Conducting polymer films fabricated by oxidative graft copolymerization of aniline on poly(acrylic acid) grafted poly(ethylene terephthalate) surfaces

A conductive polyaniline/poly(ethylene terephthalate) (PANI/PET) composite film was fabricated via the oxidative graft copolymerization of aniline (ANI) onto the plasma-induced poly(acrylic acid) (PAAc) grafted PET surface. The attenuated total reflectance Fourier transform infrared spectroscopy spectra (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS) results confirmed that PANI was successfully grafted onto the surface of the PAAc-g-PET films. The effects of the experimental conditions on the percentage of PANI grafted onto the PAAc-g-PET films were extensively investigated. A very high grafting percentage of ANI can be obtained through the acid-base reaction between the aniline monomer and PAAc on the PAAc-g-PET surface at high temperature. As a result, the grafting percentage of PANI can be increased to as high as 12.18 wt %, which causes the surface resistance of the PANI-g-PAAc-g-PET film to be reduced to about 1000 Omega/sq. We predicted that this is because of the high flexibility of the PAAc molecular chains and high solubility of aniline, both of which facilitate the binding of aniline to PAAc during this high temperature acid-base reaction. It was observed by atomic force microscopy (AFM) that the PANI-modified PET surface exhibits higher size irregularity and surface roughness, which further indicated that a much greater number of aniline molecules can be reactively bonded to and distributed along the grafted AAc chains and that the PANI-g-PAAc-g-PET surface resulting from the sequential oxidative graft copolymerization can possess higher electrical conductivity.     

SURFACE MODIFICATION OF POLYPROPYLENE MICROPOROUS MEMBRANE BY TETHERING POLYPEPTIDES

Two kinds of polypeptides were tethered onto the surface of polypropylene microporous membrane （PPMM） through a ring opening polymerization of L-glutamate N-carboxyanhydride initiated by amino groups which were introduced by ammonia plasma and y-aminopropyl triethanoxysilane treatments. X-ray photoelectron spectroscopy （XPS）, attenuated total reflectance Fourier transform infrared spectroscopy （FT-IR/ATR）, scanning electron microscopy （SEM）, together with water contact angle measurements were used to characterize the modified membranes. XPS analyses and FT-IR/ATR spectra demonstrated that polypeptides are actually grafted onto the membrane surface. The wettability of the membrane surface increases at first and then decreases with the increase in grafting degrees of polypeptide. Platelet adhesion and murine macrophage attachment experiments reveal an enhanced hemocompatibility for the polypeptide modified PPMMs. All these results give evidence that polypeptide grafting can simultaneously improve the hemocompatibility as well as reserve the hydrophobicity for the membrane, which will provide a potential approach to improve the performance of polypropylene hollow fiber microporous membrane used in artificial oxygenator.     

Characterization of N-isopropyl acrylamide/acrylic acid grafted polypropylene nonwoven fabric developed by radiation-induced graft polymerization

Radiation-induced graft copolymerization of N-isopropylacrylamide (NIPAAm) and acrylic acid (AA) mixture was carried out on polypropylene nonwoven fabric to develop a thermosensitive material and has been found to affect the thermal and physical characteristics of fabric. The grafted fabrics with different monomer ratios were characterized by thermal gravimetric analysis (TGA), fourier transform infrared spectroscopy (FTIR), differential scanning calorimetry (DSC), X-ray diffraction (XRD), contact angle and atomic force microscopy (AFM). Results of FTIR clearly indicated that poly(acrylic acid) and poly(N-isopropyl acrylamide) were successfully grafted onto the membrane surface. TGA results showed that the thermal stability of PP fabric increased after grafting of NIPAAm/AA. The crystallinity values from DSC and XRD were found to decrease with increase in degree of grafting because of the addition of grafted chains within the noncrystalline region. The decrease in contact angles of the grafted fabric with an increase of the degree of grafting shows that PNIPAAm/PAA exists as the hydrophilic component. The increase in surface roughness after grafting was observed by AFM.     

