Research on the Marine Antifouling Ability and Mechanism of Acrylate Copolymers and Marine Coatings Based on a Synergistic Effect

Marine biofouling is an urgent global problem in the process of ocean exploitation and utilization.In our work,a series of zinc-based acrylate copolymers(ACZn-x)were designed and synthesized using benzoic acid,zinc oxide(ZnO)and a random quaternion copolymer consisting of ethyl acrylate(EA),butyl acrylate(BA),acrylic acid(AA)and methacrylic acid(MAA)by free radical polymerization and dehydration condensation.The ACZn-x with a zinc benzoate side chain is able to hydrolyze in natural seawater under static conditions,resulting in the formation of a smooth surface.We investigated and confirmed the antifouling(AF)behavior of ACZn-x in the laboratory and revealed that they have better antibacterial(86%for S.aureus and 72%for E.coli)and anti-algal(≥60.1%for N.closterium and≥67.5%for P.subcordiformis)activities.We also assessed the marine AF properties of ACZn-x and corresponding coatings in Qingdao,China;the ACZn-x exhibited ideal AF properties with little silt and biological mucosa adhered to the ACZn-x surface after 6 months,and corresponding coatings exhibited little biofouling after 16 months in the ocean.Importantly,possible AF mechanisms were further proposed at the cellular level.These results could be helpful for the development and application of effective AF coatings.

Synthesis of Amine-type Adsorbents with Emulsion Graft Polymerization of 4-hydroxybutyl Acrylate Glycidylether

Radiation induced graft polymerization on polymeric matrix followed by functionalization is widely accepted for the preparation of metal adsorbents. In this paper, a pre-irradiation method was used for emulsion graft polymerization of 4-hydroxybutyl acrylate glycidylether (4-HB) onto polyethylene/polypropylene (PE/PP) nonwoven fabric. The degree of grafting (Dg) which can be calculated by weight increment was determined as a function of reaction time, irradiation dose, and monomer concentration. After 30 kGy irradiation, with 4-HB concentration of 5%, surfactant Span 20 of 0.5% at 40°C for 2 h, the trunk polymer was made grafted at a Dg of 135%. 4-HB-grafted PE/PP nonwoven fabric was modified by ethylenediamine (EDA) in isopropyl alcohol (IPA) as a solvent at 60°C. With a Dg of 135%, the amine group density of the adsorbent is 2.8 mmol/g. The adsorption test was carried out by batch experiment in several metal ion solutions, and the removal ratio from the EDA modified adsorbent of the metal ions is in the order of Cu2+ > Pb2+ > Zn2+ > Ni2+ > Li+. Compared with glycidyl methacrylate (GMA) which is a typical functional monomer for graft polymerization, 4-HB-grafted adsorbent exhibited not only better mechanical property but also higher adsorption capacity of Cu2+ and Pb2+.

EFFECT OF TEMPERATURE ON COPOLYMERIZATION PARAMETERS OF HYDROXYETHYL ACRYLATE AND METHYL METHACRYLATE

The copolymerization of 2-hydroxyethyl acrylate (HEA, M//1) and methyl methacrylate (MMA, M//2) in cyclohexanone was studied. The multiple experiments of solution copolymerization with low conversion were carried out at two sensitive composition feed points at 60, 80, 100, 120 and 140 degree C, respectively. The composition of the copolymers was analyzed by **1H-NMR. The reactivity ratios which were estimated by the Error-in-Variable Method (EVM) of Mayo-Lewis equation were found to be r//1 equals 0.328, r//2 equals 1.781 for 60 degree C; 0.375, 1.709 for 80 degree C; 0.406, 1.654 for 100 degree C; 0.439, 1.540 for 120 degree C and 0.455, 1.400 for 140 degree C, and the 95% joint confidence intervals of the reactivity ratios were also determined. According to r//1 and r//2, Arrhenius relations and the activity energy difference between the homo- and cross-propagation were calculated. (Author abstract) 12 Refs.

PREPARATION AND MECHANICAL PROPERTIES OF POLY(METHYL METHACRYLATE)/ URETHANE ACRYLATE COPOLYMERS

The urethane acrylate(UA) was made of poly(tetramethylenc oxide), 4,4’-diphenylmethane diisocyanate, and 2-hydroxyethyl methacrylate. A series of poly(methyl methacrylate) / urethane acrylate copolymers was prepared by using a redox initiating system. The copolymers had cross linked structures and two-phase morphologies as indicated by the results of the dynamic mechanical measurement and swelling test.

