Efficient and robust coatings using poly(2-methyl-2-oxazoline) and its copolymers for marine and bacterial fouling prevention

Molecular design, fabrication, and properties of thin-film coatings based on poly(2-methyl-2-oxazoline) (PMOX) and its copolymers were investigated to tackle problem of marine and bacterial fouling prevention. The ultraviolet crosslinkable macromonomer poly(2-methyl-2-oxazoline) dimethylacrylate was synthesized by cationic ring-opening polymerization in a microwave reactor initiated by 1,4-dibromobutane. In order to study the charge effect of the PMOX coatings on the adhesion of fouling organisms, PMOX surfaces with negative, neutral, and positive ζ-potential values were prepared by copolymerization with the positively charged monomer [2-(methacryloyloxy)-ethyl]trimethylammonium chloride. The coatings were stable in sea water for at least 1 month without significant reduction in the film thickness. The marine antifouling activity was evaluated against barnacle cyprids Amphibalanus amphitrite and algae Amphora coffeaeformis. Results showed that PMOX coatings provide effective reduction of the settlement regardless of the molar mass and surface charge of the polymer. Bacterial adhesion test showed that PMOX coatings effectively reduce Staphylococcus aureus and Escherichia coli adhesion. Owing to its good stability and antifouling activity PMOX has a great potential as antifouling coating for marine antifouling applications. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 275–283     

Pavidolides A-E, new cembranoids from the soft coral Sinularia pavida

Five new cembrane-based diterpenoids, namely pavidolides A-E (1-5) were isolated from the marine soft coral Sinularia pavida, together with sarcophytin and chatancin. The structures of new compounds were determined on the basis of extensive spectroscopic data analysis. Pavidolide B (2) possesses an unprecedented 6,5,7-tricarbocyclic nucleus, whereas pavidolide C (3) is characteristic of an unusual C-5 and C-9 conjuncted cembranoid. Pavidolides C and D showed moderate antifouling activity against the larval settlement of barnacle Balanus amphitrite, while pavidolides B and C exhibited inhibitory activity against the human leukemia cell line HL-60.     

Antibacterial ultrafiltration membrane with silver nanoparticle impregnation by interfacial polymerization for ballast water

Interfacial polymerization technology was employed to immobilize silver (Ag) nanoparticles on the surface of commercial polyethersulfone (PES) membrane to develop antibacterial and antifouling ultrafiltration membrane. Ag nanoparticles were prepared from the reduction of silver nitrate (AgNO₃) by sodium borohydride in the presence of polyethyleneimine (PEI) as the stabilizer. The encapsulated Ag nanoparticles in the PEI solution were embedded into the PEI membrane when trimesoyl chloride solution was used to crosslink the PEI solution with the PES membrane, forming Ag-polyamide (PA) networks through the interfacial polymerization reaction. Experimental results showed that the membrane prepared with 50 mmol/L of AgNO₃ and 20 mmol/L of PEI had the optimized antibacterial effect against Escherichia coli. Bacterial concentration and species were also investigated. Exiguobacterium aestuarii and Staphylococcus aureus which are gram-positive bacteria, needed significantly more time for the Ag-PA/PES membrane to kill the bacteria completely when compared to E.coli and Vibrio coralliilyticus which are gram-negative bacteria. This study showed that Ag nanoparticles impregnated in membrane surfaces were 100% effective in killing various types of marine bacteria and bacteria in the seawater collected off Sentosa Island in Singapore. These membranes exhibit excellent antibacterial and antifouling properties which can be used to kill bacteria in ballast water and seawater.     

Synthesis and Quantum Chemical Calculation of Benzamide Derivatives Containing Capsaicin and Their Bacteriostatic and Antifouling Properties

