EFFECTS OF ω-ACRYLOYL POLY (ETHYLENE OXIDE) MACROMONOMER ON EMULSIFIER-FREE EMULSI0N COPOLYMERIZATION OF METHYL METHACRYLATE AND n-BUTYL ACRYLATE

Well-defined nonionic hydrophilic ω-acryloyl poly(ethylene oxide) macro-monomer (PEO-A) has been prepared by living anionic polymerization of ethylene oxidewith diphenyl methyl potassium as the initiator and acryloyl chloride as the reaction termi-nating agent. The polymer was characterized by FTIR and SEC. The emulsifier-free emul-sion polymerization of methyl methacrylate (MMA) and n-butyl acrylate (BA) containingvarious concentrations of PEO-A was studied. In all cases stable emulsion coplymerizationsof MMA and BA were obtained. The stabilizing effect was found to be dependent on themolecular weight and the feed amount of the macromonomer.

Effects of Branches on the Crystallization Kinetics of Polypropylene-gPolystyrene and Polypropylene-g-Poly(n-butyl acrylate) Graft Copolymers with Well-defined Molecular Structures

Effects of branches on the crystallization kinetics of polypropylene-g-polystyrene （PP-g-PS） and polypropylene-g- poly（n-butyl acrylate） （PP-g-PnBA） graft copolymers with well-defined molecular structures were systematically investigated by DSC. The Avrami equation was used to analyze the isothermal crystallization process, while the analysis of nonisothermal crystallization process was based on the Jeziorny-modified Avrami model and Mo model. The kinetics results of isothermal and nonisothermal crystallization verified the peculiar effects of branches on the crystallization process of PP backbones in PP-g-PS and PP-g-PnBA graft copolymers： on one hand, the interaction between branches （n-n interaction between PS branches, or dipole-dipole interaction between PnBA branches） restrained the mobility and reptation ability of the PP backbones, which hindered the crystallization process; on the other hand, the heterogeneous nucleation effect resulting from the branched structure and fluctuation-assisted nucleation mechanism （caused by microphase separation between the PS or PnBA rich phase and the PP rich phase） became more pronounced with increasing branch length, which facilitated the crystallization process.

Magnesium hydroxide whisker modified via in situ copolymerization of n-butyl acrylate and maleic anhydride

Magnesium hydroxide(MH) whiskers were modified via in situ polymerization of n-butyl acrylate and maleic anhydride. Sodium dodecyl sulfonate was used as emulsifier. The modifying effect was evaluated by using contact angle and activation index. The thermal stability,functional groups, structure, morphology, phase composition and surface element valence of MH whiskers were characterized by thermogravimetry-differential scanning calorimetry(TG-DSC), Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD), scanning electron microscopy(SEM) and X-ray photoelectron spectroscopy(XPS). Results reveal that the contact angle and activation index of modified MH whiskers are 105°and 76.5%, the thermal stability shows little change, and the decomposition temperature ranges between 38 and419 ℃. The copolymer of n-butyl acrylate and maleic anhydride absorbed on the surface of MH whiskers leads to the increased diameter and makes the surface of whiskers be rougher. Furthermore, the absorption of element C on the surface of MH whiskers increases, and the diffraction intensity of C 1 s spectra increases; thus, the compatibility of whiskers in the organic phase can be improved significantly. Lastly, the surface molecular model of MH whiskers modified via in situ copolymerization of n-butyl acrylate and maleic anhydride is established.

