Thermo‐Responsive Gating Characteristics of Poly(N‐isopropylacrylamide)‐Grafted Membranes

Both hydrophilic Nylon‐6 membranes and hydrophobic poly(vinylidene fluoride) (PVDF) membranes, with a wide range of grafting yields of poly(N‐isopropylacrylamide) (PNIPAM), were prepared using the plasma‐graft pore‐filling polymerization method. The effect of the physical and chemical properties of the substrates on the thermo‐responsive gating characteristics of the PNIPAM‐grafted membranes was investigated experimentally. For both the PVDF and Nylon‐6 membranes, the grafted PNIPAM polymers were found not only on the membranes outer surface, but also on the inner surfaces of the pores throughout the entire thickness of the membrane. The thermo‐responsive gating characteristics of the PNIPAM‐grafted membranes were heavily affected by the physical and chemical properties of the porous membrane substrates. The PNIPAM‐g‐Nylon‐6 membranes exhibited a much larger thermo‐responsive gating coefficient than the PNIPAM‐g‐PVDF membranes. Furthermore, to achieve the largest thermo‐responsive gating coefficient, the corresponding optimum grafting yield of PNIPAM for the PNIPAM‐g‐Nylon‐6 membranes was also larger than that for the PNIPAM‐g‐PVDF membranes.     

Surface initiated ATRP of acrylic acid on dopamine‐functionalized AAO membranes

A facile method for surface‐initiated atom transfer radical polymerization (ATRP) on the anodic aluminum oxide (AAO) membranes has been developed. The AAO membrane was firstly functionalized by poly(dopamine), the bromoalkyl initiator was then immobilized on the poly(dopamine) functionalized AAO membrane surface in a two‐step solid‐phase reaction, followed by ATRP of acrylic acid in a aqueous solution. The poly(acrylic acid) (PAAc)‐grafted AAO membranes were characterized by X‐ray photoelectron spectroscopy, fourier transform infrared spectroscopy and scanning electron microscopy. The XPS and FTIR results indicated that PAAc was successfully grafted on the AAO membrane surface. The degree of grafting increases linearly with the increase of monomer concentration, and it reaches a plateau when the reaction time up to 4 h. The results indicate that the thickness of the grafted polymer inside the isocylindrical pores of AAO membranes could be well controlled by changing the reaction time and monomer concentration. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

“Smart” membrane materials: Preparation and characterization of PVDF‐g‐PNIPAAm graft copolymer

In this research, a smart membrane material of graft copolymer of poly(vinylidene fluoride) with poly(N‐isopropylacrylamide) (PVDF‐g‐PNIPAAm) was synthesized by atom transfer radical polymerization (ATRP) using poly(vinylidene fluoride) (PVDF) as a macroinitiator and direct initiation of the secondary fluorinated site PVDF facilitates grafting the N‐isopropylacrylamide comonomer. The copolymers were characterized by Fourier transform infrared (FTIR), ¹H NMR, gel‐permeation chromatography (GPC), and X‐ray photoelectron spectroscopy (XPS). The temperature‐sensitive membrane was prepared from the PVDF‐g‐PNIPAAm graft copolymers by the phase inversion method. The effects of temperature on the flux of pure water of membrane was investigated. The results showed that alkyl fluorides were successfully applied as ATRP initiators in the synthetic condition and the flux of pure water through the PVDF‐g‐PNIPAAm membrane depended on the temperature change. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1482–1486, 2007     

Thermoresponsive surface prepared by atom transfer radical polymerization directly from poly(vinylidene fluoride) for control of cell adhesion and detachment

Thermoresponsive surface was prepared from commercial poly(vinylidene fluoride) (PVDF) films via surface‐initiated atom transfer radical polymerization. The direct initiation of the secondary fluorinated site of PVDF facilitated grafting of the N‐isopropylacrylamide (NIPAAm) monomer. The PVDF surfaces grafted with poly(N‐isopropylacrylamide) [P(NIPAAm)] were characterized by X‐ray photoelectron spectroscopy. Kinetics study revealed that the P(NIPAAm) chain growth from the PVDF surface was consistent with a “controlled” process. The temperature‐dependent swelling behavior of the surfaces in aqueous solution was studied by atomic force microscope. At 37°C [above the lower critical solution temperature (LCST, about 32°C) of NIPAAm], the seeded cells adhered and spread on the NIPAAm grafted PVDF surface. Below the LCST, the cells detached from the P(NIPAAm)‐grafted PVDF surface spontaneously. The thermoresponsive surfaces are potentially useful as stimuli‐responsive adhesion modifiers in the biomedical fields.© 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Surface‐initiated atom transfer radical polymerization of regenerated cellulose membranes with thermo‐responsive properties

