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.

Effect of Butyl α-Hydroxymethyl Acrylate Monomer Structure on the Morphology Produced via Aqueous Emulsion Polymerization-induced Self-assembly

Polymerization-induced self-assembly(PISA) is an efficient and versatile method to afford polymeric nano-objects with polymorphic morphologies. Compared to dispersion PISA syntheses based on soluble monomers, the vast majority of emulsion PISA formulations using insoluble monomers leads to kinetically-trapped spheres. Herein, we present aqueous emulsion PISA formulations generating worms and vesicles besides spheres. Two monomers with different butyl groups, n-butyl(n BHMA) and tert-butyl(t BHMA) α-hydroxymethyl acrylate, and thus possessing different water solubilities were synthesized via Baylis-Hillman reaction. Photoinitiated aqueous emulsion polymerizations of n BHMA and t BHMA employing poly(ethylene glycol) macromolecular chain transfer agents(macro-CTAs, PEG45-CTA, and PEG113-CTA) at 40 °C were systematically investigated to evaluate the effect of monomer structure and solubility on the morphology of the generated block copolymer nano-objects. Higher order morphologies including worms and vesicles were readily accessed for t BHMA, which has a higher water solubility than that of n BHMA. This study proves that plasticization of the core-forming block by water plays a key role in enhancing chain mobility required for morphological transition in emulsion PISA.

Developing an atmospheric aging evaluation model of acrylic coatings:A semi-supervised machine learning algorithm

To study the atmospheric aging of acrylic coatings,a two-year aging exposure experiment was conducted in 13 representative climatic environments in China.An atmospheric aging evaluation model of acrylic coatings was developed based on aging data including11 environmental factors from 567 cities.A hybrid method of random forest and Spearman correlation analysis was used to reduce the redundancy and multicollinearity of the data set by dimensionality reduction.A semi-supervised collaborative trained regression model was developed with the environmental factors as input and the low-frequency impedance modulus values of the electrochemical impedance spectra of acrylic coatings in 3.5wt%NaCl solution as output.The model improves accuracy compared to supervised learning algorithms model(support vector machines model).The model provides a new method for the rapid evaluation of the aging performance of acrylic coatings,and may also serve as a reference to evaluate the aging performance of other organic coatings.

Treatment of Synovial Cysts in Relation to the Tibial Tunnel of Anterior Cruciate Ligament Grafts by Filling the Tunnel with Acrylic Cement

Introduction: Synovial cyst of the tibial tunnel in connection with anterior cruciate ligament (ACL) reconstruction is a rare but particularly troublesome complication. Medical treatment is often doomed to failure, and surgical treatment usually consists of excising the cyst and filling the tunnel with bone. The aim of this study was to evaluate the results of filling the tunnel with acrylic cement. Hypothesis: Filling the tibial bone tunnel with acrylic cement should eliminate communication between the joint cavity and the pre-tibial surface and prevent cyst recurrence. Patients and Methods: This retrospective series is composed of 13 patients, 9 men and 4 women, mean age 48.5 years (31 to 64) operated on between 2011 and 2019 for an intra- and extraosseous synovial cyst consecutive to the tibial tunnel of an ACL graft. Between 1983 and 2016, 12 of the patients had had a bone graft without bone block fixation (DI-DT or Mac Intosh) and one patient, a bone-bone transplant (KJ). The cyst was of variable size, located on the anteromedial aspect of the proximal end of the tibia, and often painful, warranting consultation. At the time of the initial operation, 9 patients had undergone meniscectomies (6 medial, 2 lateral, 1 double). In 7 knees, there were 7 cartilage lesions in the femorotibial and/or patellofemoral compartments (one stage 1 lesion, 2 stage 2 lesions, 4 stage 3 lesions, and no stage 4 lesions). Only 2 knees had neither cartilage nor meniscus lesions. After curettage of the bone tunnel /− removal of the non-resorbed or PEEK interference screw, the tunnel was filled with acrylic cement /− reinforced with a ligament staple to prevent expulsion. All patients underwent regular follow-up consultations until recovery. Results: At a maximum follow-up of 8 years, only 1 cyst recurred, representing a 7.69% failure rate. It was reoperated with another technique, which involved filling the tibial bone tunnel with bone graft taken from a half-bank head. After recovery, the cyst healed definitively. All patients were able to return to their previous activity within 15 days of surgery. Conclusion: Filling the tibial tunnel with acrylic cement reinforced /− with a ligament staple is a reliable and rapid solution for the treatment of intra- and extra-articular synovial cysts in relation to the tibial tunnel of ACL grafts.