Prevalence of gastric varices and results of sclerotherapy with N-butyl 2 cyanoacrylate for controlling acute gastric variceal bleeding

AIM： To study the prevalence, predictors and control of bleeding following N-butyl 2 cyanoacrylate （NBC） sclerotherapy of gastric varix （GV）. METHODS： We analyzed case records of 1436 patients with portal hypertension, who underwent endoscopy during the past five years for variceal screening or upper gastrointestinal （GI） bleeding. Fifty patients with bleeding GV underwent sclerotherapy with a mean of 2 mL NBC for control of bleeding. Outcome parameters were primary hemostasis （bleeding control within the first 48 h）, recurrent bleeding （after 48 h of esophagogastro-duodenoscopy） and in-hospital mortality were analyzed. RESULTS： The prevalence of GV in patients with portal hypertension was 15% （220/1436） and the incidence of bleeding was 22.7% （50/220）. Out of the 50 bleeding GV patients, isolated gastric varices （IGV-Ⅰ） were seen in 22 （44%）, gastro-oesophageal varices （GOV） on lesser curvature （GOV-Ⅰ） in 16 （32%）, and GOV on greater curvature （GOV-Ⅱ） in 15 （30%）. IGV-Ⅰ was seen in 44% （22/50） patients who had bleeding as compared to 23% （39/170） who did not have bleeding （P 〈 0.003）. Primary hernostasis was achieved with NBC in all patients. Re-bleeding occurred in 7 （14%） patients after 48 h of initial sclerotherapy. Secondary hemostasis was achieved with repeat NBC sclerotherapy in 4/7 （57%）. Three patients died after repeat sclerotherapy, one during transjugular intrahepatic portosystemic stem shunt （TIPSS）, one during surgery and one due to uncontrolled bleeding. Treatment failure-related mortality rate was 6% （3/50）. CONCLUSION： GV can be seen in 15% of patients with portal hypertension and the incidence of bleeding is 22.7%. NBC is highly effective in controlling GV bleeding. In hospital mortality of patients with bleeding GV is 6%.

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.

Percutaneous transcatheter super-selective renal arterial embolization with N-butyl cyanoacrylate for iatrogenic renal hemorrhage

Background:To evaluate the safety and efficacy of percutaneous transcatheter super-selective renal arterial embolization(SRAE)with N-butyl cyanoacrylate(NBCA)for iatrogenic renal hemorrhage.Methods:Between January 2014 and December 2019,45 patients(including 18 patients with coagulopathy),who underwent percutaneous transcatheter SRAE with NBCA for iatrogenic renal hemorrhage at our institution,were retrospectively reviewed.The technical success rate,clinical success rate,and embolization-related complications were analyzed.The values of estimated glomerular filtration rate(eGFR),serum creatinine(sCr),and serum urea(sUr)were analyzed at the time of pre-SRAE,post-SRAE,and last follow-up to evaluate the effects of NBCA-based SRAE on renal function.Results:Diagnostic renal arteriography revealed contrast extravasation in 18 patients and pseudoaneurysms in 27 patients.NBCA mixed with iodized oil in a 1:2–1:4 ratio was the sole embolic agent.No procedure-related mortality or major complications occurred.The technical and clinical success rates were both 100%.The values of eGFR,sCr and sUr were not found to be significantly different between pre-SRAE,post-SRAE and last follow-up(eGFR:91.52±21.17 vs.90.98±22.11 vs.92.14±23.51 mL/min/1.73 m^(2),p=0.729;sCr:74.73±11.08 vs.75.27±12.43 vs.73.95±10.14μmol/L,p=0.543;sUr:5.69±0.84 vs.5.71±0.96 vs.5.70±0.79,p=0.515,respectively).Conclusions:Percutaneous transcatheter SRAE with NBCA is a safe and effective treatment modality for iatrogenic renal hemorrhage with no deterioration of renal function.

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. .

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.

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.

Controlled Radical Photopolymerization of n-Butyl Methacrylate in Bluk Mediated by HTEMPO

Controlled radical photopolymerization of n-butyl methacrylate（n-BMA） mediated by 4-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy（HTEMPO） was carried out in bulk at ambient temperature. It was found that obtained n-BMA homopolymers exhibited narrow polydispersities of around 1.4, which was characterized by GPC. Plots of number-average molecular weight vs. conversion and Ln（[Mo]/[M]） vs. time were liner respectively, indicating that was a controlled photopolymerization.

