strain. The stress in the crosslinked POE is significantly larger than neat POE. For both samples, crystal orientation increases sharply within the strain range up to 88% where orientation-induced new crystals aligned in stretching direction are observed. The long period increases more in stretching direction for the crosslinked POE, consistent with larger stress in this sample, and the stress difference is more pronounced at large strains (27.3 vs. 10.9 MPa at a strain 435%). Permanent set of the crosslinked POE is smaller, consistent with less oriented crystals observed after the test for permanent set.     

Reduced graphene oxide suspension with a comb copolymer and its effects on the corrosion resistance of hydroxyl polyacrylate coatings

A comb copolymer (CC) is designed and prepared in present article, by grafting epoxy resin (E-20) on poly(styrene-co-acrylate). The CC is used as a special dispersant, which leads to a stabilizable reduced graphene oxide (rGO) suspension in organic coatings. The dispersing mechanism is deduced as π-π attraction between CC and rGO, which is supported by the analysis data of Fourier transform infrared (FTIR) spectra, Raman spectroscopy, scanning electron microscope, transmission electron microscope, and X-ray photoelectron spectroscopy. The corrosion resistance of CG suspension is determined by electrochemical impedance spectroscopy, the results implies that the anti-corrosion behavior performed obviously, and protective efficiency is up to 99.53% in Tafel analysis. © 2020 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48898.     

Dielectric elastomer film with anisotropic actuation deformation on film plane

A new dielectric elastomer (DE) film, which was able to show anisotropic large plane deformation actuated by an external electric field, was designed and synthesized. Specifically, an asymmetric di-vinyl monomer cyclohex-3-enylmethyl acrylate (CEA) was incorporated into the middle block of poly(styrene-b-butyl acrylate-b-styrene) as potential crosslinking points. By widely used UV curing technique through a mask, the DE films could be locally hardened any area one selected. This could break the symmetry of the actuation deformation on the DE film plane, maximizing the deformation in a given direction while the actuation area strain remained unchanged. The actuation strain_y/strain_x reached 2.3, strain in x direction was 10.3% while in y direction was 23%, when the DE film of S(BA-ran-CEA)S with 2.5 mol % CEA incorporated was locally hardened in the form of soft and hard belt of 1 mm width alternatively along y direction. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48795.     

Antimicrobial coatings based on hydantoin‐containing polymer networks for textiles

An advanced method with an initiator pretreatment was developed for the coating of nylon/cotton fabrics with the hydantoin‐containing monomer 3‐allyl‐5,5‐dimethylhydantoin and two water‐soluble crosslinkers N,N′‐methylene bisacrylamide and poly(ethylene glycol) 200 diacrylate. The formulations were applied to textiles by either batch coating or dip coating. In the dip‐coating process, the influence of individual parameters on the fabric modification was investigated and evaluated. After treatment with chlorine, the hydantoin structure was transformed into antimicrobial active N‐halamines. The modified fabrics exhibited potent antibacterial properties against Staphylococcus aureus and Escherichia coli. Our method, based on an initiator pretreatment and water‐soluble crosslinkers, outperformed current technologies in the degree of fabric modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Acrylic copolymers crosslinked by click chemistry: Some aspects of synthesis,curing, and crosslinking

Acrylic polymers bearing pendant azide and propargyl groups were synthesized by chemical transformation of epoxy‐ and carboxylic functional acrylic precursor polymers and were characterized. These copolymers were crosslinked by reacting them in the presence of Cu(I) catalyst via the azide–alkyne click reaction leading to triazole networks. Influence of catalyst concentration on the crosslinking cure kinetics was investigated, and the activation parameters were evaluated. The activation energy decreased from 90 kJ mol^?1 to 25 kJ mol^?1 on catalyzing the cure reaction as estimated by Ozawa method. Differential scanning calorimetric analysis indicated thermal decomposition of the residual azide groups at around 200–220°C, which was catalyzed by Cu(I) with associated activation energy of 130–94 kJ mol^?1. Isothermal cure reaction and decomposition of the azide groups were predicted using these parameters. Estimation of crosslink density by solvent swelling and dynamic mechanical analyses showed a normal crosslinking behavior. While the solvent swelling rate and the equilibrium swelling decreased, the front factor and diffusion coefficient of swelling showed a transition from non‐Fickian to Fickian as the triazole concentration increased in the network. The click reaction offered an alternate means to crosslink acrylate polymers. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 1289‐1300, 2013     

Molecular and thermal studies of carbon fiber precursor polymers with low thermal‐oxidative stabilization characteristics