Thirteen benzamide derivatives containing capsaicin (BDCCs) have been successfully synthesized via the current method (Friedel‐Crafts alkylation reaction). The resultant monomers were characterized by IR, ¹H and ¹³C NMR, elemental analysis and HRMS. Characterization results were in agreement with the proposed structures of the products. Quantum chemistry calculation yielded three parameters, namely, Δε_L‐H, HF values (total energy) and dipole that could explain activity, stability and polarity respectively, and the relationship of each parameter with antimicrobial and antifouling performance was also preliminary discussed. The bacteriostatic property of the 13 compounds was evaluated by minimum inhibitory concentration (MIC) and bacteriostatic ring tests. Experimental results indicated that these compounds can inhibit Staphylococcus aureus and Escherichia coli. The antifouling effectiveness of the novel antifoulants was investigated using panel tests at the eighth harbor, Qingdao. Four‐month exposure results were compared. The compounds exhibited better antifouling properties than the blank panel without antifouling coating or the panel with a common coating. However, test panels with the antifouling coatings were covered with trace amounts of algae and Balanus because of weakening of antifouling ability over extended periods of time. All results demonstrate that the new compounds synthesized via our method can be applied in environment‐friendly antifouling paints.     

Determination of the reactivity parameters for the copolymerization of butyl acrylate with vinyl acetate

The composition of vinyl acetate–butyl acrylate copolymers obtained with batch emulsion polymerization have been studied by ¹H-NMR. Using the integrated copolymerization Meyer–Lowry equation, the apparent reactivity ratios of the two monomers were calculated as 10.67 for r₁, the reactivity ratio of butyl acrylate (BA), and 0.024 for r₂, the reactivity ratio of vinyl acetate (VAC). These results were compared with those obtained by other methods.     

Cyclodextrins in polymer chemistry: Influence of methylated β-cyclodextrin as host on the free radical copolymerization reactivity ratios of isobornyl acrylate and butyl acrylate as guest monomers in aqueous medium

Methylated β-cyclodextrin (me-β-CD) was used to complex the hydrophobic monomers isobornyl acrylate ( 1 ) and butyl acrylate (2) yielding the water-soluble host/guest complexes isobornyl acrylate/me-β-CD ( 1a ) and butyl acrylate/me-β-CD ( 2a ). The included monomers were copolymerized in water by free-radical mechanism and the kinetics were studied. In order to evaluate these results, the corresponding uncomplexed monomers 1 and 2 were also copolymerized in organic solution. The reactivity ratios of 1a and 2a (r _1a = 0.3, r _2a = 1.7) differ significantly from the reactivity ratios of the corresponding uncomplexed acrylates 1 and 2 in organic solution (r ₁ = 1.3, r ₂ = 1.0). In addition, we found that the weight averages of the copolymers prepared by using me-β-CD are significantly higher than those of the corresponding polymers prepared from uncomplexed monomers in organic solution.     

The influence of variant PE‐b‐PEO segments on physical properties of LLDPE graft copolymers

A method was adopted to fix a series of polymers of PE‐b‐PEO with different PEO/PE segments on the chains of LLDPE. Maleic anhydride (MA) reacting with hydroxyl group of PE‐b‐PEO (mPE‐b‐PEO) was used as the intermediate. The structures of intermediates and graft copolymers were approved by ¹H NMR and FTIR. XPS analysis revealed a great amount of oxygen on the surface of grafted copolymers although the end group of PEO was fixed on the LLDPE chains through MA. Thermal properties of the graft copolymers as determined by differential scanning calorimetry (DSC) showed that PE segments in the grafted monomers could promote the heterogeneous nucleation of the polymer, increase T_c, and crystal growth rate. While the amorphous PEO segments which attached to the crystalline PE segments in LLDPE, impaired their ability to fit the crystal lattice, and depressed the crystallization of LLDPE backbones. In this study, it was also verified through the dynamic rheological data that increasing M_n of grafted monomers significantly increased the complex viscosity and enhanced the shear‐thinning behavior. Long‐branched chains formed by grafted monomers enhanced the complex moduli (G′ and G″) value and retarded relaxation rate. However, there were little influence on the rheological properties when increasing the amounts of PEO segments (or decreasing PE segments) of grafted monomers with similar molecular weight. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 506–515, 2008     

Chain Walking Ethylene Copolymerization with an ATRP Inimer for One‐Pot Synthesis of Hyperbranched Polyethylenes Tethered with ATRP Initiating Sites

A one‐pot procedure for the synthesis of hyperbranched polyethylenes tethered with ATRP initiating sites by chain walking ethylene copolymerization with an acrylate‐type ATRP inimer, 2‐(2‐bromoisobutyryloxy) ethyl acrylate (BIEA) is reported. Because of its ability to incorporate acrylate‐type comonomers and tolerance toward the α‐bromoester group, the chain walking Pd‐diimine catalyst, [(ArNC(Me) (Me)CNAr)Pd(CH₃)(NCMe)]SbF₆ (Ar = 2,6‐(iPr)₂C₆H₃), allowed the successful synthesis of a series of hyperbranched copolymers tethered with 2‐bromoisobutyryl groups at different densities. These copolymers may serve as polyfunctional macroinitiators for the ATRP of functional monomers to further synthesize core‐shell structured functionalized copolymers with a hyperbranched polyethylene core grafted with side chains of the functional monomers.

