A novel composite microsphere as a highly efficient absorbent for oils and organic solvents

A novel composite oil‐absorbent microsphere poly(stearyl methacrylate‐co‐butyl acrylate) (PSB)‐SiO₂ was prepared by introducing hydrophobic nano‐silica Aerosil R812 into the suspension polymerization system of stearyl methacrylate and butyl acrylate and was characterized by Fourier transform infrared and scanning electron microscopy energy‐dispersive spectrometer. PSB‐SiO₂ has a loose network structure and exhibits remarkably fast oil absorption speed in relatively high saturated oil absorbency. Besides, PSB‐SiO₂ has good oil retention and reusability. Moreover, the saturated oil absorbencies of PSB‐SiO₂ toward toluene, gasoline, and diesel over water are roughly equivalent to that in pure oil. Owing to its excellent oil absorption performances, PSB‐SiO₂ will find applications in removing oil spills and organic pollutants over water. Copyright © 2016 John Wiley & Sons, Ltd.     

Oil‐absorbent beads containing β‐cyclodextrin moieties: preparation via suspension polymerization and high oil absorbency

A novel type of polymeric beads with high oil absorbency was prepared via suspension polymerization technique. For this purpose, β‐cyclodextrin with vinyl groups (β‐CD‐MA) was first synthesized from β‐cyclodextrin (β‐CD) and glycidyl methacrylate, and identified by FT‐IR and ¹H‐NMR spectroscopy analyses. Suspension polymerizations were carried out with styrene and stearyl acrylate as co‐monomers, β‐CD‐MA as cross‐linking agent, poly(vinylalcohol) as stabilizer and azoisobutyronitrile as initiator, providing polymeric beads in a quantitative yield. The oil‐absorbent beads had a porous structure and exhibited high oil absorbency: 55 times the dry weight in toluene, 52 times in xylene, 75 times in CHCl₃ and 102 times in CCl₄. The novel beads also showed high absorbency toward toluene from a toluene/water mixture, demonstrating the potential applications of such novel oil‐absorbent beads for cleaning organic contaminations from water. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis of reusable macroporous St/BMA copolymer resin and its absorbency to organic solvent and oil

In this paper, a reusable macroporous high oil absorption resin for oil spills was synthesized successfully by suspension copolymerization with styrene and butyl methacrylate as monomers. In the process of suspension copolymerization, a porogenic agent was introduced into the reaction system. Structure and surface morphology of the macroporous resin were characterized by Fourier transform infrared spectrometry, X‐ray photoelectron spectroscopy, and scanning electron microscopy. In addition, effects of different reaction factors on density and particle size of macroporous resins and effects of various factors on the oil absorbency of macroporous resins were discussed. Furthermore, oil absorption kinetics and repeatability of resin and the absorbency of the macroporous resin in various oils were also studied. Compared with the resin without macroporous structure, the maximum oil absorbency of the macroporous resin to the carbon tetrachloride (CCl₄) was 28.28 g/g, which increased by 61.42%. Meanwhile, the saturated oil absorption time of resin also decreased significantly from 7.5 to 2 hr. The macroporous high oil absorption resin presents predominant performance of reuse and regeneration. Moreover, the macroporous resin had certain absorbency (8.7 g/g) to crude oil, which makes it useful for marine oil spill. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis of high oil‐absorption resins of poly(methyl methacrylate‐butyl methacrylate) by suspended emulsion polymerization

The synthesis of high oil‐absorption resins by suspended emulsion polymerization process for the first time with butyl methacrylate (BMA) and short‐chain methyl methacrylate (MMA) as the monomers was studied. And the effects of different polymerization technological parameters, such as the comonomer, initiator, crosslinker, emulsifier, dispersant agent, and the agitation rate, on the oil absorbency of high oil‐absorption resins were discussed in detail. The optimum polymerization conditions were obtained. With the increasing contents of these factors, the oil absorbency increased first, and then decreased. The highest oil absorbency to toluene was 17.6 g/g. The particle morphology of the high oil‐absorption resins was observed by scanning electron microscopy (SEM). The resins were determined by FTIR spectrometry. Compared with the high oil‐absorption resins prepared by suspension polymerization process and emulsion polymerization process, the high oil‐absorption resins prepared by suspended emulsion polymerization process had the higher oil absorbency, faster oil‐adsorbing rate, better oil‐retention, and regeneration property. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis,characterization, and evaluation of polymeric oil sorbent for remediation of hydrocarbons spillage

