丙烯酸酯类吸油树脂的合成与性能研究

以丙烯酸酯、甲基丙烯酸酯为主要单体,二丙烯酸丁二醇酯为交联剂,过氧化二苯甲酰为引发剂,采用悬浮聚合方法,合成聚丙烯酸酯类高吸油树脂.研究了分散剂、引发剂、交联剂用量及单体配比等因素对树脂吸油性能的影响.结果表明,分散剂用量为单体质量的0.12%,引发剂用量为1.0%,交联剂用量为1.5%时树脂的吸油能力最佳,吸甲苯倍率可达15倍,吸汽油倍率可达10倍,吸机油倍率可达近9倍.     

Facile fabrication of porous oil‐absorbent microspheres with high oil absorbency and fast oil absorption speed

A novel type of porous oil‐absorbent microspheres based on poly(stearyl methacrylate‐co‐butyl acrylate) was prepared via suspension polymerization. By investigating the effects of the cross‐linking agent, monomer ratio, initiator, stabilizer, water/oil ratio, and porogen agent on the oil absorbency of the prepared oil‐absorbents, an optimized oil‐absorbent microsphere OAM‐T was obtained, and characterized by FT‐IR and SEM. The oil absorbencies of OAM‐T toward chloroform, toluene, gasoline, and diesel were measured to be 61.9, 32.6, 28.8, and 28.2 g/g respectively, with oil absorption saturation time being 1.0, 1.5, 2.0, and 3.0 hr. The oil retention of OAM‐T toward the four oils is all above 95%. Besides in pure oils, OAM‐T also has high oil absorbencies in oil–water mixture. It can be reused at least 12 times with little change in oil absorbency. Owing to its excellent oil absorption performance, OAM‐T might find applications for removing oil spills and organic pollutants from water. Copyright © 2015 John Wiley & Sons, Ltd.     

改性高吸油性树脂的合成

将造成环境“白色污染”的发泡聚苯乙烯添加到由丙烯酸2-乙基已酯为单体的聚合体系中,从而合成新型的高吸油性树脂。考察了发泡聚苯乙烯的添加量、交联剂和引发剂等因素对树酯吸油性能的影响,所得树脂可吸苯22g/g,吸煤油13.5/g。     

Inverse Suspension Polymerization of Partially Neutralized and Lightly Cross-Linked Acrylic Acid: Effect of Reaction Parameters

An inverse suspension polymerization was carried out in laboratory in one Liter Buchi glass reactor to produce superabsorbent polymers (SAPs) based on acrylic monomers for hygiene applications. Strongly water absorbing polymers, based on acrylic acid, sodium acrylate were prepared by copolymerization using potassium per sulfate as initiator and N-N′ methylene-bisacrylamide (MBA) as crosslinking agent. The effect of varying monomer, crosslinker, initiator, dispersant concentration, time of reaction and degree of neutralization, on absorption capacities was investigated. In the present studies, the continuous hydrocarbon phase was taken as 50:50 mixture of n-heptane and cyclohexane (aliphatic-alicyclic) because the availability of crosslinker in the aqueous phase is controlled by the partition coefficient of the crosslinker between the aqueous phase and the continuous hydrocarbon phase. The SAPs were evaluated for their free absorption capacities in distilled water, saline (0.9% NaCl), and also absorption under load (AUL). The experimental results show that these SAPs have good absorbency both in water and NaCl solutions. It was observed that SAP synthesized from acrylic acid with about 70% degree of neutralization, containing 1% cross-linker, and 0.5–1.0% initiator concentration with 10% dispersant exhibited absorption capacities in water, saline and AUL as 220 g/g, 70 g/g and 27 g/g respectively.     