In this investigation, terpolymers, copolymers, and homopolymer of acrylonitrile with dimethylaminopropyl acrylamide (DMAPA), itaconic acid (IA) viz., poly(acrylonitrile‐ran‐3‐dimethylaminopropyl acrylamide‐ran‐itaconic acid) [P(AN‐DMAPP‐IA)], poly(acrylonitrile‐co‐3, dimethylaminopropyl acrylamide) [P(AN‐DMAPP)] were synthesized with varying amounts of comonomers using solution polymerization process. The chemical structure, composition, bonding network were determined employing infrared, 1H and, 13‐carbon nuclear magnetic resonance spectroscopic techniques. Molecular characteristics of as‐synthesized polymers such as different kinds of average molecular weights, molecular weight distribution were estimated applying solution viscometry and size exclusion chromatography. The influence of comonomers (DMPAA, IA) on the thermal stabilization characteristics of acrylonitrile terpolymers in comparison with copolymers and homopolymers of acrylonitrile were studied using differential scanning calorimetry (DSC), hyphenated thermal techniques (thermal gravimetry coupled with differential thermal analyzer).The DSC curves of P(AN‐DMAPP‐IA) exhibit a distinct broader bimodal peaks with thermal exotherm initiating at as low as 165 °C, and followed by two peaks with temperature difference of 42 °C, releasing the evolved heat at a release rate of 0.7–0.11 J g^?1s^?1over 10 min as compared to 1.2, 7.5 J g^?1s^?1 in 4.5, 2 min as observed in P(AN‐DMAPP), polyacrylonitrile, respectively. The thermal stability of P(AN‐DMAPP‐IA) and P(AN‐DMAPP), as evidenced by TGA‐DTA was found to be higher than PAN homopolymers. Specific heat capacity measurements confirmed the DSC results. Bulk densities of P(AN‐DMAPP‐IA) were in the range 0.31–0.35 g/cc. These results confirm the low‐temperature stabilization characteristics and suitability of P(AN‐DMAPP‐IA) as low cost carbon fiber precursor polymers. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46381.     

The preparation and analysis of chlorinated ethylene vinyl acetate copolymer as coating film in gas‐solid phase

In this article, the feasibility of preparing chlorinated ethylene vinyl acetate copolymer (CEVA) in gas–solid phase is investigated. Furthermore, the structure of the chlorination product and its performance as a coating material are also analyzed. Both the molecular structure and crystallinity of the product are well studied with various characterization methods, including ¹H‐NMR, Fourier transform infrared, gel permeation chromatography, differential scanning calorimeter, and so forth. The results show that the chlorination of EVA in gas–solid phase is feasible and the chlorine content of CEVA can be made over 60%. It is also found that when the chlorine content is low, chlorination can easily occur in ethylene section but rarely happens in vinyl acetate section. Nevertheless, when the chlorine content of CEVA rises over 35%, ? CH in the vinyl acetate section is also found chlorinated. The removal of hydrogen chloride is induced during chlorination, producing double bonds in the main chain. Besides, the trace of ? CCl₂ structure can also be found in the chain of CEVA. After chlorination, the crystallization will change and is negatively correlated with chlorine content. As the film forming material for coating, CEVA has its best performance with 50% chlorine content. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 41093.     

Crosslinking and ozone degradation of thermosetting resins based on maleic anhydride/diene copolymer and polyfunctional alcohols

Crosslinking and de‐crosslinking reactions of an alternating copolymer of maleic anhydride (MAn) and 2,4‐dimethyl‐1,3‐pentadiene (DMPD) by thermal curing with polyfunctional alcohols as the crosslinkers and subsequent ozone degradation are reported in this article. The ring‐opening reaction of an anhydride group by polyfunctional alcohols produces network polymers with an ester linkage. The rate of crosslinking reaction depends on the curing conditions, i.e. the structure of the used alcohols and the curing temperature and time. The crosslinking density of the alcohol‐cured copolymers is low due to a slow reaction between the anhydride and hydroxy groups, being different from the corresponding epoxy‐cured copolymer with a dense network structure reported in a previous article. The insoluble resins are readily de‐crosslinked and solubilized by ozone degradation. The polymer surface modification by ozone is also investigated. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42763.     