Using atom transfer radical polymerization (ATRP), thermo‐responsive regenerated cellulose membranes were synthesized. Regenerated cellulose membranes were firstly modified by reacting the hydroxyl groups on the surface with 2‐bromoisobutyryl bromide, followed by grafting with poly(N‐isopropylacrylamide). The membranes had obvious thermally modulated permeability properties. Analysis was carried out by means of X‐ray photoelectron spectroscopy, attenuated total reflection Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis. The results showed that N‐isopropylacrylamide had been grafted successfully on the surface of the regenerated cellulose membranes. The thermally modulated permeability properties of the grafted membranes were studied using water flux measurements. It was found that the thermally modulated permeability properties of a cellulose surface can be tailored by the use of the ATRP method. Copyright © 2010 Society of Chemical Industry     

Controlled grafting of polymer brushes on poly(vinylidene fluoride) films by surface‐initiated atom transfer radical polymerization

Controlled grafting of well‐defined polymer brushes on the poly(vinylidene fluoride) (PVDF) films was carried out by the surface‐initiated atom transfer radical polymerization (ATRP). Surface‐initiators were immobilized on the PVDF films by surface hydroxylation and esterification of the hydroxyl groups covalently linked to the surface with 2‐bromoisobutyrate bromide. Homopolymer brushes of methyl methacrylate (MMA) and poly(ethylene glycol) monomethacrylate (PEGMA) were prepared by ATRP from the α‐bromoester‐functionalized PVDF surface. The chemical composition of the graft‐functionalized PVDF surfaces was characterized by X‐ray photoelectron spectroscopy (XPS) and attenuated total reflectance (ATR)–FTIR spectroscopy. Kinetics study revealed a linear increase in the graft concentration of PMMA and PEGMA with the reaction time, indicating that the chain growth from the surface was consistent with a “controlled” or “living” process. The “living” chain ends were used as the macroinitiator for the synthesis of diblock copolymer brushes. Water contact angles on PVDF films were reduced by surface grafting of PEGMA and MMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3704–3712, 2006     

Synthesis of controlled thermoresponsive PET track‐etched membranes by ATRP method

Controlled thermoresponsive PET track‐etched membranes were synthesized by grafting N‐isopropylacrylamide (NIPAAm) onto the membrane surface via atom transfer radical polymerization (ATRP). The initial measurements were made to determine the anchoring of ATRP initiator on PET membrane surface. Thereafter, polymerization was carried out to control the mass of polymer by controlling reaction time grafted from the membrane surface and, ATR‐FTIR, grafting degree measurements, water contact angle measurements, TGA, and SEM were used to characterize changes in the chemical functionality, surface and pore morphology of membranes as a result of modification. Water flux measurements were used to evaluate the thermoresponsive capacity of grafted membranes. The results show the grafted PET track‐etched membranes exhibit rapid and reversible response of permeability to environmental temperature, and its permeability could be controlled by controlling polymerization time using ATRP method. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Preparation of temperature sensitive poly(vinylidene fluoride) hollow fiber membranes grafted with N‐isopropylacrylamide by a novel approach

In the present study, the temperature sensitive PVDF‐g‐NIPAAm HFM was prepared by grafting N‐isopropylacrylamide (NIPAAm) on poly(vinylidene fluoride) (PVDF) hollow fiber membrane (HFM) using a novel approach, alkaline treatment method. The structures of PVDF‐g‐NIPAAm HFM were characterized by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR), respectively. The effects of alkaline treatment time and grafting yield on the mechanical properties of PVDF HFM were measured and analyzed. In addition, the temperature sensitive behavior of PVDF‐g‐NIPAAm HFM and the effect of grafting yield on the temperature sensitive behavior were investigated by the flux of pure water and the rejection of ovalbumin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 833–837, 2006     

Synthesis and characterization of dual responsive graft copolymers composed of casein and poly(N-isopropylacrylamide)

A series of novel temperature- and pH- responsive water-soluble graft copolymers, casein-g-poly(N-isopropylacrylamide)(PNIPAAm), were prepared via a direct graft copolymerization of N-Isopropylacrylamide (NIPAAm) from casein. The polymerization was induced by tert-butyl hydroperoxide (TBHP) in water at general condition. Chemical structures of the graft copolymers were characterized by Fourier transform infrared spectra (FTIR), Thermo gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The effect elements on graft copolymerization, such as concentration of initiator, reaction time, reaction temperature and ratio of NIPAAm to casein were investigated in terms of NIPAAm conversion, grafting percentage (GP) and grafting efficiency (GE), respectively. The graft copolymers are stimuli-sensitive with respect to both temperature and pH in aqueous solutions. It could self-assembly into core-shell particles in aqueous solution with collapsed PNIPAAm as core as well as inverse core-hair particles with expanded casein as core on changing temperature or pH, as indicated by transmission electron microscopy (TEM).     

