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.

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.

Kinetics and Mechanism of Hydration of Acrylic Acid over Ion-exchanged Resin:Experimental Exploration and DFT Calculation

Liquid-phase acrylic acid hydration over solid-phase catalysts is a key reaction for the industrial productionof 3-hydroxypropionic acid. However, the relevant literature primarily focuses on the experimental aspects of catalystscreening and exploring reaction conditions, with few accurate descriptions of the reaction kinetics and determination ofthe reaction mechanism. Here, we combined kinetics experiments and theoretical calculations to elucidate the kinetics andmechanism of acrylic acid hydration on a resin catalyst. The pseudo-homogeneous model, and Langmuir-Hinshelwood-Haugen-Watson and Elie-Riedel (ER) heterogeneous models were used to explain the experimental kinetics data. TheER model can explain the experimental data very well, suggesting strong adsorption of acrylic acid on the surface of theresin catalyst. Furthermore, density functional theory calculations show that the hydration follows a stepwise, rather than aconcerted, reaction pathway. The present study provides theoretical insights into the reaction mechanism and kinetics, fillingthe gap in our understanding of the reaction on a fundamental level.

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

By means of initiation of the high temperature and shearing stress of an extruder,we synthesized the graft copolymer of starch with acrylate monomers based on the simple dry method.The effects of reaction conditions on graft copolymerization were discussed. Grafted starch used as a compatibilizer for the blend system of starch and polyethylene was further investigated. The results indicate that grafted starch as a compatibilizer can improve the mechanical properties and rheologic properties of the blend of starch and polyethylene.

The Evaluation of the Dietary Habits Influence on the Microhardness of Gingiva-Coloured Composite and Acrylic Denture Base Materials

Purpose: The study investigated the impact of dietary habits, specifically soda, milk kefir, water kefir, almond milk, and distilled water (control) consumption, on the microhardness of gingiva-coloured composite and acrylic denture bases. Methods: Materials included gingiva-coloured composite (Fusion Universal G1), acrylic (Imicryl), and subdivided Procryla group. Subgroups comprised 15 and 30-minute heat polymerized (Pro15, Pro30), and 1 wt% (Pro1Z) and 3 wt% (Pro3Z) zirconium added groups. Immersed in beverages for 1, 7, and 14 days, pH and microhardness were assessed. SEM examined random samples. Statistical analysis used repeated measures ANOVA, and post hoc tests (p Results: The gingiva-coloured composites displayed noteworthy time-associated microhardness changes (p 0.05). Despite variable pH levels in beverages, no substantial group interaction effects were observed (p > 0.05). Initial microhardness rankings shifted after a 14-day immersion. Conclusions: Gingiva-coloured composite exhibited the highest microhardness pre- and post-immersion, followed by Procryla30 and Imicryl groups. .

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.

MODIFICATION OF POLYETHYLENE BY in situ FORMED SODIUM ACRYLATE

To improve the water tree resistance of PE, linear low-density polyethylene （LLDPE） was compounded with sodium acrylate （NaAA） for in situ polymerization, in which NaAA was fbrmed through the neutralization of acrylic acid （AA） with sodium hydroxide （NaOH） before adding dicumyl peroxide （DCP） to initiate the in situ graft polymerization and homo polymerization. A series of LLDPE/NaAA compounds were investigated for their water absorption ratio （WAR） measurement, water treeing, mechanical and dielectric properties. The results strongly suggest that NaAA can improve the water tree resistance of LLDPE. In addition, the LLDPE/NaAA compounds possess satisfactory mechanical properties and dielectric properties. Characterization of LLDPE/NaAA compounds by using Fourier transform infrared spectrometry （FTIR） suggests that the neutralization and polymerization reaction could be achieved effectively. Using adequate DCP content is the key factor for controlling the polymerization of NaAA with precise conversion ratio.