     

Polyiodized‐PCL as multisite transfer agent: Towards an enlarged library of degradable graft copolymers

Poly(ε‐caprolactone)‐based graft copolymers were prepared via a “grafting from” technique derived from iodine transfer polymerization. This copolymerization was done thanks to a poly(ε‐caprolactone‐co‐α‐iodo‐ε‐caprolactone) (PCL‐I), which was used as a multisite transfer agent. Styrene (Sty) and n‐butyl acrylate (n‐BuA) were firstly used as model monomers to establish the feasibility of using PCL‐I as multisite transfer agent, and investigate some general properties of the polymerization. The formation of PCL‐g‐PSty and PCL‐g‐P(n‐BuA) copolymers was confirmed by SEC and NMR analyzes of the copolymers before and after degradation of the PCL backbone. This method was extended to an acrylamide monomer, namely (N,N‐dimethyl) acrylamide (DMA), to prepare original amphiphilic copolymers with PCL as hydrophobic backbone and amido‐functionalized hydrophilic grafted chains. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 5006–5016, 2009     

Control of thermal,mechanical, and optical properties of three‐component maleimide copolymers by steric bulkiness and hydrogen bonding

N‐substituted maleimides polymerize in the presence of a radical initiator to give polymers with excellent thermal stabilities and transparency. In this study, we synthesized various maleimide copolymers with styrenes and acrylic monomers to control their thermal and mechanical properties by the introduction of bulky substituents and intermolecular hydrogen bonding. Three‐component copolymers of N‐(2‐ethylhexyl)maleimide in combination with styrene, α‐methylstyrene (MSt), or 1‐methylenebenzocyclopentane (BC5) as the styrene derivatives, and n‐butyl acrylate, 2‐hydroxyethyl acrylate, 4‐hydroxybutyl acrylate, or acrylic acid as the acrylic monomers were prepared by radical copolymerization. These copolymers were revealed to exhibit excellent heat resistance by thermogravimetric analysis. Glass transition temperatures increased by the introduction of bulky MSt and BC5 repeating units. The mechanical properties of the copolymer films were improved by the introduction of intermolecular hydrogen bonding. Optical properties, such as transmittance, refractive index, Abbe number, and birefringence, were determined for the copolymers. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1569–1579     

Tailoring of polymers by combination of ionic and radical controlled polymerizations

Poly(methyl methacrylate)s with terminal bromine atom, prepared by bromination of anionically polymerized MMA, were used as ATRP macroinitiators giving di- and triblock copolymers with MMA, styrene and butyl acrylate blocks. Multifunctional ATRP macroinitiators were synthesized by introducing bromomethyl or 2-bromoacyloxy groups onto the main chain of polystyrene or poly(4-methyl styrene) and used for ATRP grafting of tert-butyl acrylate leading to densely grafted copolymers with more or less uniform grafts.     

Alternating copolymerization of methyl acrylate with donor monomers having a protected amine group

Attempts were made to copolymerize p-aminostyrene, p-acetamidostyrene, N-methyl-p-aceta-midostyrene, N-(4-vinylphenyl) phthalimide, N-vinyl succinimide, and N-vinyl phthalimide with methyl acrylate complexed with ethyl aluminum sesquichloride. Only reactions involving N-(4-vinylphenyl)phthalimide and N-vinyl phthalimide yielded alternating copolymers. N-vinyl succinimide gave nonalternating copolymers insoluble in common solvents and the other monomers did not copolymerize. In some cases, the conventional radical copolymers were prepared for comparison purposes. The reactivity ratios of the free-radical initiated copolymerization of methyl acrylate (I) with N-(4-vinylphenyl)phthalimide (II) were r₁ = 0.14 and r₂ 1.56. The alternating copolymers were studied by ¹H-NMR and ¹³C-NMR spectroscopy. The alternating copolymer of N-(4-vinylphenyl)phthalimide with methyl acrylate was hydrazinolyzed to form the alternating copolymer of methyl acrylate with p-aminostyrene. Hydrazinolysis of the alternating copolymer of methyl acrylate with N-vinyl phthalimide removed the phthalimide moiety and generated vinyl amine units which readily cyclized with neighboring methyl acrylate units to form copolymers that contained five-membered lactam rings. The infrared (IR) spectra of the hydrazinolyzed products contain bands due to amine or amide groups and are devoid of the characteristic bands of the phthalimide ring.     

