The electrospinning of the copolymer of styrene and butyl acrylate for its application as oil absorbent
© The Author(s) 2016
Received: 17 March 2016
Accepted: 15 July 2016
Published: 22 August 2016
Electrospun polystyrene materials have been employed as oil absorbents, but they have visible drawbacks such as poor strength at low temperature and unreliable integrity because of brittleness and insufficient cohesive force among fibers. Butyl acrylate can polymerize into flexible chains, and its polymer can be used as elastomer and adhesive material. Thereby it is possible to obtain the material that has better performance in comparison with electrospun polystyrene material through the electrospinning of the copolymer of styrene and butyl acrylate. In this work, a polymer was synthesized through suspension polymerization by using styrene and butyl acrylate as comonomers. The synthesis of the copolymer of styrene and butyl acrylate was verified through dissolution and hydrolysis experimental data; as well through nuclear magnetic resonance spectrometry. The viscous flow activation energy of the solution consisting of copolymer and N, N-dimethylformamide was determined via viscosity method and then adopted to establish the entanglement characteristics of butyl acrylate’s chain segments. Finally, in order to electrospin the copolymer solution into fibrous membrane, the effects of monomer feed ratio and spinning parameters were investigated. The prepared fibrous membrane was found to have a potential use as oil absorbent.
Due to the thriving development of industry around the world, oily organic liquids have been manufactured massively and caused water pollution. These liquids are usually toxic and insoluble in water, thus they spread on water surface to cause severe damage for ecological environment and human being’s health (Nriagu et al. 2016; Adamu et al. 2015; Wan et al. 2014). As a result, it is an urgent task for mankind to control the pollution in time. In addition, it is also important to reclaim valuable organic liquids from the polluted water.
In order to separate oily organic liquids from the polluted water, oil absorbents have been used widely. Wu et al. (2014) prepared polyurethane sponge via surface modification, and they found that the sponge had an oil absorption capacity of more than 100 g/g. Zhang et al. (2015) chose carbonyl iron powders as magnetic material to prepare magnetic poly(styrene–divinylbenzene) monoliths with porous structure and lipophilicity through direct molding and controlled polymerization, and they found that the monoliths had an oil intake capacity of approximately 23 times its own weight. Yati et al. (2016) prepared an oil absorbent with a cross-linked 3-dimensional network via the condensation of poly(tetrahydrofuran) with tris[3-(trimethoxysilyl)propyl] isocyanurate, and they found that the absorbent had a high and fast swelling capacity in various oils. Up to now, some achievements have been made in the field of absorbents preparation. However, granular absorbents can induce a secondary pollution since they can hardly be collected from water after application; spongeous or monolithic absorbents can be collected from water after application, but they exhibit relatively low specific surface area, thus the application values of these absorbents have been shrunk greatly.