FREE RADICAL RING OPENING POLYMERIZATION OF CYCLIC ACRYLATES

Cyclic acrylates, 2,2- dimethyl-5-methylene-1 , 3-dioxolan-4 -one and 2- phenyl-5-methylene-1,3-dioxolan-4-one, were synthesized successfully. The monomers were characterized by ~1H NMR, ^(13)C NMR, IR and elemental analysis or HRMS. Polymerization of the monomers were carried out at 120℃ with di-t-butylperoxide as initiator. The polymers were studied by ~1H NMR, ^(13)C NMR, UV and hydrolysis. The molecular weights of the resulting polymers were estimated by viscosity measurement and the extent of ring opening was estimated also by ~1H NMR and hydrolysis of the polymers and further confirmed by UV spectra.

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.

Synthesis and properties of UV curable polyurethane acrylates based on two different hydroxyethyl acrylates

Two kinds of UV curable polyurethane acrylate oligomers （PUPA and PUCA） were synthesized via the addition reaction between isophorone diisocyanate （IPDI） and polyethylene glycol monoacrylate （PEA6） or polycaprolactone modified hydroxyethyl acrylate （PCLA2）. The structures of PUPA and PUCA were characterized by Fourier transform infrared spectroscopy （FT-IR）, IH nuclear magnetic resonance （^H NMR）, gel permeation chromatography （GPC） and differential scanning calorimeter （DSC）, and the thermal stability and dynamic mechanical thermal properties of their cured films were measured by thermogravimetric analysis （TGA） and dynamic mechanical analysis （DMA）, respectively. The viscosity of the oligomers and mechanical properties of the cured films were also studied. The results show that both oligomers have narrow molecular weight distribution. The viscosity of PUPA is 2.310 Pa.s at 25 ℃, while that of PUCA is： up to 3.980 Pa-s. The UV cured PUPA and PUCA films have homogeneous phase structure, and the PUCA film shows higher glass transition temperature and storage modulus. Furthermore, the PUCA film possesses better mechanical properties than PUPA, while the latter shows better alkali resistance.

UV-curing of hyperbranched polyurethane acrylate-polyurethane diacrylate/SiO_2 dispersion and TGA/FTIR study of cured films

UV-curable hyperbranched polyurethane acrylate-polyurethane diacrylate/SiO2 dispersion （HBPUA-PUDA/SiO2） was prepared with isophorone diisocyanate （IPDI）, hyperbranched polyester Boltorn H20 （H20）, hydroxy-ethyl acrylate （HEA）, polyethyleneglycol （PEG-200）and nano-SiO2. The UV curing kinetics of the films was investigated by FTIR. The results show that the curing speed of the films increases with the adding of nano-SiO2 and decreases with the adding of PUDA due to the slower chain movement. The thermal stability of the HBPUA-PUDA/SiO2 films was studied by using thermogravimetric analysis coupled with Fourier transform infrared spectroscopy （TGA/FTIR）. The results show that all films exhibit two degradation stages located at about 320 and 440℃ corresponding to the degradation for hard segments of urethane-acrylate and the degradation for soft segment and polyester core. In addition, the results from the analysis of TGA/FTIR also indicate that the decomposition temperature of HBPUA-PUDA/SiO2 film is 15℃ higher than that obtained for pure polymer. The degradation mechanism was proposed according to TGA/FTIR results.

Evaluation of Catalysts and Optimization of Reaction Conditions for the Dehydration of Methyl Lactate to Acrylates

The production of acrylates from biomass-originated lactic acid is of extraordinary importance, to overcome the increasing worldwide shortage of petroleum. In this study, the catalytic dehydration of methyl lactate over a calcium sulfate catalyst, with various promoters, has been carried out to identify potential catalyst/promoter combinations for acrylate production. The best catalyst for methyl acrylate formation in this study has been calcium sulfate, with cupric sulfate and phosphates as promoters. The optimal mass ratio of m（CaSOa） ： m（CuSOa） ： m（Na2HPO4） ： m（KH2PO4） is 150.0 ： 13.8 ： 2.5 ： 1.2. Effects of carrier gas, reaction temperature, feed concentration as well as contact time on the dehydration of methyl lactate have been investigated. With nitrogen as a carrier gas, a combined yield of acrylic acid and methyl acrylate is 63.9% from 60% （by mass） methyl lactate at 400℃ with 7.7 seconds contact time.