Gating Characteristics of Thermo‐Responsive Membranes with Grafted Linear and Crosslinked Poly(N‐isopropylacrylamide) Gates

Thermo‐responsive porous membranes with grafted linear and crosslinked poly(N‐isopropylacrylamide) (PNIPAM) gates are successfully prepared at temperatures above and below the lower critical solution temperature (LCST) of PNIPAM by using a plasma‐induced grafting polymerization method, and the effects of operation pressure and grafting temperature on the thermo‐responsive gating characteristics of the prepared membranes are investigated systematically. The fluxes of water through the grafted membranes increase simply with increasing the operation pressure no matter whether the environmental temperature is 40 °C or 25 °C. Under high operation pressure (e.g., higher than 0.14 MPa), the grafted linear PNIPAM gates deform to a certain extent, whereas the grafted crosslinked PNIPAM gates do not deform. For both membranes with grafted linear and crosslinked PNIPAM gates, the membranes prepared at 25 °C (below the LCST of PNIPAM) show larger thermo‐responsive gating coefficients than those prepared at 40 °C (above the LCST of PNIPAM), which results from different distributions of grafted PNIPAM gates in the membrane pores. When the PNIPAM gates are grafted at 25 °C, the grafted layer near the membrane surface is much thicker than that inside the membrane pores; on the other hand, when the PNIPAM gates are grafted at 40 °C, the grafted layer is homogeneously formed throughout the whole pore length. Both linear and crosslinked grafted PNIPAM gates in the membrane pores exhibit stable and repeatable thermo‐responsive “open‐close” switch performances under the operation pressure of 0.26 MPa. The results in this study provide valuable guidance for designing, fabricating, and operating thermo‐responsive gating membranes with desirable performances.     

Preparation of cationic exchange membranes based on organo‐montmorillonite/poly(vinylidene fluoride) by two‐step chemically induced grafting method

In this research, OMMT/PVDF‐based cationic exchange membranes were prepared by two‐step chemically induced grafting method. The various preparation conditions, such as alkaline treatment, initiation, and grafting conditions, and the relationship between the preparation conditions and the cationic exchange membrane performance, such as area resistance and cationic permselectivity, were investigated. The chemical and crystal changes on the membrane surface were characterized by Fourier transform infrared spectroscopy (FTIR), energy dispersive spectrum (EDS), and X‐ray diffraction (XRD), respectively. Surface morphological changes were also characterized by scanning electron microscopy (SEM). The results reveal that the OMMT/PVDF‐based cationic exchange membrane was successfully prepared by this method. The OMMT/PVDF‐based cationic exchange membrane doped 8.5% OMMT prepared using optimum preparation parameters showed excellent basic properties. The area resistance was measured as low as 1.8 Ω cm², while the cationic permselectivity was as high as 93.4%. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 2753–2763, 2013     

紫外接枝丙烯酸对PVDF膜表面改性的研究

以二苯甲酮为光引发剂,通过紫外辐照将亲水性单体丙烯酸接枝于聚偏氟乙烯(PVDF)膜的表面。考察了光引发剂浓度和辐照时间对接枝率的影响,并利用衰减全反射光谱和扫描电子显微镜对接枝后PVDF膜表面的化学组成和微观形貌进行了表征。结果表明:随着光引发剂浓度的增大,丙烯酸的接枝率先增大后减小。通过纯水接触角和吸水率研究了接枝后的PVDF膜的亲水性,发现接枝后的PVDF膜的亲水性得到明显改善。     

Structure and performance of temperature‐sensitive poly(vinylidene fluoride) hollow fiber membrane fabricated at different take‐up speeds

