Design and Synthesis of Novel Fluorine-containing Acrylates

A series of novel fluorine-containing acrylates 6a-6g were synthesized via the condensation of ethyl cyanoacetate and trifluoroacetic anhydride, followed by chloridization and the coupling reaction with amines. These new compounds exhibited some biological activity as preliminary bioassay indicated. A plausible reaction mechanism was outlined and discussed.

FT-IR Study on Crosslin king Reaction of Acrylates Copolymer Emulsions

Introduction The emulsion of acrylate copolymers with actively functional groups have been widely developed and used as coating, adhesive and handling agent in spinning and weaving industry. Bessett, D. R. et al. studied the thermoset of N-(isobutoxymethyl) acrylamide by thermal evolution analysis and thermal gas chromatogram. Krejcar,

Synthesis of Novel C_(2)-Symmetrical Bidentate Phosphoramidite Ligands for Rh-catalyzed Asymmetric Hydrogenation of β-(Acylamino)acrylates

Two new C2-symmetrical bidentate phosphoramidite ligands were synthesized and employed in the Rh-catalyzed asymmetric hydrogenation of β-（acylamino）acrylates, up to 89% ee with full conversions was obtained.

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.

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.

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.

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.

SEED SEMICONTINUOUS EMULSION MULTI-COPOLYMERIZATION OF (METH) ACRYLATES WITH HIGH-SOLID CONTENT: EFFECT OF THE OPERATION CONDITIONS

The seeded semicontinuous emulsion multi-copolymerization of butyl acrylate (BA), 2-ethylhexyl acrylate (2EHA), methyl methacrylate (MMA), 2-hydroxyl propyl acrylate (HOPA) and acrylic acid (AA) was used to prepare the acrylic latexes with high-solid content. The effects of monomer emulsion feed rates (R(a)) and (R/E)(E) values, the ratio of emulsifier amount between the initial charge (R) and the addition monomer emulsion (E), on the polymerization reaction features, the viscosities, surface tensions,particle sizes and particle sizes distributions of latexes, T-g and the insoluble fractions of films, the 180 degrees peel strength, tack and holding power of pressure-sensitive adhesive (PSA) tapes, prepared from the latexes, were studied. Experimental study shows that the grafting and crosslinking fraction in the PSA tapes must be controlled within a suitable range to keep the balance of the 180 degrees peel strength, tack and holding power.

POLYMERIZATION OF(METH)ACRYLATES WITH ALUMINUM-BASED INITIATORS

A simple and effective way to prepare poly（acrylate）s, such as poly（methacrylate）, poly（butyl acrylate） and poly（butyl methacrylate）, has been achieved by using the single component aluminum-based compounds, such as modified methylaluminoxane （MMAO）, triisobutylaluminium （TIBA） and triethylaluminium （TEA） as initiators. Effective initiations and high molecular weight polymers with unimodal molecular weight distributions could be easily obtained by varying the reaction parameters of systems under mild conditions. Although these aluminum compounds were inefficient initiators for methyl methacrylate （MMA） polymerization, they exhibited remarkable catalytic activity for butyl methacrylate （BMA） polymerization, affording high molecular weight poly（BMA）s.

Bio-rational design of photosystem Ⅱ inhibitors (Ⅷ)——Molecular design, synthesis and inhibitory activity of acrylates (acrylamides)

Molecular modeling of acrylates (acrylamides) with D1 protein of Pisum sativum is presented. Studies show that the binding force mainly includes H-bond interaction, Van der Waals and π-ring stacking interaction. It was found that SER 268 in Dl protein might be an important binding site. It is important for high inhibitory activity of compounds whether an electronegative atom in alkyl of ester linkage could make H-bond interaction with SER 268 in Dl protein. Thus some new acrylates (acrylamides) were designed and synthesized, Bioassay indicated that these new compounds showed expected Hill reaction inhibitory activity.

Direct Three-Component Synthesis of a-Cyano Acrylates Involving Cascade Knoevenagel Reaction and Esterification

A direct three-component approach has been developed for the synthesis of a-cyano acrylates starting from al- dehydes, alcohols and a-cyano acetamide by employing cyanuric chloride as an organocatalyst. A class of structur- ally diverse a-cyano acrylates have been provided with good to excellent yields via the cascade transformation of Knoevenagel condensation and amide esterification.

A novel Ireland-Claisen rearrangement/Diels-Alder tandem reaction of propargylic acrylates with acyclic dienophiles

Received 18 October 2012 Received in revised form 14 December 2012 Accepted 21 December 2012 Available online 29 January 2013

One-pot Sequential Reaction for the Synthesis of Polysubstituted 3-（3-Nitro-2-phenylchroman-4-yl）-3-arylaminoacrylates

The one-pot sequential reaction of arylamines, methyl propiolate and 2-aryl-3-nitrochromenes without any catalyst in refluxing ethanol afforded the polysubstituted 3-（3-nitro-2-phenylchroman-4-yl）-3-arylaminoacrylates in good yields and with high diastereoselectivity. Reaction mechanism was believed involving the initial formation of β-enamino ester and sequential Michael addition.

Diastereoselective Synthesis of Arylidene Bis（3-arylamino- acrylates） via One-pot Domino Reactions

The functionalized arylidene bis（3-arylaminoacrylates） were efficiently prepared by FeCl3 catalyzed one-pot domino reactions of primary amines, methyl propiolate and aromatic aldehydes. When isatins were utilized under similar conditions, only 2-oxoindolinyl 3-arylaminoacrylates were obtained in moderate yields. ^1H NMR data and single crystal structures indicated that this reaction has high diastereoselectivity.

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.

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.

Size-controlled preparation of hollow silica spheres and glyphosate release

Different-sized hollow SiO2 spheres of 249–1348 nm in diameter were successfully prepared by using Na2SiO3 as the precursor and using polystyrene and polystyrene-methyl acrylic acid latexes as the templates. The diameter and shell thickness of the hollow SiO2 spheres increase with increasing the latex template diameter at a given mass ratio of SiO2 to latex template. The diameter and shell thickness of the hollow SiO2 spheres also increase with increasing the mass ratios of SiO2 to latex template. The presence of carboxylic acid groups on the surfaces of polystyrene-methyl acrylic acid latex templates favors the formation of dense and uniform SiO2 shells. The hollow SiO2 sphere is constructed by mesoporous shell with large specific surface area. When glyphosate is used as a release model chemical, glyphosate release rate is tuned by varying the shell thickness.

Incorporation of Reactive Corrosion Inhibitor in Waterborne Acrylic Polyurethane Coatings and Evaluation of its Corrosion Performance

Hydroxyl-epoxy phosphate （HEP） as a reactive corrosion inhibitor was innovatively synthe- sized by the reaction of bisphenol A epoxy resin with phosphoric acid. HEP was mixed with hydroxyl acrylate resin, and crosslinked with waterborne isocyanate curing agent, which was used to form waterborne HEP/acrylic polyurethane composite （HEP-APU） coatings on Q235 steel surfaces. Electrochemical impedance spectroscopy and polarization curves were applied to analyze the corrosion behavior of the HEP-APU coatings in 3.5wt% NaCl solutions. The results indicated that the HEP-APU coatings show a superior passivation property and efficient corrosion protection of Q235 steel. The waterborne acrylic polyurethane coating containing 0.5wt% HEP exhibited the best corrosion performance among all the coating specimens. The improved flash-rust resistance can be attributed to the introduction of the phosphate group which could form phosphate film on the steel substrate.