Fibrous materials are well-known for large specific surface area, fast absorption rate, and excellent actual operability. Some researchers have reported a lot of fibrous materials which can be used as oil absorbents, for example, the fibers prepared via dry-wet spinning (Feng and Xiao 2006), gelation spinning (Xu and Xiao 2010), wet spinning (Zhao et al. 2011), melt spinning (Zhao et al. 2012), reactive extrusion-melt spinning (Ma et al. 2013), and graft modification (Li and Wei 2012). Due to good practicability and wide applicability, non-woven fabrics, such as melt blown polypropylene non-woven fabric (Zhao et al. 2013a, b), are another important fibrous material which can be used as oil absorbent (Radetic et al. 2008). The above-mentioned fibrous materials involving the fibers and non-woven fabrics can absorb a large amount of oily organic liquids; however, since the fibrous materials are composed of thick fibers, they absorb organic liquids at a relatively slow rate, which has an adverse effect on their application. Electrospun fibrous materials are of great advantage to oil absorption rate for the reason that the diameter of electrospun fibers can reach nanometer level (Zhu et al. 2011). In recent years, some polymers, such as polyacrylonitrile (Su et al. 2012; Liu et al. 2014), poly(m-phenylene isophthalamide) (Tang et al. 2013), and cellulose acetate (Shang et al. 2012), have been electrospun into fibrous materials and used as oil absorbents to separate oil from water. Polystyrene, as a commonly solvent-soluble and thermoplastic polymer, has more excellent electrospinnability in comparison with other polymers, thus electrospun polystyrene fibrous material has been used widely as oil absorbent (Lin et al. 2012, 2013; Lee et al. 2013; Wu et al. 2012). However, polystyrene is a kind of rigid polymer, thus its electrospun fibrous material exhibits some disadvantages. First, some fibers can fall off the fibrous material due to weak cohesive force among fibers. Second, owning to low temperature brittleness, some fibers break at low temperature, and the fibrous material shows poor strength. Therefore, it is very necessary to improve the performance of electrospun polystyrene fibrous material. The previous work showed that electrospun poly (meth)acrylate fibers could adhere to each other to provide a strong cohesive force for fibrous material (Mo et al. 2014); additionally, poly (butyl acrylate) has good low temperature resistance because it has the properties similar to those of natural rubber. Thereby it was proposed that to copolymerize with butyl acrylate was an effective approach to supply electrospun polystyrene material with good cohesive force and flexibility. As a consequence, the shortages of electrospun polystyrene material could be remedied easily.
In this study, suspension polymerization was first adopted to synthesize a polymer of styrene and butyl acrylate in the presence of benzoyl peroxide and polyvinyl alcohol as initiator and stabilizing agent. Dissolution and hydrolysis means, along with nuclear magnetic resonance (NMR) spectrometry, were used to prove the successful copolymerization of styrene with butyl acrylate. Thereafter, the viscous flow activation energy determined via viscosity test was used to confirm the entanglement characteristics of butyl acrylate’s chain segments. Finally, field emission scanning electron microscopy (FESEM) was employed to analyze the effect of spinning parameters on morphological structure of fibrous membrane. Oil absorption capacities of the fibrous membranes of polystyrene and poly (styrene-co-butyl acrylate) were compared preliminarily, and morphological difference between the fibrous membranes of polystyrene and poly (styrene-co-butyl acrylate) was used to explain the difference of oil absorption. In addition, the mechanism of oil absorption was proposed.
Butyl acrylate (BA) was provided by Tianjin Guangfu Fine Chemical Research Institute. Styrene (St) was purchased from Tianjin Fuchen Chemical Reagents Factory. Benzoyl peroxide (BPO) was purchased from China National Pharmaceutical Group Corp. Shanghai Chemical Reagent Co., Ltd. N, N-dimethylformamide (DMF) was supplied by Tianjin Guangfu Science and Technology Development Co., Ltd. Motor oil was provided by Shell Tongyi (Beijing) Petroleum Chemical Co., Ltd. Soybean oil was provided by Kerry Oils & Grains (Tianjin) Co., Ltd. Pump oil was provided by Tianjin Shifang Chemical Co. Ltd. Isopropanol was provided by Tianjin Fengchuan Chemical Reagent Co. Ltd. The above-mentioned materials were used as-received. Polyvinyl alcohol (PVA) was supplied by Hunan Xiangwei Co., Ltd. and used after water washing and drying in a vacuum oven.
A solution was first prepared by dissolving 2.25 g PVA in 100 ml deionized water at 80 °C, and the solution was then cooled down to room temperature. Another solution was subsequently obtained by mixing BPO whose mass was equal to 0.5 % of the total mass of St and BA with the mixture of St and BA at room temperature. The mass fraction of BA in the mixture of St and BA with a total volume of 150 ml was assigned to 0, 20, 30, or 40 %. Thereafter, the two solutions and 350 ml deionized water were stirred to react at 85 °C for 3 h and 95 °C for 3 h in a three-neck flask under nitrogen atmosphere. After being separated from the solution of PVA and deionized water via vacuum filtering, the resultants were washed initially with hot water and subsequently with deionized water. Finally, four kinds of polymers synthesized when the mass fraction of BA was equal to 40, 30, 20, or 0 % were labeled as 1#, 2#, 3#, and 4# after drying in a vacuum oven at 33 °C.