Graft copolymer (PVDF‐g‐PNIPAAm) having poly(vinylidene fluoride) (PVDF) backbones and poly(N‐isopropylacrylamide) (PNIPAAm) side chains was synthesized via radical copolymerization and its hollow fiber membrane was fabricated from dry–wet spinning technique with N, N‐dimethylformamide as the solvent and poly(ethylene glycol) (10,000) as the additive. The effects of spinning condition (take‐up speeds) on the structures and performances of resulting fiber membranes were systematically considered. The structures and performances of fiber membranes were characterized by element analysis, X‐ray photoelectron spectroscopy, water contact angle measurement, scanning electron microscope, atom force microscope, and filtration experiments. The results indicate that PNIPAAm side chains tended to enrich on the membrane surface and pore surface and especially tended to aggregate on the inner surface due to the effect of bore fluid. The hollow fiber membrane exhibits an obvious temperature‐sensitive property. The pure water flux increases remarkably around 32°C, while the retention of albumin egg decreases accordingly, when the permeation temperature rises from 20 to 45°C. As the take‐up speed increases, both the inner and outer diameters of fiber membranes decrease. A higher take‐up speed favors higher pure water permeation flux, which allows larger molecules to permeate through the fiber membrane. POLYM. ENG. SCI. 2013. © 2012 Society of Plastics Engineers     

Preparing polymer brushes on poly(vinylidene fluoride) films by free radical polymerization

Grafting of polymer brushes on the poly(vinylidene fluoride) (PVDF) films was carried out by the surface‐initiated free radical polymerization. Surface‐initiators were immobilized on the PVDF films by surface hydroxylation and esterification of the surface‐tethered hydroxyl groups with 4,4′‐azobis(4‐cyanopentanoic acid) (ACP). Homopolymer brushes of methyl methacrylate (MMA) were prepared by free radical polymerization from the azofunctionalized PVDF surface. The chemical composition and topography of the graft‐functionalized PVDF surfaces were characterized by X‐ray photoelectron spectroscopy (XPS), attenuated total reflectance (ATR) FTIR spectroscopy, and atomic force microscopy (AFM). Kinetics study revealed an exponential increase in the graft concentration of polymer brushes with the reaction time, indicating that the chain growth from the surface was consistence with a chain polymerization. Water contact angles on PVDF films were reduced by surface grafting of MMA. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 857–862, 2006     

Influence of pore size and pore shape on thermo‐sensitive properties of poly[(ethylene terephthalate)‐graft‐(N‐isopropylacrylamide)] track membranes

BACKGROUND: The main aim of this work was to prepare poly[(ethylene terephthalate)‐graft‐(N‐isopropylacrylamide)] (PET‐graft‐NIPAAm) track membranes with various pore shapes and pore sizes, and to investigate the influence of pore shape and pore size on the thermo‐sensitive properties of the membranes. The PET‐graft‐NIPAAm track membranes were prepared using UV illumination, chemical etching and γ‐irradiation polymerization. Their thermo‐sensitive properties were investigated using conductimetry. RESULTS: PET track membranes with four kinds of pore shapes and sizes were prepared using chemical etching by changing the UV illumination time. After γ‐irradiation, NIPAAm was grafted into the etched PET track membranes both inside the pores and on the membranes. Conductimetric measurements showed that only membranes with appropriate pore shape and pore size had thermo‐sensitive properties. When the grafting ratio was 5 wt%, membranes with both small double cone‐shaped pores and with very large cylinder‐shaped pores showed no thermo‐sensitive properties. CONCLUSION: Along with the grafting ratio, the pore shape and pore size also have an influence on the thermo‐sensitive properties of PET‐graft‐NIPAAm track membranes. Copyright © 2009 Society of Chemical Industry     

Modification of cellulose/chitin mix fibers with N‐isopropylacrylamide and poly(N‐isopropylacrylamide) under cold plasma conditions

A two‐step grafting procedure was applied to cellulose/chitin (CC) mix fibers, namely: activation under the action of cold plasma discharges, followed by reaction with N‐isopropylacrylamide (NIPAAm) and poly(N‐isopropylacrylamide) (PNIPAAm) to obtain fibers with responsiveness to external stimuli. The graft samples were characterized using attenuated total reflection Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy (XPS), X‐ray diffraction, scanning electron microscopy coupled with energy‐dispersive X‐ray microanalysis and antimicrobial testing. All obtained results confirm the morphological and structural changes after plasma treatment which determine the modification of cellulose fiber properties. It was estimated from XPS data that the degrees of modification/grafting were about 23% for CC/NIPAAm and 13% for CC/PNIPAAm. Such treatment could be transferred to practical technologies, particularly in textile applications and special applications in the medical field. Copyright © 2012 Society of Chemical Industry     

Studies on the effect of anions of various lithium salts in PEMA gel polymer electrolytes