The preparation and evaluation of polymeric oil sorbent based on styrene acrylate ester and ethylhexyl acrylate (EHA) are the main target of this work. In this respect, poly styrene-co-p-chloromethyl styrene (PSCMS) was synthesized through radical copolymerization of p-CMS with styrene in the presence of benzoyl peroxide initiator. Then, the PSCMS was reacted with acrylic acid to produce macromonomer containing polymerizable C?C poly {styrene-co-[4-(methyl acrylate) styrene]} (PSSMA) that subsequently copolymerized with EHA in the presence of a cross-linker to obtain the cross-linked copolymers PSSMA/EHA (organogel). The prepared compounds were characterized by using FTIR, ¹H NMR, and gel permeation chromatography. The thermal properties of the cross-linked oil absorbents were investigated using thermogravimetric analysis, and the morphology was characterized by scanning electron microscope (SEM). The oil absorbency of oil gel was determined through oil absorption tests; the highest oil absorbencies of oil gel were found to be 82.6, 74.4, 46.7, and 38.1 g/g in N,N-dimethyl formamide, CHCl₃, toluene, and diesel, respectively.     

Super-hydrophobic carrageenan cross-linked graphene sponge for recovery of oil and organic solvent from their water mixtures

A novel ultra-light, superhydrophobic graphene based carrageenan sponge (GCS) absorbent was synthesized by one pot hydrothermal method, for the use of selective adsorption of oils and organic solvents from their water mixtures. The GO nanosheets were reacted in the presence of formaldehyde by the insertion of carrageenan, forming hydrophobic cross-linked structure in between them. The structure and properties of this GCS are well characterized by Fourier transform infrared spectroscopy, X-ray diffraction, Thermal gravimetric analysis, Scanning electron microscopy, and Water contact angle. The as-prepared GCS has good thermal stability (400 °C), low density (20 mg/cm⁻³), excellent hydrophobicity (water contact angle of 136.24°), and selective absorption capacity (25.2–35.95 g/g) of oils and organic solvents from their water mixtures. GCS has excellent oil sorption capacity in the range of 25.2–50 g of oil per gram of adsorbent. GCS could be easily reused by simple solvent treatment. Therefore, the adsorption capacity still retained even after 10 cycles. The present work suggests that GCS using biobased resources has high potentials for many widespread applications in industry to control environmental pollution.     

Preparation and morphology control of three‐dimensional interconnected microporous PDMS for oil sorption

This study described an approach to impart controlled morphology and improved pore interconnectivity to poly(dimethylsiloxane) (PDMS) sponges for oil sorption by partially fusing the sugar particles together prior to creation of a continuous PDMS matrix. PDMS sponges with high absorption capacity, low water pickup, and remarkable reusability were fabricated by the polymerization of the PDMS prepolymer and a curing agent in cyclohexane. The PDMS sponge showed oil absorbency in the range from 790% to 4000% for various oils solvents, with the maximum absorption capacity reaching up to 23 times of its weight. Compressive modulus of PDMS subjected to sugar fusion for 24 hr was significantly increased to 1900 Mpa. The sponge also exhibited excellent repellency to corrosive strong acid and alkali. Besides, oil can be quickly adsorbed in tens of seconds and maintained for several months. Furthermore, PDMS sponges showed little loss of their absorption capacities and owned weights after 20 absorbing/recovering cycles. Copyright © 2015 John Wiley & Sons, Ltd.     

链转移剂对ST-AA-AM吸水剂吸水性能的影响

分别以抗坏血酸、甲酸、亚硫酸氢钠、异丙醇为链转移剂,研究了不同的链转移剂对淀粉―丙烯酸―丙烯酰胺(ST-AA-AM)吸水剂吸水性能的影响。实验结果表明:异丙醇、甲酸、亚硫酸氢钠、抗坏血酸用量分别为单体总质量的0.0375%、0.045%、0.075%、0.01%时,吸水率分别为498.1 g/g、347.9 g/g、549.0 g/g、407.7 g/g。将链转移剂进行复配,亚硫酸氢钠与异丙醇复配的效果最佳,当复合链转移剂用量占单体总质量的0.08%,异丙醇/亚硫酸氢钠(质量比)=1∶2时,吸水剂的吸水率最高,为653.5 g/g。     