STUDY ON THE STARCH GRAFTED ACRYLATE MONOMERS AND ITS COMPATIBILITY FOR THE BLEND SYSTEM OF STARCH AND POLYETHYLENE

研究采用高温和剪切力的作用直接引发淀粉与丙烯酸酯单体的接枝共聚合反应．讨论了各种反应条件对接枝反应的影响，并进一步研究了接枝物在淀粉聚乙烯共混体系中的增容作用．实验结果表明，高温和剪切作用力可以引发淀粉与丙烯酸酯单体的接枝共聚合反应。接枝物作为增容剂，对淀粉聚乙烯共混体系的力学性能和流变学性能均有所改善．

新型Acrylic/TiNi复合材料阻尼与力学性能研究

兼具优良吸能特性和高阻尼性能的金属基复合材料有着广泛的应用需求。采用“均混-压制-脱溶-烧结”的四阶段粉末冶金技术制备三维通孔的TiNi多孔材料,并以TiNi多孔材料为基体,基于真空负压渗流技术制备新型Acrylic/TiNi复合材料。内耗测试表明:新型复合材料阻尼能力远高于相应的多孔材料,尤其在室温附近。分析表明,复合材料阻尼能力的提高除与Acrylic的本征高阻尼有关,还与复合材料的多孔TiNi基体和Acrylic之间新增的大量界面阻尼有关。准静态压缩力学性能测试表明:Acrylic/TiNi复合材料可实现和TiNi多孔合金相近的能量吸收效率,这源于复合材料更长且更光滑的压缩平台区。此外,增强相Acrylic的充分渗入,极大提高复合材料的能量吸收能力和屈服强度。压缩形变机制分析表明,复合材料吸能特性的综合提高与压缩过程中TiNi多孔基体和Acrylic填充物之间相互补偿和耦合有关。

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.

PROPERTIES AND MORPHOLOGY OF UNSATURATED POLYESTER/ACRYLATE-TERMINATED POLYURETHANE/ORGANO-MONTMORILLONITE NANOCOMPOSITES

Unsaturated polyester resin （UPR）/acrylate-terminated polyurethane （ATPU）/organo-modified montmorillonite （OMMT） nanocomposites were prepared by the in situ intercalative polymerization method. Samples were prepared by the sequential mixing, i.e. mixture of the ATPU and styrene （S） and OMMT were prepared in the first step; UPR was then added to the pre-intercalates of ATPU/S/OMMT. Results indicate that the mechanical properties and thermal properties of UPR/ATPU/OMMT nanocomposites greatly depend on the amount of ATPU and OMMT. Results show that the addition of ATPU could increase the impact strength of UPR/ATPU composites, but the tensile strength, flexural strength and heat resistance of the materials are obviously decreased. When the weight ratio between UPR, ATPU and OMMT were 82：15：3, the impact strength and heat distortion-temperature of nanocomposite were greatly improved, meanwhile there was little change for other properties of the nanocomposites. The synergistic enhancement effects of ATPU and OMMT on the composites were observed. The structures and morphology of the composites were investigated by X-ray diffraction, scanning electron microscopy and transmission electron microscopy.

Preparation and Surface Properties of Silicon-Containing Waterborne Polyurethane Functionalized with Fluorine-Containing Acrylate and Micro-Nano Silica

In order to prepare hydrophobic waterborne polyurethane coatings with better performances, the silicon-containing waterborne polyurethane（SiWPU） with functional chain extender hydroxyethyl acrylate（HEA） was prepared first, and then a series of silicon＆fluorine-containing polyurethane/acrylate（FSiPUA） emulsions were obtained with flourine containing acrylic monomer by seed emulsion polymerization, introducing micro-nano SiO2 into FSiPUA emulsion to make the final hybrid emulsion. The properties of Si WPU, FSiPUA and SiO2/FSiPUA were investigated by fourier transform infrared spectra（FTIR）, transmission electron microscope（TEM）, Scanning Electron Microscope（SEM） and some other analytical methods. The results revealed that FSiPUA emulsion particles possessed composite core-shell structure and FSiPUA films with suitable ratio performed better than Si WPU films in hardness, water resistance and solvent resistance. The SiO2/FSiPUA films with micro-nano dual roughness structure showed a water contact angle of 136° with good resistance to acid and alkali.

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.

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.

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.

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.

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.

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.

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.