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 of crosslinked poly(butyl methacrylate‐co‐pentaerythritol triacrylate) gel by single electron transfer‐living radical polymerization and its oil‐absorbing properties

A novel high oil‐absorbing crosslinked gel was synthesized by copolymerization of butyl methacrylate (BMA) with a small amount of pentaerythritol triacrylate (PETA) crosslinker using single electron transfer‐living radical polymerization (SET–LRP) initiated with carbon tetrachloride (CCl₄) and catalyzed by Cu(0)/hexamethylenetetramine (HMTA) in N, N‐dimethylformamide (DMF). The polymerization followed first‐order kinetics as indicated by linear increase of monomer concentration with reaction time. Effects of reaction temperature, crosslinker, initiator, and catalyst on the oil‐absorbing properties of the crosslinked gel were investigated in detail. The oil absorptions of the crosslinked gel to chloroform, toluene could reach 51.9, 34.5 g/g, respectively. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

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.     

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 molecularly imprinted polymers by atom transfer radical polymerization for the solid‐phase extraction of phthalate esters in edible oil

Novel molecularly imprinted polymers of phthalate esters were prepared by atom transfer radical polymerization using methyl methacrylate as functional monomer, cyclohexanone as solvent, cuprous chloride as catalyst, 1‐chlorine‐1‐ethyl benzene as initiator and 2,2‐bipyridyl as cross‐linker in the mixture of methanol and water (1:1, v/v). The effect of reaction conditions such as monomer ratio and template on the adsorption properties was investigated. The optimum condition was obtained by an orthogonal experiment. The obtained polymers were characterized using scanning electron microscopy. The binding property was studied with both static and dynamic methods. Results showed that the polymers exhibited excellent recognition capacity and outstanding selectivity for ten phthalate esters. Factors affecting the extraction efficiency of the molecularly imprinted solid‐phase extraction were systematically investigated. An analytical method based on the molecularly imprinted coupled with gas chromatography and flame ionization detection was successfully developed for the simultaneous determination of ten phthalate esters from edible oil. The method detection limits were 0.10–0.25 μg/mL, and the recoveries of spiked samples were 82.5–101.4% with relative standard deviations of 1.24–5.37% (n = 6).     

玉米淀粉与丙烯酸接枝共聚合成高吸水树脂

高吸水性树指是七十年代迅速发展起来的一种新型功能高分子材料,由于它吸水速度快且能吸收自身重量数百倍乃至上千倍的水,吸水膨胀后生成的凝胶在加压条件下不易将水析出,而在周围环境缺水的条件下,又可将水缓慢释放出来,因此在农业、园林、医药卫生、沙漠治理、通信电缆等领域具有广泛的用途。近年来,随着高吸水树脂应用范围的不断拓展,其需求量迅速增加,平均年增长率高达30—40％。高吸水树脂根据合成原料的不同,主要分为合成树脂类、纤维素类和淀粉类,合成树脂类生产工艺简单,具有优良的吸水保水能力,但难于降解;纤维素类虽然可降解,但吸水率较低;淀粉类由于原料来源广泛,价格低廉,在自然界中可生物降解,对环境友好,成为吸水树脂领域的研究重点。我国在进行高吸水树脂的研究方面起步较晚,     

Synthesis and application of a nanoporous ion‐imprinted polymer for the separation and preconcentration of trace amounts of vanadium from food samples before determination by electrothermal atomic absorption spectrometry

A vanadium ion‐imprinted polymer was synthesized in the presence of V(V) and N‐benzoyl‐N‐phenyl hydroxyl amine using 4‐vinyl pyridine as the monomer, ethylene glycol dimethacrylate as the cross linker and 2,2’‐azobis(isobutyronitrile) as the initiator. The imprinted V(V) ions were completely removed by leaching the polymer with 5 mol/L nitric acid, and the polymer structure was characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. The ion‐imprinted polymer was used as the sorbent in the development of the solid‐phase extraction method for V(V) prior to its determination by electrothermal atomic absorption spectrometry. The maximum sorption capacity for V(V) ions was 26.7 mg/g at pH 4.0. Under the optimum conditions, for a sample volume of 150.0 mL, an enrichment factor of 289.0 and a detection limit of 6.4 ng/L were obtained. The developed method was successfully applied to the determination of vanadium in parsley, zucchini, black tea, rice, and water samples.     