同时吸附油和六价铬离子复合材料的制备及性能

以亲油疏水型三元乙丙橡胶(EPDM)作为基体, 焙烧Fe2O3和阴离子交换树脂201Х7作为填料, 利用熔融共混的方法, 制备一种可以同时吸附油和六价铬离子的用于污水处理的复合材料, 这种材料能够悬浮于油水界面处. 当焙烧Fe2O3和阴离子交换树脂的用量比例不同时, 材料吸附性能变化很大. 实验结果表明, 在保证复合材料密度介于油水密度之间的前提下, 随着焙烧Fe2O3含量的增加, 材料的吸油性能不断增大; 随着阴离子交换树脂含量的增加, 材料对六价铬的吸附性能不断增加. 在油水共存体系中, 复合材料对两种污染物的吸附率同时达到最佳时, 两种填料的比例可以确定, 因油品的不同而不同. 在油水共存体系中, 复合材料对油和六价铬的总吸附能力要远大于复合材料分别在单一吸附介质中的吸附能力.     

Hybridization of Al2O3 microspheres and acrylic ester resins as a synergistic absorbent for selective oil and organic solvent absorption

In this study, we have focused on the synthesis, characterization, and oil absorption properties of Al₂O₃ microspheres/acrylic ester resin (AER) hybrids. The Al₂O₃ microspheres are prepared by a combined hydrothermal and sintering processes, followed by surface modification with silane coupling agent (KH 570). The Al₂O₃ microspheres/AER hybrids with a rough surface are synthesized by a microwave polymerization route by using modified Al₂O₃ microspheres as modifiers. In this hybrid materials system, the Al₂O₃ microspheres with porous structures may provide fast oil absorption due to the low oils absorption energy and short diffusion lengths. The resin hybrids exhibited reversible oils and organic solvents adsorption with maximum absorption capacities up to 29.85 g/g. This study suggests potential environmental advantage in using metal oxide microspheres in improving the oil absorption properties of oil‐absorbing resins as absorbents for recovering oil and organic solvent from water.     

氧化淀粉基高吸水性树脂的制备及表征

以过硫酸铵为引发剂,N,N’-亚甲基双丙烯酰胺为交联剂,制备氧化淀粉―丙烯酸―丙烯酰胺高吸水性树脂,并采用红外光谱、X射线衍射等手段对产品的结构进行表征。通过单因素实验优化其制备工艺,最佳工艺条件为:氧化淀粉基体用量为50%,丙烯酸/丙烯酰胺质量比为4∶1,丙烯酸中和度为70%,引发剂过硫酸铵用量为0.5%,交联剂N,N’-亚甲基双丙烯酸胺用量为0.15%,反应温度为80℃,反应时间为3 h。此条件下,氧化淀粉基高吸水性树脂的吸水率达到972.4 g/g。     

A Scalable Chemical Approach for the Synthesis of a Highly Tolerant and Efficient Oil Absorbent

In the past, bio‐inspired extreme water repellent property has been strategically embedded on commercially available sponges for developing selective oil absorbents. However, most of the reported materials lack physical and chemical durability, limiting their applicability at practically harsh settings. Herein, a stable dispersion of polymeric nanocomplexes was exploited to achieve a chemically reactive coating on the highly compressible melamine foam. A superhydrophobic melamine foam (SMF) was achieved after post‐covalent modification of the reactive coating through 1,4‐conjugate addition reaction at ambient conditions. The durability of the embedded extreme water repellent property in the as‐modified melamine foam has been elaborately demonstrated through exposing it to severe physical manipulations, chemically harsh aqueous media including pH 1, pH 12, surfactant contaminated water, river water, seawater and prolonged UV irradiation. Thus, the highly tolerant SMF was utilized as an efficient oil absorbent wherein oils of varying densities could be selectively recovered from an oil/water interface with high (e.g., 137 g g^?1 for chloroform and 83 g g^?1 for diesel) oil absorption capacity. Moreover, the selective oil absorption capacity of the as‐synthesized material remained unaffected at practically relevant severe chemical and physical settings, and the extreme water repellency of the material remained unaltered even after repetitive (at least 50 cycles) use for oil/water separation.     

