Hydrolyzed Polymaleic Anhydride Research Articles

Kilogram scale facile synthesis and systematic characterization of a Gd-macrochelate as T1-weighted magnetic resonance imaging contrast agent

To overcome the problems of commercial magnetic resonance imaging (MRI) contrast agents (CAs) (i.e., small molecule Gd chelates), we have proposed a new concept of Gd macrochelates based on the coordination of Gd3+ and macromolecules, e.g., poly(acrylic acid) (PAA). To further decrease the r2/r1 ratio of the reported Gd macrochelates that is an important factor for T1 imaging, in this study, a superior macromolecule hydrolyzed polymaleic anhydride (HPMA) was found to coordinate Gd3+. The synthesis conditions were optimized and the generated Gd-HPMA macrochelate was systematically characterized. The obtained Gd-HPMA29 synthesized in a 100 L of reactor has a r1 value of 16.35 mM−1 s−1 and r2/r1 ratio of 2.05 at 7.0 T, a high Gd yield of 92.7% and a high product weight (1074 g), which demonstrates the feasibility of kilogram scale facile synthesis. After optimization of excipients and sterilization at a high temperature, the obtained Gd-HPMA30 formulation has a pH value of 7.97, osmolality of 691 mOsmol/kg water, density of 1.145 g/mL, and viscosity of 2.2 cP at 20 ℃ or 1.8 cP at 37 ℃, which meet all specifications and physicochemical criteria for clinical injections indicating the immense potential for clinical applications.Graphical

Anti-scale performance degradation of carboxylic acid scale inhibitors under corrosion conditions

The anti-scale performance of two typical carboxylic acid scale inhibitors, hydrolyzed polymaleic anhydride (HPMA) and polyaspartic acid (PASP), was investigated under different corrosion conditions of carbon steel. It reveals that steel corrosion induces the anti-scale performance degradation of the carboxylic acid scale inhibitors at steel-water interface, due to the preferential chelation of Fe2+ and carboxylic acid group. The anti-scale performance of scale inhibitor can be fully exerted when corrosion processes are inhibited. Otherwise, uninhibited cathodic oxygen reduction and anodic iron oxidation will induce interfacial pH rising and chelated Ca2+ being replaced, respectively, leading to CaCO3 deposition on steel surface.

Phosphorus recovery from incinerated sewage sludge ash using electrodialysis coupled with plant extractant enhancement technology

Phosphorus (P) is an integral mineral nutrient for the growth of plants and animals. As the increasing population worldwide, the demand for P resources keeps increasing. Therefore, it is necessary to recover P from secondary resources. Unlike conventional P recovery processes, this work focused on the recovery of P from incinerated sewage sludge ash (ISSA) using electrodialysis as the main technology coupled with plant extractants. In this study, Amaranthus and hydrolyzed polymaleic anhydride (HPMA) were used as P extractants, investigating the effects of HPMA concentration and pH of the compound agent on the migration of P and heavy metals from ISSA. The results showed that the concentration of HPMA and pH of the compound agent had a significant influence on the mobility of P and heavy metals. Meanwhile, the impacts of eggshell additions and voltage on the recovery efficiency of P was also studied by using waste eggshells as calcium sources. We found that when eggshells were added at 10 g/L and the voltage was 10 V, the recovery efficiency of P reached 96.05%. Moreover, XRD patterns revealed that the mineral phase of recovered P-containing products was predominantly hydroxyapatite, which had good environmental benefits. Generally, the favorable results have been achieved in the recovery efficiency of P and has practical implications for P recovery from ISSA.

Effects of hydrolyzed polymaleic anhydride addition combined with vermicomposting on maturity and bacterial diversity in the final vermicompost from the biochemical residue of kitchen waste.