Effect of Oxygen on Surface Properties and Drug Release Behavior of Plasma Polymer of n-Butyl Methacrylate

The effects of oxygen on the chemical structure, morphology, hydrophilicity and drug release behavior of radio-frequency plasma poly n- butyl methacrylate （PPBMA） thin film were carded out for the first time. ATR-FTIR and XPS showed that oxygen had little influence on the chemical structure and composition of PPBMAs, which did not agree with the thought that the presence of oxygen gas would increase the oxidized carbon functionalities in the plasma polymer. SEM and static contact angle measurement indicated that in case of deposition with oxygen, the smoothness and hydrophilicity of PPBMA were dramatically improved. The drug release behavior showed that drug release from the PPBMA coating without oxygen was biphasic patterns, while from PPBMA coating with oxygen was Higuchi release. These results were helpful for the design and tailoring of the PPBMA polymer film and other of plasma polymers film, but could provide a new idea for the drug release controlled form.

Safety of bronchial arterial embolization with n-butyl cyanoacrylate in a swine model

AIM: To compare the efficacy and safety of bronchial artery embolization (BAE) with n-butyl cyanoacrylate (NBCA) and gelatin sponge particles (GSPs). METHODS: Six healthy female swine were divided into two groups to be treated with BAE using NBCA-lipiodol (NBCA-Lp) and using GSPs. The occlusive durability, the presence of embolic materials, the response of the vessel wall, and damage to the bronchial wall and pulmonary parenchyma were compared. RESULTS: No animals experienced any major complication. Two days later, no recanalization of the bronchial artery was observed in the NBCA-Lp group, while partial recanalization was seen in the GSP group. Embolic materials were not found in the pulmonary artery or pulmonary vein. NBCA-Lp was present as a bubble-like space in bronchial branch arteries of 127-1240 μm, and GSPs as reticular amorphous substance of 107-853 μm. These arteries were in the adventitia outside the bronchial cartilage but not in the fine vessels inside the bronchial cartilage. No damage to the bronchial wall and pulmonary parenchyma was found in either group. Red cell thrombus, stripping of endothelial cells, and infiltration of inflammatory cells was observed in vessels embolized with NBCA-Lp or GSP. CONCLUSION: NBCA embolization is more potent than GSP with regard to bronchial artery occlusion, and both materials were present in bronchial branch arteries≥100 μm diameter.

High-gravity technology intensified Knoevenagel condensation-Michael addition polymerization of poly (ethylene glycol)-poly (n-butyl cyanoacrylate) for blood-brain barrier delivery

Poly(ethylene glycol)-poly(n-butyl cyanoacrylate)(PEG-PBCA)is a remarkable drug delivery carrier for permeating blood-brain barrier.In this work,a novel high-gravity procedure was reported to intensify Knoevenagel condensation-Michael addition polymerization of PEG-PBCA.A series of PEG-PBCA containing different block ratios were synthesized with narrow molecular weight distribution of polydispersity indexes less than 1.1.Furthermore,the reaction time reduced 60%compared to conventional stirred tank reactor process.Chemical structures of as-prepared polymers were characterized.In vitro drug delivery performance was evaluated.The cytotoxicity of PEG-PBCA to brain microvessel endothelial cells(BMVEC)decreases with the extension of the PEG chain and the shortening of the PBCA chain.The polymer cellular uptake to BMVECs was better after improving hydrophilicity by PEG block.Results of bloodbrain barrier permeability demonstrated that medium length of PBCA chain and short PEG chain are favorable for hydrophobic Nile red permeation,while long PEG chain and short PBCA chain are beneficial to delivery water-soluble doxorubicin hydrochloride(Dox).The average apparent permeability coeffi-cient increased 1.7 and 0.25 times than that of raw Nile red and Dox,respectively.High-gravity intensi-fied condensation polymerization should have great potential in brain drug delivery system.

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.

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.

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.

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.

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.