Chain-length dependence of the antifouling characteristics of the glycopolymer-modified polypropylene membrane in an SMBR

Membrane-bioreactor processes have increased considerably in recent years. However, the natural disadvantages of common membrane materials, such as hydrophobic surface, cause membrane fouling and cumber further extensive applications. In this work, hydrophilic surface modification of polypropylene microporous membranes was carried out by the sequential photoinduced graft polymerization of d-gluconamidoethyl methacrylate (GAMA) to meet the requirements of wastewater treatment and water reclamation applications. The grafting density and grafting chain length were controlled independently in the first and second step, respectively. Attenuated total reflection–Fourier transform infrared spectroscopy (FT-IR/ATR) and X-ray photoelectron spectroscopy (XPS) were employed to confirm the surface modification on the membranes. Water contact angle was measured by the sessile drop method. Results of FT-IR/ATR and XPS clearly indicated that GAMA was grafted on the membrane surface. It was found that the grafting chain length increased reasonably with the increase of the UV irradiation time. Water contact angle on the modified membrane decreased with the increase of the grafting chain length, and showed a minimum value of 43.2°, approximately 51.8° lower than that of the unmodified membrane. The pure water fluxes for the modified membranes increased systematically with the increase of the grafting chain length. The effect of the grafting chain length on the antifouling characteristics in a submerged membrane-bioreactor for synthetic wastewater treatment was investigated. After continuous operation in the submerged membrane-bioreactor for about 70 h, reduction from pure water flux was 90.7% for the virgin PPHFMM, and ranged from 80.8 to 87.2% for the modified membranes, increasing with increasing chain length. The flux of the virgin PPHFMM membrane after fouling and subsequent washing was 31.5% of the pure water flux through the unfouled membrane; for the modified membranes this ranged from 27.8 to 16.3%, decreasing with increasing chain length. These results demonstrated that the antifouling characteristics for the glucopolymer-modified membranes were improved with an increase in GAMA chain length.     

聚丙烯表面接枝PNIPAAm膜Ⅰ.光接枝反应和表面形态结构研究

以氧杂蒽酮或二苯甲酮为引发剂 ,通过紫外光引发表面接枝聚合的方法在聚丙烯薄膜表面引入了具有温度敏感特性的聚异丙基丙烯酰胺 (PNIPAAm)接枝聚合物层 .提高紫外光强度和接枝反应温度均有利于接枝率增大 ,而单体浓度对接枝率的影响存在最佳值 ,为 0 1 8mol L .在引发剂预浸渍引发接枝和休眠基引发接枝这两种方式中 ,后者能够实现更高的接枝率 .红外光谱 (FTIR)、X射线光电子能谱化学分析 (ESCA)和扫描电子显微镜 (SEM)等对接枝层组成的表征结果证实了接枝层的存在 .在不同温度下 ,接枝膜的FTIR谱图中酰胺I带和酰胺II带特征吸收峰发生位移 ,表明它具有温度敏感特性 .同时 ,SEM研究发现由于接枝膜的温度敏感特性而导致的球状表面形态结构     

Electron-beam graft-modified membranes with externally controlled flux

Pre-irradiation grafting as a means to modify commerical poly(vinylidene fluoride) (PVDF) membranes has been studied. The membranes prepared were weak cation-exchange membranes (acrylic acid functionality), anion-exchange membranes (trimethyl ammonium functionality) and temperature-sensitive membranes (N-isopropyl amide functionality). Different graft loads were obtained by varying reaction time, radiation dose and in the case of acrylic acid the graft solution composition. The trimethyl ammonium chloride functionality was obtained by grafting vinyl benzyl chloride onto a PVDF membrane and aminating the benzyl chloride groups in a 45% trimethyl amine–water solution. For a membrane grafted with 9 wt% acrylic acid the flux increased approximately 70 times when the pH was decreased from 6 to 2. For a membrane with 5 wt% trimethyl ammonium functionality the flux increased both when pH was decreased below 3 and increased above 11. For a membrane grafted with 18 wt% N-isopropyl acrylamide a sharp increase of flux was observed when the temperature was raised above 32°C.     