A large amount of kitchen waste is produced all over the world. Biochemical disposal is an effective method for the reduction and safe utilization of kitchen waste. However, high salinity, low maturity and poor biocompatibility were encountered when utilizing the biochemical residue of kitchen waste (BRKW) as a kind of soil amendment. To reduce the high salinity, accelerate the maturity and improve the biocompatibility in the BRKW, this study used the BRKW as the main feedstock for earthworms after hydrolyzed polymaleic anhydride (HPMA) was added and focused on revealing the effect of HPMA addition combined with the vermicomposting process on the growth of earthworms and on the basic physicochemical properties and the microbial diversity of the derived vermicompost. The results showed that HPMA addition can promote earthworm growth and reproduction. The pH, electric conductivity, organic matter content, C/N and NH4+-N/NO3--N were decreased in the final vermicompost, while total nitrogen, total phosphorus and total potassium contents, and the seed germination index were increased. Scanning electron microscopy analysis showed that there was more disintegration in the final vermicompost. Meanwhile, adding the HPMA also helped to decrease the total number of fungi while increasing the populations of nitrogen-fixing bacteria, phosphorus-solubilizing bacteria and potassium-solubilizing bacteria as well as amount of total bacteria and actinomycetes. The vermicomposting process increased the bacterial phyla that promote the degradation of OM, such as Actinobacteria, Firmicutes and Acidobacteria, decreased the pathogenic Enterobacter and increased the bacterial genera that promote the maturity and quality, such as Cellvibrio and Pseudomonas. Thus, HPMA addition combined with vermicomposting can promote the growth of beneficial bacteria that promote the degradation of lignocelluloses and accelerate maturity while inhibiting some potential bacterial pathogens, which helps guarantee the safety of vermicomposting products from BRKW. Hence, employing HPMA to promote BRKW vermicomposting can possibly reduce salt content and improve the maturity and biocompatibility of the final vermicompost. This approach may help realize the safe utilization of BRKW and further promote the biochemical disposal of kitchen waste.

The inhibitory effects of four inhibitors on the solution adsorption of CaCO3 on Fe3O4 and Fe2O3 surfaces

This study presents the inhibitory effects of four scale inhibitors, including polyacrylic acid (PAA), hydrolyzed polymaleic anhydride (HPMA), polyepoxysuccinic acid (PESA) and polyaspartic acid (PASP), on the adsorption of CaCO3 on the surfaces of Fe3O4 and Fe2O3. Samples were characterized using SEM and EDS and the average atomic number ratios of Ca/Fe were calculated. Inhibition effects followed the trend: PESA > PAA > PASP > HPMA and PESA > PASP > HPMA > PAA for Fe3O4 and Fe2O3, respectively. Molecular dynamics simulations based on the adsorption model of the scale inhibitor on the surface and calculations of the adsorption energy between the scale inhibitor molecule and the surface revealed that the relatively high scale inhibitory effect is due to low adsorption energy between the inhibitor molecule and the surface. Density Functional Theory (DFT) calculations of the model after adsorption revealed that the relatively low adsorption energy depends on the number of H-O bonds formed as well as those with higher Mulliken population values between the scale inhibitor and the surface.

The inhibition effect mechanisms of four scale inhibitors on the formation and crystal growth of CaCO3 in solution

The experimentation, molecular dynamics simulation and DFT calculation were used to study the inhibition effects of four scale inhibitors, including polyacrylic acid (PAA), hydrolyzed polymaleic anhydride (HPMA), polyepoxysuccinic acid (PESA) and polyaspartic acid (PASP), on formation and crystal growth of CaCO3 in solutions. According to concentrations of Ca2+ in solutions, the sequence of inhibition effects of scale inhibitors on formation of CaCO3 in the solution was PESA > PASP > HPMA > PAA. Characterization of CaCO3 crystals by XRD and a laser particle size analyzer indicated that the sequence of inhibition effects of scale inhibitors on crystal growth of CaCO3 in solutions was PESA > HPMA > PASP > PAA. Interaction energies between the scale inhibitor molecule and Ca2+, and between the scale inhibitor molecule and the CaCO3 (104) surface indicated that the difference of the inhibition effects was derived from the difference in the interaction energy. The results of DFT calculation indicated that the difference between the interaction energies of these inhibitors and Ca2+ was derived from differences of number and the Mulliken population values of the chemical bonds which formed between the inhibitor molecule and Ca2+ and between the inhibitor molecule and the CaCO3 surface.