Anti-fouling ultrafiltration membrane prepared from polysulfone-graft-methyl acrylate copolymers by UV-induced grafting method

Membrane fouling is one of the most important challenges faced in membrane ultrafiltration operations. The copolymers of polysulfone-graft-methyl acrylate were synthesized by homogeneous photo-initiated graft copolymerization. The variables affecting the degree of grafting, such as the time of UV （Ultraviolet-visible） irradiation and the concentrations of the methyl acrylate and photoinitiator, were investigated. The graft copolymer membranes were prepared by the phase inversion method. The chemical and morphological changes were characterized by attenuated total reflection-Fourier transform infrared spectroscopy （ATR/FT-IR）, scanning electron microscopy, and water contact angles measurements. Results revealed that methyl acrylate groups were present on the membranes and the graft degree of methyl acrylate had remarkable effect on the performance of membranes. Pure water contact angle on the membrane surface decreases with the increase of methyl acrylate graft degree, which indicated that the hydrophilicity of graft copolymer membranes was improved. The permeation fluxes of pure water and bovine serum albumin solution were measured to evaluate the antifouling property of graft copolymer membranes, the results of which have shown an enhancement of antifouling property for graft copolymer membranes.

EFFECTS OF PHENOL RESIN ADDITIVE ON DYNAMIC MECHANICAL PROPERTIES OF ACRYLATE RUBBER AND ITS BLENDS

The dynamic mechanical properties of a new blend system consisting of phenol resin and polar polymer (acrylaterubber and/or chlorinated polypropylene) were investigated. It was found that the addition of phenol resin to acrylate rubberand its incompatible blend can cause a remarkable improvement in the temperature dependence of the loss tangent. As a result, the present blends are very good damping materials.

A novel epoxy methacrylate resin containing phthalazinone moiety for UV coatings

A novel ohthalazinone modified epoxy acrylate resin for the high temperature resistant ultravioet （UV） curable coating.was syn-thesized.The methacrylated epoxy resins obtained were utilized to UV radiation curing by taking 2.5% （wt%） of photoinitiator in combination with 20% （wt%） of diluent, and generated the interpenetraring polymer networks. The cured film had good thermal and chemical stability.

Synthesis of a Novel UV-curable Prepolymer Polypropyleneglycol Diglycidyl Ether Diacrylate

A novel UV-curable prepolymer polypropyleneglycol diglycidyl ether diacrylate （PPGGEA） was synthesized by utilizing polypropyleneglycol diglycidyl ether （PPGGE） and acrylic acid （AA） as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimum synthetic conditions were in the following： the concentration of N, N-dimethylbenzylamine was 0.80 wt% of reactants, the concentration of p-hydroxyanisole was 0.3 wt% of reactants, the reaction temperature was 90-110 ~C, and the molar ratio of PPGGE to AA was 1：2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-cured initiator was added to the synthesized PPGGEA to prepare a kind of UV-cured coating. The mechanical properties of the UV-cured films were determined, giving 29.99 MPa of tensile strength, 834.27 MPa of the Young＇s modulus and 5.66% of elongation at tear.

Influence of Carboxyl Groups on the Particle Size and Rheological Properties of Polyacrylate Latices

The PAL was synthesized with BA,MMA and some monomers containing carboxyl groups（for example,acrylic acid（AA） and methacrylic acid（MAA）） as co-monomers by semi-continuous seeded emulsion polymerization technique.The influences of alkalinization temperature,the feeding manner of AA or MAA on the particles size,rheological properties and carboxyl distribution of the latex were discussed,and the rheological mechanism was analyzed.The experimental results show that the PAL system has preferable viscosity and particle size when the alkalinization temperature is 50 ℃.Different distribution of carboxyl group in the particles and different resultant rheological properties are obtained by different feeding manner of AA or MAA into the system.The TEM images show that the particle is a smooth globe with carboxyl group concentrating on the surface and stabilized with electric double layer and nonionic adsorbed layer.The concentration of carboxyl functional group on the surface of particles can be achieved by the specific polymerization technique.The rheologyical properties are determined by accretion of particle volume and variation of the two phase volume ratio resulted from the carboxyl group spreading layer.

PHOTOINITIATED INVERSE EMULSION POLYMERIZATION OF SODIUM ACRYLATE

Photoinitiated inverse emulsion polymerization of sodium acrylate(AANa)in kerosene was carried out at room orlower temperature,using 2,2-dimethoxy-2-phenylacetophenone(DMPA)as the initiator.Kinetic investigations indicated thatthe polymerization could be completed in about 30 min and produce polymer with high molecular weight(10~6～10~7).It wasfound that monomer droplets are the main sites for the polymerization(nucleation).With the increase of DMPAconcentration,polymerization rate(R_p)reaches a maximum value while molecular weight of the produced polymer has anadverse result,but the dependence of R_p on incident light intensity is similar.Influences of other parameters such asmonomer concentration,emulsifier content and reaction temperature,etc.were also studied.At lower pH values of waterphase,R_p depends strongly on the pH due to the electrostatic interaction between the ionized radicals and the monomer.Athigher pH,R_p shows a slight dependence on pH.