Synthesis and characterization of fluorinated organic–inorganic hybrid coatings on tinplate

Fluorinated organic–inorganic hybrid coatings with interpenetrating network for corrosion protection of tinplate were prepared by hydrolysis and condensation reaction of tetraethoxysilane and 3‐methacryloxypropyltrimethoxysilane, followed by radical polymerization of trimethylolpropane triacrylate dodecafluoroheptyl methacrylate. The highly crosslinked organic network was developed and attached to the inorganic moieties through covalent Si–C bonds. The hybrid coatings were characterized by scanning electron microscope, water contact angle, Fourier transformed infrared spectroscopy, and thermogravimetric analysis. Their anticorrosion performances were evaluated by potentiodynamic polarization, electrochemical impedance spectroscopy and salt spray test. The results indicated that the fluorinated hybrid coatings exhibited excellent anticorrosion ability by forming a hydrophobic physical barrier between tinplate substrate and its external environment. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42428.     

Toughening of epoxy thermosets with nano-sized or micron-sized domains of poly(ethylene oxide)-b-poly(butadiene-co-acrylonitrile)-b-poly(ethylene oxide) triblock copolymers synthesized using room temperature ester coupling reaction

Poly(ethylene oxide)-b-poly(butadiene-co-acrylonitrile)-b-poly(ethylene oxide) (PEO-b-PBN-b–PEO) triblock copolymers with three different compositions were synthesized from poly(ethylene glycol) methyl ethers and carboxylic acid-terminated poly(butadiene-co-acrylonitrile) (CTBN) by ester coupling reaction at room temperature. The PEO-b-PBN-b-PEO was incorporated into anhydride cured epoxy thermosets to improve the fracture toughness by the formation of either nano-sized spherical micelles or micron-sized vesicles. The polymer chemical structure was confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance, and gel permeation chromatography. The morphology of PEO-b-PBN-b–PEO within the epoxy thermosets was investigated using a transmission electron microscope, an atomic force microscope, and a scanning electron microscope. Also, we conducted impact testing and plane-strain fracture toughness testing to evaluate the fracture toughness in terms of the impact strength and the critical stress intensity factors (K_IC) for the modified epoxy thermosets. The results revealed that all the PEO-b-PBN-b-PEO triblock copolymers are more effective in the toughening of epoxy thermoset compare to CTBN. We found that the 5 wt% PEO-b-PBN-b-PEO modified epoxy thermoset containing micron-sized vesicles exhibited the highest K_IC, which was 3.23 times as high as the K_IC of pristine epoxy thermoset. Besides, the glass transition temperature remained and the tensile modulus did not reduce remarkably when the amount of PEO-b-PBN-b-PEO added into epoxy was 5 wt%.     

Synthesis and properties of UV-curable waterborne urethane modified acrylic coatings with varying vinyl content

It has been an effective method to improve the metal protective performance of UV-curable waterborne coatings by increasing the crosslinking degree. Hence, a series of UV-curable waterborne urethane modified acrylic (UV-WUA) coatings with different vinyl content were prepared. Firstly, a functional prepolymer containing carboxyl and hydroxyl groups was synthesized by free radical copolymerization (FRCP) using acrylic acid (AA), 2-hydroxyethyl acrylate (HEA), methyl methacrylate (MMA) and butyl acrylate (BA). Next, it was grafted with different amounts of semi-adduct of isophorone diisocyanate (IPDI) and HEA (IPDI-HEA), and finally neutralized and hydrated, obtaining UV-WUA dispersions which were then cured by UV to acquire cured films and coatings. Meanwhile, molecular structures, molecular weights, particle sizes, and Zeta potentials were characterized. Then, the heat resistance, mechanical performance, adhesion and the pencil hardness of the coatings were also investigated. Moreover, their protective performance was tested by electrochemical methods, and the surface morphology was analyzed by atomic force microscopy. The results showed that the coating had desirable comprehensive performance when vinyl content reached 0.86 mmol·g⁻¹.     

Heterogeneous method of chitosan film preparation: Effect of multifunctional acid on film properties

The heterogeneous crosslinking method was applied to chitosan films with citric acid to observe and understand the effect of a multifunctional acid at a low concentration on film properties. Neat and neutralized chitosan films and films containing 15% (w/w) citric acid (denoted as CA films) were characterized by mechanical, water vapor permeability (WVP), and thermogravimetric analysis tests. The CA films displayed a higher tensile strength by 10%, lower WVP by 30%, and higher thermal stability, compared to neutralized films. The crystalline structure converted back from tendon to Type II after the addition of citric acid, as determined by X-ray diffraction. Neat films displayed a lower water contact angle (72°) compared to neutralized and CA films (78°–79°). The heterogeneous method was also applied to incorporate a plasticizer into a neutralized film to potentially observe the glass transition using dynamic mechanical analysis. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48648.