Evaluation of maleic acid‐based copolymers containing polyoxyethylene ether as inhibitors for CaCO3 scale

ABSTRACTPolymer scale inhibitors have been widely used to reduce the loss caused by mineral scaling in circulating cooling water systems. In this article, four maleic acid‐based copolymers [hydrolyzed polymaleic anhydride (HPMA)‐AEO] containing different fatty alcohol polyoxyethylene ether (such as AEO‐9, AEO‐10, AEO‐15, and AEO‐20) are prepared by the way of free‐radical copolymerization and characterized using Fourier transform infrared (FTIR), 1H NMR, and gel permeation chromatographic (GPC) techniques. The effects of HPMA‐AEO on CaCO3 scale are studied in several aspects (such as dose, Ca2+ concentration, temperature, inhibition time, pH, the ratio of EO:carboxyl, and the relative supersaturation of CaCO3 solution) by static experiments. The CaCO3 scaling process with dosing of HPMA‐AEO‐9 is investigated under dynamic tests. CaCO3 deposits and precipitate in the presence of HPMA‐AEO‐9 are analyzed using scanning electronic microscope (SEM) and X‐ray diffraction (XRD). The results show that the performance of HPMA‐AEO against CaCO3 scale highly depends upon the ratio of EO:carboxyl; the introduction of AEO group can significantly improve the performance of HPMA‐AEO to tolerate high alkalinity, high hardness, and high temperature; the presence of HPMA‐AEO‐9 can obviously affect the CaCO3 scaling process on the tube wall through interfering with nucleation process and crystal growth process and significantly alter the surface morphology and crystal form of CaCO3 deposits. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47470

Effect of optimized three-component antiscalant mixture on calcium carbonate scale deposition.

The mixture of 1-hydroxyethane-1,1-diphosphonic acid (HEDP), and polyacrylic acid (PAA) and synthesized hydrolyzed polymaleic anhydride (HPMA) was optimized by using simplex lattice of Design-Expert software through calcium carbonate precipitation method. The optimum mass ratio of HEDP, PAA and synthesized HPMA was obtained at 10/10/80, which showed excellent performance on controlling calcium carbonate deposition. The antiscale efficiency of the optimum mixture was 84% and 95%, respectively, in the calcium carbonate precipitation test and the calcium carbonate scale deposit test. The optimum mixture could disturb the crystal growth of calcium carbonate and then affect the morphology and crystal structure of the calcium carbonate precipitates.

Molecular dynamics simulation on the interaction between polymer inhibitors and anhydrite surface

Investigation on the microscopic interaction between polymer inhibitors and calcium sulfate will be helpful for understanding its scale inhibition mechanism and can provide a theoretical guidance to developing new scale inhibitors. In this work, molecular dynamics simulations with COMPASS force field have been performed to simulate the interaction between hydrolyzed polymaleic anhydride (HPMA), polyaspartic acid (PASP), polyepoxysuccinic acid (PESA), polyacrylic acid (PAA) and the (001) and (020) surfaces of anhydrite (AD) crystal with and without water. The results show that the sequence of binding energies between four polymer inhibitors and AD (001) and (020) with water is PESA > PASP > HPMA > PAA. The binding energy of the same polymer inhibitor on AD (001) is smaller than that on AD (020). Water molecules weaken the deformations of HPMA and PAA but aggravate those of PASP and PESA. Natural bond orbital (NBO) charges of the repeat units of polymer inhibitors were calculated by B3LYP/6‐31G* method. The Coulomb interaction is formed between the O atoms of polymer inhibitors and the Ca atoms of AD crystal. The system of polymer–AD is mainly contributed from the non‐bonding interaction. Polymer inhibitors do not interact directly with AD crystal, but indirectly through the interactions between inhibitor–H2O and H2O–AD, i.e. water molecules participate in scale inhibition of polymer inhibitors to AD crystal. Water molecules cannot be ignored when the interaction models are constructed, i.e. solvent effect cannot be ignored. Copyright © 2015 John Wiley & Sons, Ltd.