Synthesis and Characterization of the Polyacrylonitrile-block- poly(methyl acrylate) by RAFT Technique

Polyacrylonitrile-block-poly（methyl acrylate）（P（AN-b-MA）） was synthesized by reversible addition-fragmentation chain transfer （RAFT） polymerization employing macro-RAFT agent （PAN-RAFT） as the chain transfer agent and azobis（isobutyronitrile） （AIBN） as the initiator. A linear relationship between ln（[M]0/[M]1） and reaction time was observed. The molecular structure of P（AN-b-MA） was characterized by ^1H-NMR, element analysis, FTIR and SEC. The molecular weight distribution （MWD） was less than 1.40, the Mn could be controled from 0.733 to 4.834×10^4, and the molar content of MA in P（AN-b-MA） were from 15.6 to 75.0 percentage, respectively.

Hyperbranched Polyurethane Acrylate Applied to UV Curable Flame Retardant Coatings

UV curable hyperbranched prepolymers based on amine-ester, ester-amide and ether-amide started with AB_2-type monomers have been prepared by the authors. A series of work on allyl ether maleate hyperbranched polyesters for UV curing coatings by Hult and his colleagues has been reported. However, the UV cured films from those materials are all flammable when attached to fire without addition of flame retardants.

Reactive extraction for intensifying 2-ethylhexyl acrylate synthesis using deep eutectic solvent [Im:2PTSA]

2-Ethylhexyl acrylate(2-EHA)is one of the most widely used acrylates in the polymer industry,which is synthesized via Fisher esterification that is limited by chemical equilibrium.To intensify the esterification process,in this work,reactive extraction concept is proposed,with halogen-free deep eutectic solvent(DES[Im:2PTSA])as dual solvent-catalyst that consists of imidazole(Im)and p-toluenesulfonamide(PTSA).The bifunctional effects of the DES[Im:2PTSA]are evaluated by thermodynamic analysis and experimental study.Favorable phase splitting is verified byσ-potential analysis predicted by COSMO-RS theory,combined with experiments,and the optimal acid-to-alcohol molar ratio is set to 1.2.The esterification kinetics is then experimentally determined and fitted using the molar-based and activity-based pseudo-homogeneous(PH)models,respectively.The activity-based PH model,that considers the bifunctional roles of the DES,proves to be more accurate with small RMSD of 0.0344.The stability of DES after recycling is validated to further confirm the industrial prospects of DES[Im:2PTSA]in 2-EHA production.

Synthesis of a Novel UV-curable Prepolymer Hexanediol Diglycidyl Ether Diacrylate and Its Cured Film Tensile Property

A novel UV-curable prepolymer hexanediol diglycidyl ether diacrylate （HDGEA） was synthesized by utilizing hexanediol diglycidyl ether （HDGE） and acrylic acid （AA） as starting materials, N, N-dimethylbenzylamine as catalyst and p-hydroxyanisole as inhibitor. The optimal synthetic conditions were that the concentration of N, N-dimethylbenzylamine was 0.80 wt% of reactants, the concentration of p-hydroxyanisole was 0.3 wt% of reactants, the reaction temperature was 90-110 ℃, and the molar ratio of HDGE to AA was 1︰2.2. Meanwhile, 1-hydroxycyclohexyl phenyl ketone of a UV-curing initiator was added to the synthesized HDGEA to prepare a kind of UV-curing coating. The mechanical properties of the UV-cured films were determined, giving 31.87 MPa of tensile strength, 871.88 MPa of Young＇s modulus and 6.77% of elongation at tear.

Preparation and characterization of a novel antibacterial acrylate polymer composite modified with capsaicin

A novel antibacterial acrylate polymer composite modified with capsaicin was successfully synthesized by a two-step reaction.Capsaicin and acryloyl chloride were firstly esterified,and then applied to solution polymerization with acrylate monomers and styrene.The yield of the esterified products was about 85.3%.The polymer was characterized by Fourier transform infrared spectroscopy(FTIR),gel permeation chromatography(GPC),thermogravimetric analysis(TGA),contact angle(CA)and antibacterial ring tests.The number-average molecular weight(M_n)of the polymer was 27214,based on the capsaicin-acrylate dosage of 6.5 wt%.The TGA revealed a stable thermal property.The contact angles of the polymers films on tinplate increased from 77.5°to 86.2°with the increasing amount of capsaicin-acrylate.The antibacterial tests demonstrated excellent antimicrobial capability of the polymers.