Functional and surface-active membranes from poly(vinylidene fluoride)-graft-poly(acrylic acid) prepared via RAFT-mediated graft copolymerization

Poly (vinylidene fluoride) (PVDF) with "living" poly (acrylic acid) (PAAc) side chains (PVDF-g-PAAc) was prepared by reversible addition-fragmentation chain transfer (RAFT)-mediated graft copolymerization of acrylic acid (AAc) with the ozone-pretreated PVDF. The chemical composition and structure of the copolymers were characterized by elemental analysis, Fourier transform infrared spectroscopy, and thermogravimetric analysis. The copolymer could be readily cast into pH-sensitive microfiltration (MF) membranes with enriched living PAAc graft chains on the surface (including the pore surfaces) by phase inversion in an aqueous medium. The surface composition of the membranes was determined by X-ray photoelectron spectroscopy. The morphology of the membranes was characterized by scanning electron microscopy. The pore size distribution of the membranes was found to be much more uniform than that of the corresponding membranes cast from PVDF-g-PAAc prepared by the "conventional" free-radical graft copolymerization process. Most important of all, the MF membranes with surface-tethered PAAc macro chain transfer agents, or the living membrane surfaces, could be further functionalized via surface-initiated block copolymerization with N-isopropylacrylamide (NIPAAM) to obtain the PVDF-g-PAAc-b-PNIPAAM MF membranes, which exhibited both pH- and temperature-dependent permeability to aqueous media.     

Synthesis and Characterization of Poly(methyl methacrylate)-b-Polystyrene/TiO2 Nanocomposites Via Reversible Addition-Fragmentation Chain Transfer Polymerization

A diblock copolymer, poly(methyl methacrylate)-b-polystyrene (PMMA-b-PS), was grafted onto the surface of nano-titania (nano-TiO₂) successfully via reversible addition-fragmentation chain transfer (RAFT) polymerization. The surface of TiO₂ nanoparticles was modified initially by attaching dithioester groups to the surface using silane coupling agent 3-(chloropropyl)triethoxy silane and sodium ethyl xanthate. The polymerization of methyl methacrylate and styrene were then initiated and propagated on the TiO₂ surface by RAFT polymerization. The resulting composite nanoparticles were characterized by means of XPS, FT-IR, ¹H NMR and TGA. The results confirmed the successful grafting of poly(methyl methacrylate) (PMMA) and diblock copolymer chains onto the surface of TiO₂. The amount of PMMA grafted onto the TiO₂ surface increased with the polymerization time. Moreover, the kinetic studies revealed that the ln([M]₀/[M]), where [M]₀ is the initial and [M] is the time dependent monomer concentrations, increased linearly with the polymerization time, indicating the living characteristics of the RAFT polymerization.     

Grafting of regenerated cellulose membrane by surface‐initiated atom transfer radical polymerization and its pH‐resposive behavior

Regenerated cellulose (RC) membranes which have pH modulated permeability have been prepared by anchoring the hydroxyl groups on the membrane surface with 2‐bromoisobutyryl bromide, followed by grafting with acrylic acid (AA) using atom transfer radical polymerization (ATRP). The obtained membranes were analyzed by X‐ray photoelectron spectroscopy (XPS), Fourier transform infrared attenuated total reflection spectrometer (ATR‐FTIR), scanning electron microscopy (SEM), TGA and the results showed that AA had been grafted onto the membrane surfaces successfully. Then the pH modulated permeability properties were tested by water flux measurement. All results show that the pH modulated permeability properties of a RC membrane can be obtained by surface‐initiated ATRP. Copyright © 2010 John Wiley & Sons, Ltd.     

Novel interpenetrating smart polymer networks grafted onto polypropylene by gamma radiation for loading and delivery of vancomycin

Gamma radiation was used in every step of the synthesis of a sequential interpenetrating polymer network made of two “smart” polymers: poly(acrylic acid) (PAAc) and poly (N-isopropylacrylamide) (PNIPAAm), the latter grafted onto polypropylene (PP) films (PP-g-PNIPAAm) with the aim of developing medicated coatings for medical devices. Three steps were followed for obtaining net-PP-g-PNIPAAm-inter-net-PAAc: graft copolymerization of PNIPAAm onto PP films by gamma pre-irradiation oxidative method, cross-linking of PP-g-PNIPAAm by gamma irradiation in water to form the first network, with or without N,N′-methylenebis(acrylamide) (MBAAm), and finally the formation of the second network through the polymerization and cross-linking of AAc inside cross-linked PP-g-PNIPAAm by a low gamma radiation dose of 2.5 kGy. The films were characterized regarding the amount of grafted polymers and their composition (FTIR-ATR), thermal behavior (DSC), temperature- and pH-responsive swelling and contact angle (critical pH 6 and lower critical solution temperature ∼33 °C), and loading and release rate of vancomycin. Drug loading was driven by specific interactions between vancomycin and PAAc. Drug-loaded films sustained the delivery for several hours at pH 7.4 and provided release rate values adequate for killing bacteria attempting to adhere the surface of the films.     