Block copolymer preparation by atom transfer radical polymerization under emulsion conditions using a nanoprecipitation technique

Living‐radical polymerization of acrylates were performed under emulsion atom transfer radical polymerization (ATRP) conditions using latexes prepared by a nanoprecipitation technique previously employed and optimized for the polymerization of styrene. A macroinitiator of poly(n‐butyl acrylate) prepared under bulk ATRP was dissolved in acetone and precipitated in an aqueous solution of Brij 98 to preform latex particles, which were then swollen with monomer and heated. Various monomers (i.e. n‐butyl acrylate, styrene, and tert‐butyl acrylate) were used to swell the particles to prepare homo‐ and block copolymers from the poly(n‐butyl acrylate) macroinitiator. Under these conditions latexes with a relatively good colloidal stability were obtained. Furthermore, amphiphilic block copolymers were prepared by hydrolysis of the tert‐butyl groups and the resulting block copolymers were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The bulk morphologies of the polystyrene‐b‐poly(n‐butyl acrylate) and poly(n‐butyl acrylate)‐b‐poly(acrylic acid) copolymers were investigated by atomic force microscopy (AFM) and small angle X‐ray scattering (SAXS). © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 625–635, 2008     

Synthesis,characterization, and property of amphiphilic fluorinated abc‐type triblock copolymers

Novel amphiphilic fluorinated ABC‐type triblock copolymers composed of hydrophilic poly(ethylene oxide) monomethyl ether (MeOPEO), hydrophobic polystyrene (PSt), and hydrophobic/lipophobic poly(perfluorohexylethyl acrylate) (PFHEA) were synthesized by atom transfer radical polymerization (ATRP) using N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA)/CuBr as a catalyst system. The bromide‐terminated diblock copolymers poly(ethylene oxide)‐block‐polystyrene (MeOPEO‐b‐PSt‐Br) were prepared by the ATRP of styrene initiated with the macroinitiator MeOPEO‐Br, which was obtained by the esterification of poly(ethylene oxide) monomethyl ether (MeOPEO) with 2‐bromoisobutyryl bromide. A fluorinated block of poly(perfluorohexylethyl acrylate) (PFHEA) was then introduced into the diblock copolymer by a second ATRP process to synthesize a novel ABC‐type triblock copolymer, poly(ethylene oxide)‐block‐polystyrene‐block‐poly(perfluorohexylethyl acrylate) (MeOPEO‐b‐PSt‐b‐PFHEA). These block copolymers were characterized by means of proton nuclear magnetic resonance (¹H NMR) and gel permeation chromatography (GPC). Water contact angle measurements revealed that the polymeric coating of the triblock copolymer (MeOPEO‐b‐PSt‐b‐PFHEA) shows more hydrophobic than that of the corresponding diblock copolymer (MeOPEO‐b‐PSt). Bovine serum albumin (BSA) was used as a model protein to evaluate the protein adsorption property and the triblock copolymer coating posseses excellent protein‐resistant character prior to the corresponding diblock copolymer and polydimethylsiloxane. These amphiphilic fluoropolymers can expect to have potential applications for antifouling coatings and antifouling membranes. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis of copolymer brushes endowed with adhesion to stainless steel surfaces and antibacterial properties by controlled nitroxide-mediated radical polymerization

Novel copolymer brushes have been synthesized by a two-step "grafting from" method that consists of the electrografting of poly(2-phenyl-2-(2,2,6,6-tetramethyl-piperidin-1-yloxy)-ethylacrylate) onto stainless steel, followed by the nitroxide-mediated radical polymerization of 2-(dimethylamino ethyl)acrylate and styrene or n-butyl acrylate, initiated from the electrografted polyacrylate chains. The grafted copolymers were quaternized in order to endow them with antibacterial properties. Peeling tests have confirmed the strong adhesion of the grafted copolymer onto the stainless steel substrate. Quartz crystal microbalance experiments have proven that fibrinogen adhesion is lower on the hydrophilic quaternized films compared to the nonionic counterpart. Such quaternized copolymers exhibit significant antibacterial activity against the Gram-positive bacteria S. aureus and the Gram-negative bacteria E. coli.     