中国东北肇东盐碱土壤中水溶性胶体的研究

近来的研究结果显示土壤中的水溶性胶体可能对营养物质和各种污染物的迁移和转化起到关键作用。然而，目前国内外对土壤中水溶性胶体的系统研究和报道比较少。本文对中国东北肇东盐碱土壤中的水溶性胶体进行了提取和研究。使用了原子力显微镜,X射线衍射法和光电子能谱等技术对获得的水溶性胶体进行了表征。原子力显微镜观察结果显示这些水溶性胶体呈现为较大的片状固体以及粒径范围很广的球体。X射线衍射法和光电子能谱测定表明这些水溶性胶体是由高岭石，伊利石、方解石、石英石所组成。我们同时也对经过水解聚马来酸酐(HPMA)处理后的盐碱土壤中水溶性胶体以及邻近的农业土壤中水溶性胶体进行了测定和比较。测定结果揭示了盐碱环境有利于产生大量不同粒径的胶体而经过水解聚马来酸酐(HPMA)处理的盐碱土壤和农业土壤中则含有较少量的粒径较小的胶体。本研究所得到的结果可加深研究者对盐碱土壤的认识以及水解聚马来酸酐(HPMA)治理盐碱土壤的基本原理。 Recent studies indicated that water-dispersible colloids play important roles in transportation of nutrients and contaminants in soils. However, there are few systematic studies on the water-dis- persible colloids in soil so far. In this study, the water-dispersible colloids in the saline-alkali soils in Zhaodong, northeast of China, were extracted and further characterized by Atomic force microscopy (AFM), X-ray Diffraction (XRD), X-ray photoelectron spectroscopy (XPS). AFM observation indicated that the water-dispersible colloids contain some large plates and many small spherical particles with a wide range of size distribution. XRD and XPS measurement revealed that the wa-ter-dispersible colloids are composed of kaolinite, illite, calcite, quartz and humic acid. The wa-ter-dispersible colloids extracted from the saline-alkali soils pretreated with hydrolyzed polymaleic anhydride (HPMA) and an agricultural soil were also investigated and compared. The differences of the water-dispersible colloids in the saline-alkali soils and agricultural soil implied that the saline-alkali condition facilitate the formation of the large colloids. The present study is very useful for enriching the knowledge of the saline-alkali soils and understanding the reclamation mechanism of HPMA for the saline-alkali soils.

Investigation on defect control for final chemical mechanical polishing of aluminum alloy

In acid final chemical mechanical polishing (CMP) of aluminum alloy, the addition of a small amount of nitric acid (HNO3) is proved to be the effective measure for reducing the orange peel defect due to the protective film produced by HNO3 on aluminum alloy; however, it makes point defects worse. The effect of hydrolyzed polymaleic anhydride (HPMA) on point defects is investigated. HPMA adsorbs on the surface of aluminum alloy first, and the composite film formed by both HPMA and HNO3 is proved to be efficient for controlling both the orange peel and point defects. When the aluminum alloy is polished by the acid original slurry with 0.7 wt% HNO3 and 0.1 wt% HPMA, the roughness of the aluminum alloy surface is low to 0.678 nm.

Molecular dynamics simulation on the interaction mechanism between polymer inhibitors and calcium phosphate

Investigation on the microscopic interaction between polymer inhibitors and calcium phosphate contributes to the understanding of their scale inhibition mechanism. The results obtained may provide a theoretical guidance to developing new scale inhibitors. In this study, molecular dynamics simulations have been performed to simulate the interaction between hydrolyzed polymaleic anhydride (HPMA), polyaspartic acid (PASP), polyepoxysuccinic acid (PESA), polyacrylic acid (PAA) and the (001) and (110) surfaces of hydroxyapatite (HA) crystal with and without water. Results show that the simulations of polymer inhibitors and the (001) surface of HA with water is closer to the actual situation. On the same HA (001), binding energy of four polymer inhibitors with water has the order of HPMA > PASP > PESA> PAA. On the different surface of HA, the binding energy does not vary much between the same polymer and the two surfaces of HA. But, deformation energies of the same polymer with and without water vary widely. Pair correlation function of Ca (HA)-O (-C=O) implies that the Ca-O bonds formed between the calcium atoms of HA crystal and oxygen atoms of the carboxyl groups in polymers, and water molecules change the distances between polymer inhibitors and HA crystal. The system of polymer-HA is mainly contributed by the non-bond interaction. Polymer inhibitors do not interact directly with HA crystal, but indirectly through the interactions between inhibitor–H2O and H2O–HA. Water molecules cannot be ignored when the interaction models are constructed, i.e., solvent effect must be considered.