Fabrication and properties of a novel superabsorbent composite based on coco peat and poly (acrylic acid) cross‐linked trimethylolpropane trimaleate under ultraviolet irradiation

A series of novel poly(acrylic acid)/coco peat (PAA/CP) superabsorbent composites were prepared via the ultraviolet irradiation copolymerization of acrylic acid monomer (PAA) and coco peat cellulose (CP) in the presence of the cross‐linker trimethylolpropane trimaleate. The physico‐chemical structures of obtained PAA/CP were characterized by Fourier transform infrared spectroscopy, thermogravimetry/derivative thermogravimetry, X‐ray diffraction, and scanning electron microscopy, respectively. The critical parameters of affecting the water absorbency of PAA/CP, including the cross‐linker level, amount of CP and reaction time, were studied in detailed. The experimental results showed that the PAA/CP samples exhibited the maximum swelling value of 523.09 g/g in distilled water and 40.52 g/g in 0.9 wt % NaCl solution. The swelling behaviors of PAA/CP were significantly relied on the concentration of salt solution and the pH of external solution. The effect of ions species on the swelling performance was in the order: Na⁺ > Ca²⁺ > Fe³⁺ , and in pH 2.2 and 7.2 aqueous solutions PAA/CP composites displayed better pH‐responsiveness and reversible on‐off switching characteristics. Urea, as an agrochemical model, was loaded into PAA/CP substrate to supply with nitrogen nutrient. The test of their loading and releasing diffusion performance of urea suggested that the urea loading percentage of PAA/CP was remarkably dependent on the concentration of aqueous urea solutions and the release of urea from loaded PAA/CP samples in water followed a non‐Fickian mechanism. Owing to their considerable good water absorption capacity, slow urea release, economical and environment‐friendly merits, PAA/CP composites could be exploited for the agriculture applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Fabrication and characteristics of polyHEMA artificial skin with improved tensile properties

PolyHEMA-based hydrogel synthesized by the UV-radiation induced polymerization technique is used to prepare the strength-proved artificial skin in order to improve the handling procedure for curing the burned wound. The tensile strength of the artificial skin membrane is measured following the ASTM standard. The strength decreases with increasing amount of the initial water added to the mixture of HEMA (2-hydroxyethyl methacrylate) monomer, ethylene glycol dimethacrylate (EGDMA) cross linker and benzoin isobutyl ether (BIE) initiator. The maximum strength of the artificial skin membrane reaches 9 kg/cm², as the hydrogel contains equilibrium water around 30 wt%. The artificial skin so fabricated presents several additional characteristics including good wettability, complete transparency and dimensional change during water absorption and evaporation.     

Poly(methyl methacrylate‐co‐pentaerythritol tetraacrylate‐co‐butyl methacrylate)‐g‐polystyrene: Synthesis and high oil‐absorption property

Well‐defined high oil‐absorption resin was successfully prepared via living radical polymerization on surface of polystyrene resin‐supported N‐chlorosulfonamide group utilizing methyl methacrylate and butyl methacrylate as monomers, ferric trichloride/iminodiacetic acid (FeCl₃/IDA) as catalyst system, pentaerythritol tetraacrylate as crosslinker, and L ‐ascorbic acid as reducing agent. The polymerization proceeded in a “living” polymerization manner as indicated by linearity kinetic plot of the polymerization. Effects of crosslinker, catalyst, macroinitiator, reducing agent on polymerization and absorption property were discussed in detail. The chemical structure of sorbent was determined by FTIR spectrometry. The oil‐absorption resin shows a toluene absorption capacity of 21 g g^?1. The adsorption of oil behaves as pseudo‐first‐order kinetic model rather than pseudo‐second‐order kinetic model. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Fabrication of tailorable pH responsive cationic amphiphilic microgels on a microfluidic device for drug release