Synthesis and properties of acrylate latex modified by vinyl alkoxy siloxane

Acrylate latex modified by vinyl triisopropoxy silane (C-1706) was synthesized by seeded emulsion polymerization with anionic emulsifier sodium dodecyl sulphonate(SDS) and nonionic emulsifier OP-10 as the multiple emulsifiers at (78±2) ℃. The effects of different factors, such as the emulsifier, C-1706 monomer and its feeding manner on the properties of acrylate latex modified by C-1706 were investigated. The particle size distribution and the structure, the configuration, the weather durability and stain resistance of copolymer latex were characterized by particle size analyzer, Fourier transform infrared spectroscopy (FT-IR), transmission electron microscope(TEM), scanning electron microscope(SEM) and ultraviolet aging instrument respectively. The results show that SDS to OP-10 as multiple emulsifiers can lead to coordinated efficiency, the optimal emulsifier dosage is 2.4%?3.2%(mass fraction), and the mass ratio of SDS to OP-10 is 1?1? 1?2. The seeded emulsion polymerization can effectively introduce a organic-siloxane bonding in a macromolecule inter polymer, and the obtained acrylate latex modified by organic-siloxane possesses narrow distribution of particle size with mean diameter of 51.8?76.6 nm and has the excellent properties in weather durability and stain-resistance especially.

Water-soluble UV curable urethane methyl acrylate coating：preparation and properties

Two kinds of water-soluble and ultraviolet (UV) curable oligomers were synthesized and characterized. The oligomers were evaluated as resins for water-based UV curable coating. The rheology of the two oligomers' aqueous so-lutions was investigated in terms of solid fraction, pH dependence, and temperature dependence. The solutions were found to be Newtonian fluid showing rather low viscosity even at high solid fraction of 0.55. The drying process of the coatings and the properties of the cured coatings were studied by comparing them with water-dispersed UV-curable polyurethane methyl acrylate. It was evident that the water-soluble coating dried more slowly; and that the overall properties were inferior to those of the water-dispersed coating.

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, morphology and mechanical properties of acrylate-modified polyurethane/unsaturated polyester resin graft-IPNs

Acrylate modified polyurethane resin was first synthesized, and interpenetrated with unsaturated polyester resin to form IPNs and gradient IPNs which cured at room temperature. The polymerization process was traced by an IR spectroscopy technique and the simultaneous interpenetrating techniques were determined. The morphology of these IPNs were estimated by TMA and TEM methods. The results indicated that large amount of interpenetrating and entanglement make T g linked up effectively, and domains between two phases can be in nanometre ranges, which changed with composition ratios. The mechanical properties results showed that IPNs varied from elastomeric to plastic materials. It was noteworthy that, with the introduction of modified groups and the formation of graft construction in IPNs, the miscibility in the systems was improved a lot. These further led to the improved mechanical properties of IPNs with elastomer reinforced and plasticizer toughened as well. The reinforced miscibility between the networks can apparently change mechanical property especially for the gradient ones when the materials are elongated.

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.

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.

Gel time of calcium acrylate grouting material

Calcium acrylate is a polymerized grout, and can polymerize in an aqueous solution. The polymerization reaction utilizes ammonium persulfate as a catalyst and sodium thiosulfate as the activator. Based on the theory of reaction kinetics, this study on the relation between gel time and concentration of activator and catalyst showed that gel time of calcium acrylate is inversely proportional to activator and catalyst concentration. A formula of gel time is proposed, and an example is provided to verify the proposed formula.

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.