Preparation and Performance Research of the Environment-Friendly Corrosion and Scale Inhibitor

A new non-phosphorus composite water treatment agent m (PASP) : m (PESA) : m (HPMA) : m (BTA) = 8:12:10:5 was developed from polyaspartic acid (PASP), polyepoxysuccinic acid (PESA), hydrolyzed polymaleic anhydride (HPMA) and benzotriazole (BTA). The performance of corrosion and scale inhibition were evaluated by rotary hanging-piece, electrochemical and bubble experiments. The corrosion testing piece was characterized by SEM. The results show that the new environment-friendly composite water treatment agent has good performance of corrosion and scale inhibition. Further dynamic simulated test also indicates that the water treatment agent meet the use demand of circulating cooling water.

The Preparation and Performance Study of a Phosphate-Free Corrosion/Scale Inhibitor

By using acrylic acid copolymer, sodium citrate, hydrolyzed polymaleic anhydride (HPMA), corrosion inhibitor D and Zn2+ synergist as raw materials, a multi-component phosphate-free corrosion and scale inhibitor was developed. The performance of the composite phosphate-free corrosion and scale inhibitor was evaluated using the rotary hanging sheet corrosion test, the static scale inhibition test and the corrosion electrochemical test. And the surface morphology of the carbon steel was observed by scanning electronic microscope (SEM). Orthogonal experiment results indicated that the optimal mass ratios of amino acid: Zn2+ synergist: HPMA: corrosion inhibitor D: acrylic acid copolymer was 0.5:10:12:1:8. It was also observed that phosphate-free corrosion and scale inhibitor based on an anodic reaction through the electrochemical corrosion experiment, its annual corrosion rate and scale inhibition rate reached 0.0176 mm·a–1 and 98.3%, respectively, showing excellent corrosion and scale inhibition performance.

Study on a Novel Composite Eco-Friendly Corrosion and Scale Inhibitor for Steel Surface in Simulated Cooling Water

The use of organophosphorus inhibitor is diminishing because of its toxic effects on aquatic and other life. In this study, a composite eco-friendly phosphate-free corrosion and scale inhibitor HS has been developed using hydrolyzed polymaleic anhydride (HPMA), sodium gluconate, Zn2+ synergist and sulfamic acid. And the formula ratio of each component is 9:5:4:2. The performance of the corrosion and scale inhibitor was evaluated by weight loss experiment and the static scale inhibition test, respectively. The results indicated that HS had positive corrosion and scale inhibition effect at a dosage of 40 mg.L–1 or higher. Potentiodynamic polarization curves indicated that HS inhibits the corrosion of steel based on controlling the anodic reaction. And the surface morphology of the carbon steel was studied by scan-ning electronic microscope (SEM). The inhibition effects were due to the formation of protective films.

A New Evaluation Method of Scale Inhibitors for Controlling CaCO<sub>3</sub> Scale in Reverse Osmosis System Based on pH Measurement

A new rapid evaluation method of reverse osmosis (RO) scale inhibitors based on pH measurement has been reported. Five scale inhibitors, Amino Trimethylene Phosphonic Acid (ATMP), Hydrolyzed Polymaleic Anhydride (HPMA), GE-Argo, PTP-0100 and TPTO-150, each at the dose of 1 ppm was added for evaluating the performance of CaCO3 scale controlling. Brine pH was the only measured parameter at periodic time intervals. The criterion was that the pH drops, the precipitate occurs. We can compare the efficacy against CaCO3 by calculating the supersaturation value of CaCO3. The test results show that Argo is the best effective inhibitor and HPMA is the worst of all. This method with high sensitivity and accuracy is fit for screening out scale inhibitors before RO dynamic test.