Graft copolymerization kinetics of acrylic acid onto the poly(ethylene terephthalate) surface by atmospheric pressure plasma inducement

After one atmospheric pressure plasma treatment of poly(ethylene terephthalate) (PET) film, acrylic acid (AAc) in aqueous solution was successfully graft‐copolymerized onto PET films. The effects of reaction time, AAc monomer concentration and reaction temperature on grafting behavior of AAc were systematically studied. Possible reaction kinetics of plasma‐induced graft copolymerization, starting from initial hydroperoxide decomposition, were proposed. Through the Arrhenius analysis about graft copolymerization kinetics of AAc monomers on PET surface, it was revealed that the activation energies of decomposition, propagation and termination were 98.4, 63.5, and 17.5 kJ/mol, respectively. The temperature around 80 °C was favorable not only for the formation of oxide radicals through the thermal decomposition of hydroperoxide on PET surface but also for the extension of graft copolymer chain through direct polymer grafting. Poly(acrylic acid) (PAAc) grains grafted onto PET surfaces possessed relatively uniform size and both PAAc grain size and surface roughness increased with increasing the grafting degree of AAc. The increase of grain size with increasing grafting degree results from the possibility of forming long chain graft copolymers and their shielding of reactive sites. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1594–1601, 2008     

Novel reversible thermoresponsive nanogel based on poly(ionic liquid)s prepared via RAFT crosslinking copolymerization

In this study, a facile strategy for the preparation of thermo‐ and pH‐responsive nanogels through reversible addition–fragmentation transfer (RAFT) crosslinking copolymerization of ionic liquid‐based monomers is demonstrated. The use of chain transfer agents (CTAs) containing carboxyl group in the RAFT polymerizations is the key to producing highly thermoresponsive nanogels. Experimental results demonstrate that the critical gelation temperature of the as‐prepared nanogels can be tuned by adjusting the feed ratio of monomer and CTA. Variable temperature Fourier transform infrared measurements and control experiments indicate that hydrogen‐bonding interactions between the carboxyl groups of CTAs are responsible for the thermoresponsive behaviors of poly(ionic liquid) (PIL)‐based nanogels. Furthermore, PIL‐based nanogels are also found to be pH‐sensitive, and can be further decorated by poly(N‐isopropylacrylamide) (PNIPAAm) via surface grafting polymerization. PNIPAAm‐grafted nanogel aqueous solutions can be reversibly transformed into macrogels upon a change in temperature. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 169–178     

Effect of rate retardation in RAFT grafting polymerization from silicon wafer surface

Polystyrene and poly(butyl acrylate) were grafted from silicon wafer surface by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Three RAFT agents were immobilized onto silicon wafer through their leaving/initiating groups (R group). Grafting polymerization of butyl acrylate (BA) and styrene (St) was then carried out from the immobilized RAFT agents. The immobilization of the RAFT agents and the subsequent grafting polymerization of St and BA were evaluated by ellipsometry and X‐ray photoelectron spectroscopy. It was found that type of monomer, structure of RAFT agent, and local RAFT concentration on the surface have dramatic influences on the thickness of grafted polymer layer. The grafting polymerization with more severe rate retardation effect yielded thinner polymer films on the silicon wafer. Selection of a RAFT agent with little rate retardation was critical in the grafting polymerization to achieve thick films. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 970–978, 2008     

Mitigated membrane fouling in an SMBR by surface modification

Fouling is a major obstacle in membrane processes applied in membrane bioreactor. To improve the antifouling characteristics of polypropylene hollow fiber microporous membranes (PPHFMMs) in a submerged membrane bioreactor (SMBR), the PPHFMMs were surface modified by NH₃, CO₂ plasma treatment, photoinduced graft polymerization of acrylamide and acrylic acid. The structural and morphological changes on the membrane surface were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflection-Fourier transform infrared spectroscopy (FT-IR/ATR) and field emission scanning electron microscopy (FE-SEM). The change of surface wettability was monitored by contact angle measurements. The results of XPS and FT-IR/ATR clearly indicated the successful modification on the membrane surface. The static water contact angle of the modified membrane reduced obviously. The antifouling characteristics of the modified membranes in an SMBR were evaluated. The modified membranes showed better filtration performances in the submerged membrane bioreactor than the unmodified one, and the acrylic acid-grafted membrane presented the best antifouling characteristics. The results demonstrated that (1) the surface carboxyl-containing membranes were better than the surface amido-containing membranes; (2) surface-grafted membranes were better than the plasma-treated membranes.     