MODIFIED ULTRAVIOLET-CURABLE WATER DISPERSIBLE POLYURETHANE-ACRYLATES

Three kinds of UV-curable self-emulsified polyurethane-acrylate (PUA) prepolymer, i.e., conventional, chain extended and grafted PUAs, were prepared. The relatively small particle size of the PUA dispersions indicates that the PUA prepolymers exhibit sufficient aqueous dispersibility. The PUA prepolymers can substantially lower the interfacial tension of water. Chain-extended PUA dispersions exhibit pseudoplastic behavior and thixotropy to a greater extent than do their conventional counterpart. The chain-extended and grafted PUA photocure to higher conversion than do the conventional PU equivalent. The results of DSC measurement suggest that there exists phase mixing between the hard and the soft segment phases for the PUAs based on PEG 400 that is the comparatively short soft segment in the prepolymer. For the PUA prepolymers based on PEG having higher M-n values, chain-extending and grafting could impede the phase separation between the hard and the soft segment domains. The adhesion, impact strength and flexibility of the photocured films were tested.

Heteropolyacids Catalysis in Synthesizing Butylacrylate

The catalytic activities of some heteropolyacids(HPAs) in synthesizing butyl acrylate are reported. It has been demonstrated that 12 tungstophosphoric acid is the most effective catalyst among more than 20 HPA(salts). Various factors concerned in this reaction have been investigated. The optimum conditions have been found, that is, the molar ratio of alcohol to acid is 1.2∶1.0 , the catalyst concentration 1%(mass fraction), the reaction time 2 h, the temperature 98—124 ℃ and a certain amount of polymerization inhibitor exists.

Crystal Structure of a Novel Supramolecule Made Up of Bis(μ_2-aqua)aqua(3-carboxy acrylate) monosodium(Ⅰ)

The title compound, bis( μ 2 aqua)(aqua)(3 carboxy acrylate) monosodium(Ⅰ), was synthesized in an ethanol water solution and its crystal structure was determined by means of X ray diffraction. The crystal is triclinic , space group P 1 with the cell parameters a =0 592 4(2) nm, b =0 635 7(3) nm, c =1 117 7(6) nm, α =104 18°, β =91 53°, γ =100 19°, V =0 400 6(3) nm 3, Z =2, the final R value is 0 033 5. The supramolecule is made up of coordination chains, which are further extended into a three dimensional network via the hydrogen bonding interactions.

PHOTO-INDUCED DOPED POLYANILINE BY THE VINYLIDENE CHLORIDE AND METHYL ACRYLATE COPOLYMER AS PHOTO ACID GENERATOR

The emeraldine base form of polyaniline (PANI) can be doped by a photo-induced doping method. In this method a. copolymer of vinylidene chloride and methyl acrylate (VCMAC) was used as photo acid generator which can release proton when it is exposed to ultraviolet light (lambda = 254 nm). The structure of PANI-VCMAC system before and after irradiation was characterized by elemental analysis, IR, XTP, anti SEM images. Results obtained indicate that the photo-induced doping characteristics, such as doping position and type of charge carriers, are similar to that of PANI doped with HCl. The poor room-temperature conductivity (similar to 10-S-5/cm) of PANI-VCMAC system after irradiation may be due to low doping degree (similar to pH=3) and the difference in morphology as compared with PANI-HCl film.

Nonionic Polymerizable Emulsifier in High-Solids-Content Acrylate Emulsion Polymerization

Stable high-solids-content acrylate emulsion were obtained with a nonionic polymerizable emulsifier allyloxy nonylphenoxy poly （ethyleneoxy） （10） ether （ANPEO10）, and a conventional emulsifier OP-10 as a reference sample. 1H NMR proves that the polymerizable emulsifier ANPEO10 has been incorporated into the resulted acrylate polymers. TEM demonstrates that there are some differences in the particle morphologies. AFM proves that the polymerizable emulsifier ANPEO10 migrating to the surface of the emulsion film was much less than the conventional emulsifier OP-10. The polymerizable emulsifier ANPEO10 can enhance the adhesion with glass plate compared to the conventional emulsifier. Furthermore, with increasing amount of emulsifier, the surface free energy of the films first decreased and then increased, and the adhesion with glass plate is initially enhanced and then attenuated. The water-resistance and solvent-resistance of the films prepared by the polymerizable emulsifier ANPEO10 are superior to those prepared by the conventional emulsifier OP-10.