The effect of synthesized hydrolyzed polymaleic anhydride (HPMA) on the crystal of calcium carbonate

Precipitation of calcium carbonate followed by the adhesion of precipitates to equipment surfaces is the main problem of mineral scaling in cooling water systems. Many chemicals and antiscalants have been widely used to mitigate the mineral scaling problems. Hydrolyzed polymaleic anhydride (HPMA) was synthesized and used as antiscalant. The effect of Synthesized HPMA on the crystal of calcium carbonate was investigated through the calcium carbonate precipitation experiments. The synergetic effect of synthesized HPMA with 1-hydroxyethane-1,1-diphosphonic acid (HEDP) and polyacrylic acid (PAA) was also investigated. It was indicated that the order of the ability to prevent the precipitation of Ca 2+ from bulk solution was HEDP / HPMA / PAA > HEDP ≈ HPMA > PAA. The morphologies and the crystal structure of the precipitates were investigated using Scanning Electron Microscope (SEM) and X-ray Diffractometer (XRD). It was indicated that HPMA could change the morphologies and crystal structures of CaCO 3 precipitates. The irregular framboid spherical shape and vaterite crystal was observed in the presence of HPMA. HEDP and PAA could enhance the effect of synthesized HPMA on the crystal of calcium carbonate. The synthesized HPMA together with HEDP and PAA showed higher antiscale efficiency and synergetic effect on the crystal of calcium carbonate.

MOLECULAR DYNAMICS SIMULATION THE HYDROXYAPATITE SCALE INHIBITION MECHANISM OF WATER-SOLUBLE POLYMERS

Molecular dynamics (MD) method was used to simulate the interaction between water-soluble polymers, such as polyacrylic acid (PAA), polymethylacrylic acid (PMAA), acrylic acid-methylacrylate copolymer (AA-MAE), acrylic acid-hydroxypropyl acrylate copolymer (AA-HPA), hydrolyzed polymaleic anhydride (HPMA), acrylic acid-maleic acid copolymer (AA-MA), and hydroxyapatite crystal. The sequence of binding energies of polymers binding with the (100) crystal surface of hydroxyapatite was as follows: AA-HPA > AA-MA > HPMA > PAA > AA-MAE > PMAA. After analyzing various energy components and pair correlation functions of all systems, it could be concluded that binding energies were mainly determined by Coulomb interaction. Polymers deformed during their combining with the hydroxyapatite crystal, but all the deformation energies were far less than respective nonbond energies. The dynamics behavior of carboxyls located at different positions of the polymer chains manifested different features during the processes of MD runs. Carboxyls at the ends of the polymer chains oscillated more acutely than those in the middle of the chains; therefore, the latter ones inhibited scale crystal growth more effectively than the former ones because they combined with hydroxyapatite crystal more firmly.

Addition of HPMA affects seed germination, plant growth and properties of heavy saline-alkali soil in northeastern China: comparison with other agents and determination of the mechanism

China has a large area of inland saline-alkali land, equivalent to 40% of the total cultivated land in the country. The principal features of these lands are high salt content, high pH, and poor soil structure with low water infiltration and poor drainage. These conditions effectively prevent the exploitation of such land for agriculture. In this study, we have compared 17 soil conditioning agents for their abilities to promote seed germination and growth under both laboratory and field conditions. One of these, Hydrolyzed Polymaleic Anhydride (HPMA), was identified as a highly effective agent for soil improvement. Laboratory germination experiments and laboratory and field cultivation of a variety of plants both showed that addition of HPMA could significantly increase the germination percentage and plant growth rate. Distinct from other Ca-carrier agents such as gypsum, HPMA increases the dissolution of CaCO3, which is abundant in the calcareous saline-alkali soils. This allows Ca2+ in soil solution to displace the over-abundant Na+ in the soil colloids. This process greatly improves soil properties such as the bulk density, which decreased, and the capillary soil rise height of water and soil water infiltration rate, which increased. Direct SEM and AFM imagery showed flocculent soil precipitation (soil aggregates) after HPMA addition, and a looser structure of those aggregates. The addition of HPMA also reduced the soil pH and EC. These changes in soil chemical and physical properties are a likely explanation for the soil improvement effected by HPMA. The high content of insoluble CaCO3 in saline-alkali land such as that in northeastern China (up to 13%) favors the further exploration of HPMA as an ameliorative agent.