Cationic, amphiphilic microgels of differing compositions based on hydrophilic, pH, and thermoresponsive 2‐(dimethylamino)ethyl methacrylate (DMAEMA) and hydrophobic, nonionic n‐butyl acrylate (BuA) are synthesized using a lab‐on‐a‐chip device. Hydrophobic oil‐in‐water (o/w) droplets are generated via a microfluidic platform, with the dispersed (droplet) phase containing the DMAEMA and BuA, alongside the hydrophobic cross‐linker, ethylene glycol dimethacrylate, and a free radical initiator in an organic solvent. Finally, the hydrophobic droplets are photopolymerized via a UV light source as they traverse the microfluidic channel to produce the cationic amphiphilic microgels. This platform enables the rapid, automated, and in situ production of amphiphilic microgels, which do not match the core‐shell structure of conventionally prepared microgels but are instead based on random amphiphilic copolymers of DMAEMA and BuA between the hydrophobic cross‐links. The microgels are characterized in terms of their swelling and encapsulation abilities, which are found to be influenced by both the pH response and the hydrophobic content of the microgels. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 59–66     

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.     

甲基丙烯酸十二酯精制及其树脂性能研究

对工业级甲基丙烯酸十二酯单体进行了精制提纯,采用悬浮聚合法合成了甲基丙烯酸十二酯树脂。利用傅立叶变换红外光谱(FTIR)对精制前后单体以及树脂的结构进行了表征、利用热分析仪(TG)和差式扫描量热仪(DSC)对树脂的热性能进行了分析,同时研究了精制时碱液浓度对树脂饱和吸油率、吸油速率以及充分溶胀后树脂剩余率的影响。结果表明,精制后单体合成的树脂耐热性能有了明显改善,热降解温度大大提高;精制前后单体合成的树脂,由于杂质存在的缘故,其低温玻璃化转变类型明显不同;经6wt%碱液和8wt%碱液精制后单体的纯度有了明显提高,由其合成的树脂饱和吸油率,吸油速率都有较大提高,甚至接近化学纯单体合成树脂的饱和吸油率。     

Highly absorbing superabsorbent polymer

Acrylic acid (AA)–acrylamide (AM) based superabsorbent polymers (SAP) were synthesized by inverse suspension polymerization using potassium‐persulfate as the initiator, N,N′‐methylene bisacrylamide (BIS) as a crosslinker, sorbitan monostearate (Span 60) as the dispersant, cyclohexane as the solvent, and bis(methacryloylamino)‐azobenzene as the hydrophobic surface crosslinker. The influence of the polymerization parameters on the properties of the SAPs, water absorption (Q), morphology of the SAPs, swelling kinetics, salt resistance, and the reversibility of water absorption were investigated. The prepared SAPs have excellent water absorption, rapid water uptake, and good resistance to NaCl solutions. Furthermore, they show better reversible water uptake than the previously reported SAPs. The average water absorbency is 2800 g/g and 181 g/g of liquid absorbance in 0.025M NaCl solution. The initial water uptake rate is 1357 g/g/min and the reversibility of water absorption is 200 g/g in the repeated fourth cycle. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1357–1364, 2008     

Application of phase-titrations for estimation of adulteration of gasoline and high-speed diesel with kerosene

A simple, cheap and quick routine method based on phase-titration has been developed for the estimation of adulteration of gasoline and high-speed diesel with kerosene. Since no instrumentation is required, the method can be used as a field method for analysis at filling stations. Adulteration of gasoline with kerosene can be determined to +/-1%, and of diesel with kerosene to +/-2%. Even non-technical personnel with a few day's training can analyse fuel samples by this method.     

淀粉基高吸水性树脂吸水性能的测定条件评价

研究了测定条件对淀粉基高吸水性树脂吸水性能的影响,分别考察了测定方法、树脂粒径、初始加水量、水介质pH、温度及溶液中盐的质量分数对树脂吸水倍率和吸水速率的影响.结果表明,采用100目网筛过滤法测定树脂的吸水性能结果较准确;当吸水介质与干树脂的质量比为2 400∶1,pH为7时,可以使树脂达到最大饱和吸水倍率;在树脂粒径96～180μm范围内,随着树脂粒径的减小、水介质温度的升高及盐浓度的降低,树脂的吸水倍率和吸水速率增大.