Antifeedant and antifouling briaranes from the South China Sea gorgonian <Emphasis Type="Italic">Junceella juncea</Emphasis>

A new briarane diterpene, juncin ZII (1), along with three known briaranes (2–4), was isolated from the EtOH/CH₂Cl₂ extracts of the South China Sea gorgonian Junceella juncea. The structure of 1 was established by extensive spectroscopic analysis, including 1D and 2D NMR data. For compounds 1–4 and eight other briaranes (5–12) isolated from J. juncea previously, the antifeedant activity against second-instar larvae of Spodoptera litura and cytotoxicity against S. litura cells were investigated, and it was observed that they all exhibit medium antifeedant activity. Compounds 1, 8, 9, and 12 also showed potent antifouling activity against the larval settlement of barnacle Balanus amphitrite at nontoxic concentrations with EC₅₀ values of 0.004, 0.005, 2.82, and 0.447 μg/mL, respectively, while all compounds did not show obvious cytotoxicity against tumor cell lines K562, A549, Hela, and Hep-2. Their structure-activity relationship was discussed. Published in Khimiya Prirodnykh Soedinenii, No. 1, pp. 44–47, January–February, 2009.     

Synthesis and Mechanical Properties of Polypropylene-based Polymer Hybrids via Controlled Radical Polymerization

Isotactic polypropylene-based graft copolymers linking poly(methyl methacrylate), poly(n-butyl acrylate) and polystyrene were successfully synthesized by a controlled radical polymerization with isotactic polypropylene (iPP) macroinitiator. The hydroxylated iPP, prepared by propylene/10-undecen-1-ol copolymerization with a metallocene/methyl-aluminoxane/triisobutylaluminum catalyst system, was treated with 2-bromoisobutyryl bromide to produce a Br-group containing iPP (PP-g-Br). The resulting PP-g-Br could initiate controlled radical polymerization of methyl methacrylate, n-butyl acrylate and styrene by using a copper catalyst system, leading to a variety of iPP-based graft copolymers with a different content of the corresponding polar segment. These graft copolymers demonstrated unique mechanical properties dependent upon the kind and content of the grafted polar segment.     

Synthesis of ion exchange membranes from ozonized high density polyethylene

The synthesis and the characterization of graft copolymers prepared from ozonized high density polyethylene (HDPE) are described. The powder of HDPE was treated with ozone in well defined conditions and then copolymerized with monomers, such as, acrylic acid (AA), N,N-dimethylamino-2 ethylmethacrylate (MADAME) and vinyl phosphonic acid (VPA). Cationic exchange membranes were prepared from the grafted copolymers of AA and VPA and anionic exchange membrane from the grafted copolymer of MADAME. The obtained copolymers were characterized by the grafting rate, FTIR spectroscopy, scaning electronic microscopy, thickness, exchange capacity and electrical resistance.     

Long-lived polymer radicals. III. Synthesis of block copolymer by the reaction of living poly(N-methylacrylamide) radical with some vinyl monomers

N-Methylacrylamide (NMAAm) was polymerized quantitatively by using di-tert-butyl peroxide as photosensitizer to be, for the most part, incorporated in living poly(NMAAm) radical. The living polymer radical reacted effectively with acrylate monomers to yield block copolymer. Longer alkyl chain of the acrylate monomer caused a decrease in the conversion of the second monomer. Methacrylate monomers, such as methyl methacrylate and cyclohexyl methacrylate, showed relatively low reactivities in comparison with acrylates. Styrene exhibited a much lower conversion. The resulting block copolymers showed different thermochromic behaviors in methyl benzoate from that of poly(NMAAm). This is explained on the basis of the difference between refractive indexes of the block copolymers and poly(NMAAm).