3D hierarchical MnO2 aerogels with superhydrophobicity for selective oil–water separation

Inorganic nanowire aerogel with low density, high specific surface area and high porosity has received increasing attention in the field of materials physics and chemistry because of not only the unique structural and physical features of metallic oxide but also low cost, environmental friendliness and earth abundant of precursor materials. In this work, MnO₂ nanowire aerogels (MNA) with ultralow density, and stable 3D hierarchical structures was successfully fabricated by freeze‐drying processes using MnO₂ nanowire as building blocks. The length of MnO₂ nanowires exceeds 100 μm, making it easier to cross‐link and self‐assemble into a 3D network of aerogels, and the acid and alkali resistance of MnO₂ enables it to adapt to extreme environments. Simultaneously, the monodispersed MnO₂ nanowire was prepared by the hydrothermal method, followed by acid treatment. To obtain superhydrophobic properties and achieve selective oil adsorption, the surfaces of nanowire aerogels were grafted the hydrophobic groups with low surface energy via vapor deposition. It is indicated that the obtained 3D hierarchical MNA show both superhydrophobic and super‐lipophilic properties simultaneously with a high‐water contact angle of 156°  ±  2° and an oil contact angle of 0°. And the MNA exhibited a high oil adsorption capacity of 85–140 g/g, thereby indicating its potential applications in oil/water separation. More importantly, the resulting MNA can be recycled ten cycles without loss of oil absorption capacity (more than 120 g/g). The results presented in this work demonstrate that the as‐prepared nanowire aerogel may find applications in chemical separation and environmental remediation for large‐scale absorption of oils from water.     

Effect of Ce4+ pretreatment on swelling properties of cellulosic superabsorbents

Cellulosic superabsorbents are prepared by pretreating the wood pulp (WP) with Ce⁴⁺ initiator, followed by the graft copolymerization of acrylamide (AM) monomer onto Ce⁴⁺‐pretreated WP (Ce⁴⁺ · WP) in acidic medium and in the presence of N,N′‐methylenebisacrylamide (MBAM) cross‐linker. The rate of AM copolymerization of Ce⁴⁺ · WP is significantly faster than that of the untreated WP. The obtained polyAM (PAM)‐grafted cellulosic copolymers (PAM‐g‐Ce⁴⁺ · WP copolymers) are alkaline‐hydrolyzed to produce the water‐absorbents. As PAM grafting yield increases, the absorbency increases rapidly and reaches the maximum value at a yield of 210–240%. The maximum water and saline absorbencies are around 2500 and 50 g g^?1, respectively. The optimum feed concentration of Ce⁴⁺ pretreatment on the maximum water and saline absorbencies is 5.0 × 10^?3 mol L^?1. The water and saline absorbencies of the PAM‐g‐Ce⁴⁺ · WP water‐absorbents are remarkably higher in comparison with that of the untreated WP (with a similar grafting yield) due to uniform PAM‐grafting onto Ce⁴⁺ · WP specimen. In addition, as the amount of cross‐linker increases, the grafting yield is not changed whereas the water and saline absorbencies are remarkably decreased. Copyright © 2008 John Wiley & Sons, Ltd.     

Graft Copolymerization of Artemisia Seed Gum with Acrylic Acid under Microwave and its Water Absorbency

A super‐absorbent polymer was prepared by grafting copolymerization of acrylic acid onto Artemisia seed gum, using microwave irradiation and ammonium persulfate as an initiator. The effect of various preparation conditions on its water absorbency, such as the ratio of acrylic acid to Artemisia seed gum, degree of acrylic acid neutralization, amount of initiator and microwave irradiation time, was investigated by orthogonal tests. The optimal reaction conditions were 3 min (irradiation time), 70% neutralization degree of acrylic acid and 2% initiator on the basis of the mass of acrylic acid used. When the mass ratio of acrylic acid to Artemisia seed gum is 5:0.5, the product has a water absorbency close to 400 times at room temperature in distilled water, this indicated that is has a high water absorbency. The structure of the graft copolymer was confirmed by Fourier transform infrared spectrometer (FT‐IR) and thermogravimetric analysis (TGA). Further more, this microwave irradiation processing method to prepare water absorbent materials has no industrial cast off produced, that is to say, this method is environmentally friendly.     