This research synthesized graft copolymers of chitosan‐g‐poly(N‐isopropyl acrylamide) (CS‐g‐PNIPAAm) by UV‐initiated free‐radical polymerization of NIPAAm monomer to CS selectively at the C‐6 position of pyranose ring. First, amino groups in CS were protected by reaction with phthalic anhydride (PA) to form PACS. The degree of phthaloylation was carefully controlled to ensure that most amino groups were protected, and only a very small amount of hydroxyl groups were reacted. In the second step, the vinyl functional group was introduced to the PACS by reaction with a vinyl compound containing an isocyanate group (3‐isopropenyl‐αα′‐dimethylbenzyl isocyanate), through the urethane linkage with hydroxyl groups at the C‐6 position. The phthaloyl groups were then removed by hydrazine to recover the amino groups in CS. Finally, PNIPAAm was grafted to the vinyl CS at the C‐6 position by UV‐initiated free‐radical polymerization. The synthesized CS‐g‐PNIPAAm copolymers were confirmed to have a structure of an AB‐crosslinked graft copolymer. Respectively, these copolymer hydrogels exhibited pH‐ and thermal‐responsive swelling properties in an aqueous solution due to their CS and PNIPAAm components. The test of cell viability with L929 fibroblast revealed that the CS‐g‐PNIPAAm copolymers having a grafting ratio lower than 1.7 had cellular compatibility as good as pure CS. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Functionalization of poly(ester‐urethane) surface by radiation‐induced grafting of N‐isopropylacrylamide using conventional and reversible addition–fragmentation chain transfer‐mediated methods

The functionalization of poly(ester‐urethane) (PUR) surface was conducted using radiation‐induced grafting. A thermosensitive layer constructed from N‐isopropylacrylamide (NIPAAm) was introduced onto a polyurethane film and characterized using attenuated total reflection Fourier transform infrared and X‐ray photoelectron spectroscopies and contact angle measurements. Size exclusion chromatography was used to analyse the PUR‐graft‐PNIPAAm copolymers and homopolymers formed in solution. Additionally, reversible addition–fragmentation chain transfer (RAFT) polymerization was performed in order to obtain PNIPAAm‐grafted surfaces with well‐defined properties. Atomic force microscopy was used to evaluate the surfaces synthesized via conventional and RAFT‐mediated grafting methods. The results of various techniques confirmed the successful grafting of NIPAAm from PUR film. © 2015 Society of Chemical Industry     

Thermo‐ and pH‐responsive behaviors of graft copolymer and blend based on chitosan and N‐isopropylacrylamide

Thermo‐ and pH‐sensitive polymers were prepared by graft polymerization or blending of chitosan and poly(N‐isopropylacrylamide) (PNIPAAm). The graft copolymer and blend were characterized by Fourier transform‐infrared, thermogravimetric analysis, X‐ray diffraction measurements, and solubility test. The maximum grafting (%) of chitosan‐g‐(N‐isopropylacrylamide) (NIPAAm) was obtained at the 0.5 M NIPAAm monomer concentration, 2 × 10⁻³ M of ceric ammonium nitrate initiator and 2 h of reaction time at 25°C. The percentage of grafting (%) and the efficiency of grafting (%) gradually increased with the concentration of NIPAAm up to 0.5 M, and then decreased at above 0.5 M NIPAAm concentration due to the increase in the homopolymerization of NIPAAm. Both crosslinked chitosan‐g‐NIPAAm and chitosan/PNIPAAm blend reached an equilibrium state within 30 min. The equilibrium water content of all IPN samples dropped sharply at pH > 6 and temperature > 30°C. In the buffer solutions of various pH and temperature, the chitosan/PNIPAAm blend IPN has a somewhat higher swelling than that of the chitosan‐g‐NIPAAm IPN. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1381–1391, 2000     

Quick Polymerization from Electrospun Macroinitiators for Making Thermoresponsive Nanofibers

Thermoresponsive nanofibers by very fast grafting of N,N‐isopropylacrylamide (NIPAAm) from electrospun atom transfer radical polymerization (ATRP) macroinitiator are presented in this work. The heterogenous grafting of NIPAAm onto macroinitiator fibers could be done in few minutes, i.e., in less than 5 min. The procedure involved electrospinning of an ATRP macroinitiator and subsequent PNIPAAm grafting using “grafting from” technique. The ATRP Macroinitiator was based on a copolymer of methyl methacrylate (MMA) and 2‐hydroxyethyl methacrylate (HEMA). The growth of the PNIPAAm layer on electrospun fibers was followed by IR‐spectroscopy and SEM analysis. The temperature‐dependent‐phase transition was proven by contact angle measurements and could be shown on the same surface for many cycles.