A solution was first prepared by dissolving 2.25 g PVA in 100 ml deionized water at 80 °C, and the solution was then cooled down to room temperature. Another solution was subsequently obtained by mixing BPO whose mass was equal to 0.5 % of the mass of BA with 150 ml BA at room temperature. Thereafter, the two solutions and 350 ml deionized water were stirred to react at 85 °C for 5 h and 95 °C for 1 h in a three-neck flask under nitrogen atmosphere. After being separated from the solution of PVA and deionized water via vacuum filtering, the resultants were washed initially with hot water and subsequently with deionized water. Finally, poly (butyl acrylate) (PBA), labeling as 5#, was obtained through drying in a vacuum oven at 33 °C.
An Avance 300 MHz (Bruker Corp., Germany) nuclear magnetic resonance (NMR) spectrometer was used to analyze the macromolecular structure of the above-synthesized polymer. The test was performed at resonance frequencies of 300 and 75 Hz for 1H and 13C nuclei at 20 °C. The spectra were obtained by using deuterated chloroform (CDCl3) as solvent, and chemical shifts were referenced to tetramethylsilane (TMS).
Spinning solution preparation
The above-synthesized polymer with a mass of 3 g was mixed with 17 g DMF in a beaker, and the mixture was then stirred at 80 °C until the polymer completely dissolved. The solution was preserved with a dry and clean beaker for later use.
The spinning solutions of the polymer 1# or 4# were used for analysis, their viscosities were measured by using a SNB-1A rotary digital viscometer (Shanghai Fangrui Instrument Co., Ltd., China). The test was performed at 30, 40, 50, 60, and 70 °C when the rotor 21# rotated with a speed of 20 r/min.
Fibrous membrane preparation
The surface of fibrous membrane was first coated with gold via an electro-deposition method, and its surface morphology was then observed by a NOVA NANOSEM 230 (FEI, America) field emission scanning electron microscopy (FESEM) at an accelerating voltage of 15.0 kV.
Oil absorption capacity test
Results and discussion
Viscous flow active energy
Effect of spinning parameters
Oil absorption property
Styrene reacted with butyl acrylate during suspension polymerization to form a copolymer, poly (styrene-co-butyl acrylate). Soft and flexible butyl acrylate chain segments prompted poly (styrene-co-butyl acrylate) chains to entangle with each other in spinning solution. Rigid polystyrene chains did not relax during electrospinning so that its fibrous membrane owned a morphological structure without beads; however, poly (styrene-co-butyl acrylate) chains relaxed at a faster rate to result in that the fibrous membrane fabricated from poly (styrene-co-butyl acrylate) had a morphological structure of beads-on-a-string. Extrusion rate and applied voltage imposed a great impact on the relaxation of polymer chains through affecting strain rate and fiber formation duration. The fibrous membranes prepared at different extrusion rates or applied voltages showed different morphological structures. Due to the different morphological structures, the fibrous membrane electrospun from poly (styrene-co-butyl acrylate) had a potential use as absorbent for low viscosity oils while electrospun polystyrene fibrous membrane could be used as absorbent for high viscosity oils.
NX carried out a lot of research works, and participated in the whole study and drafted the manuscript. JC conceived of the study, and participated in its design and helped to revise the manuscript. YL helped to arrange some data and draw some figures by origin software. All authors read and approved the final manuscript.
The authors acknowledge the financial supports provided by Liaoning key laboratory of functional textile materials.
The authors declare that they have no competing interests.
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