单一化学交联与物理化学复合交联高吸油树脂的比较

提出在单一化学交联吸油树脂中引入物理交联的设想，并采用悬浮聚合法了单一化学交联和物理－化学复合交联的聚丙烯酸酯系高吸油树脂，对两种不同树脂的吸油速率，低亲油性单体树脂的吸油性能，最佳单体配比以及化学交联剂含量的影响进行了比较，结果表明物理交联的引入加快了树脂的吸油速率，提高低亲油性单体树脂的吸油能力，并且还使最佳单体配比中低亲油性单体含量增加，同时表明部分物理交联吸油树脂有一最佳化学交联剂含量区。     

Synthesis and properties of clay-based superabsorbent composite

A novel superabsorbent composites based on acrylic acid, acrylamide, and inorganic clay mineral-attapulgite were synthesized through a solution polymerization to improve water and saline absorbencies. The superabsorbent composite was characterized by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). The effects of saline solutions, amount of initiator, crosslinker and attapulgite on the water absorbency of superabsorbent composites were investigated. The water retention test of superabsorbent composites were also carried out. The superabsorbent composite exhibited improved water and saline absorbencies compared with that of crosslinked poly(acrylic acid-co-acrylamide) superabsorbent polymer. The water absorbency of the superabsorbent composite synthesized under optimal synthesis conditions with an attapulgite content of 10% reaches more than 1400 g H₂O/g and 110 g H₂O/g in distilled water and 0.9% NaCl solution, respectively.     

Synthesis of a novel oil‐absorption resin and optimization of its performance parameters using response surface design

A novel porous oil absorbing resin with the main monomers of stearyl methacrylate and isooctyl methacrylate was synthesized using suspension polymerization. The synthesis experiments were conducted using the response surface design method. And the influences of initiator concentration, cross‐linker concentration, and dispersant concentration were investigated. Through analyzing the second‐order polynomial mathematical models and the corresponding data, the mutual effects between these factors on the oil‐absorption performance were obtained. The response surface was used to analyze the oil (gasoline, diesel, and kerosene) absorption performance in the pure oil samples and oily water samples, respectively. The content of initiator and cross‐linker exhibited a necessary effect on the absorption of gasoline and kerosene. Moreover, the two most significant factors for diesel are the amount of initiator and dispersant. The experimental results showed that the oil‐absorbing resin synthesized under the optimized condition could achieve better oil‐absorption rate on all three oils. The absorption rates of gasoline, diesel, and kerosene are 10.14, 10.73, and 11.69 g/g, respectively, which the deoiling rate can reach closed 100% in the water sample containing gasoline and kerosene.     

碳纳米管复合聚丙烯酸钠的制备及吸水性能

以过硫酸铵(APS)为引发剂,N,N′-亚甲基双丙烯酰胺(MBA)为交联剂,采用水溶液聚合法制备了碳纳米管/聚丙烯酸钠高吸水树脂。系统考察了碳纳米管质量分数、引发剂、交联剂和聚合温度对树脂吸水性能的影响。结果表明,以单体丙烯酸质量为基准,当交联剂,引发剂和碳纳米管质量分数分别为0.04%、0.3%和0.3%,聚合温度75℃时,所合成树脂的吸水性能最佳。添加碳纳米管后树脂表面粗糙和形成孔结构导致了其吸水性能的变化,使得碳纳米管/聚丙烯酸钠的吸水量和吸水速率明显提高,其吸去离子水和生理盐水能力分别达到1423和104g/g。该树脂重复吸水5次后,其吸水能力为1081.5g/g,达到最大吸水倍数的76.0%。     

Biomimetic Superhydrophobic/Superoleophilic Highly Fluorinated Graphene Oxide and ZIF‐8 Composites for Oil–Water Separation

Superhydrophobic/superoleophilic composites HFGO@ZIF‐8 have been prepared from highly fluorinated graphene oxide (HFGO) and the nanocrystalline zeolite imidazole framework ZIF‐8. The structure‐directing and coordination‐modulating properties of HFGO allow for the selective nucleation of ZIF‐8 nanoparticles at the graphene surface oxygen functionalities. This results in localized nucleation and size‐controlled ZIF‐8 nanocrystals intercalated in between HFGO layers. The composite microstructure features fluoride groups bonded at the graphene. Self‐assembly of a unique micro‐mesoporous architecture is achieved, where the micropores originate from ZIF‐8 nanocrystals, while the functionalized mesopores arise from randomly organized HFGO layers separated by ZIF‐8 nanopillars. The hybrid material displays an exceptional high water contact angle of 162° and low oil contact angle of 0° and thus reveals very high sorption selectivity, fast kinetics, and good absorbencies for nonpolar/polar organic solvents and oils from water. Accordingly, Sponge@HFGO@ZIF‐8 composites are successfully utilized for oil–water separation.