Raft mediated surface grafting of t‐butyl acrylate onto an ethylene–propylene copolymer initiated by gamma radiation

RAFT mediated grafting of poly(t‐butyl acrylate) onto the surface of a commercial poly(ethylene‐co‐propylene), Elpro, has been carried out using initiation by ⁶⁰Co γ‐radiation at 298 and 273 K. The polymerizations were in bulk monomer and using the RAFT agent 1‐phenylethyl phenyldithioacetate. The rates of homopolymerization and grafting were found to decrease with increasing RAFT agent concentration, indicating that both polymerization processes involve participation of the RAFT agent. There was good agreement between the predicted and experimental molecular weights of the homopolymer that had a narrow polydispersity. The poly(t‐butyl acrylate) grafts were hydrolyzed by trifluoroacetic acid to form poly(acrylic acid) grafts, which could either be further functionalized or used to control the surface polarity of the Elpro. ATR‐FTIR spectroscopy was used to characterize the grafts and Raman spectroscopy was used to assess the depth of the grafts. The water contact angle for the Elpro surface grafted with poly(acrylic acid) was found to be linearly dependent on the amount of the graft present. The living nature of the grafted chains was demonstrated by the addition of a second block of polystyrene. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1074–1083, 2007     

Preparation of dual stimuli‐responsive PET track‐etched membrane by grafting copolymer using ATRP

A dual stimuli‐responsive (pH and thermo) polyethylene terephthalate (PET) track‐etched membrane has been prepared using atom transfer radical polymerization (ATRP). First, ATRP initiator 2‐bromoisobutyryl bromide was anchored onto the membrane surface. Then, 2‐hydroxyethyl‐methacrylate (HEMA) and N‐isopropylacrylamide (NIPAAm) were grafted onto the membrane surface using ATRP. X‐ray photoelectron spectroscopy, ATR‐Fourier transform infrared spectroscopy, scanning electron microscopy and thermogravimetric analysis were used to characterize the membrane structure and thermal properties; water flux measurement was used to investigate the double stimuli‐responsive property of the obtained membrane. The results indicate that the PHEMA and PNIPAAm binary grafted PET track‐etched membrane has double environmental responsiveness. This method provides a potential modification method for preparing functional membranes. Copyright © 2012 John Wiley & Sons, Ltd.     

Thermosensitive graphene nanocomposites formed using pyrene‐terminal polymers made by RAFT polymerization

Thermosensitive graphene‐polymer composites have been prepared by attaching poly(N‐isopropylacrylamide) (PNIPAAm) onto the basal plane of graphene sheets via π‐π stacking. Pyrene‐terminated PNIPAAm was synthesized using reversible addition fragmentation chain transfer (RAFT) polymerization via a pyrene‐functional RAFT agent. Aqueous solutions of the graphene‐polymer composites were stable and thermosensitive. The lower critical solution temperature (LCST) of pyrene‐terminated PNIPAAm was measured to be 33 °C. When the pyrene‐functional polymer was attached to graphene the resultant composites were also thermosensitive in aqueous solutions exhibiting a reversible suspension behavior at 24 °C. Atomic force microscopy (AFM) analysis revealed that the thickness of a graphene‐PNIPAAm (M_n: 10,000 and PDI: 1.1) sheet was ～5.0 nm. The surface coverage of polymer chains on the graphene basal plane was calculated to be 7.2 × 10^?11 mol cm^?2. The graphene‐PNIPAAm composite material was successfully characterized using X‐ray photoelectron spectroscopy (XPS), attenuated total reflection infrared (ATR‐IR) spectroscopy, and thermogravimetric analysis (TGA). © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 425–433, 2010     

通过RAFT聚合制备SiO2/接枝共聚物纳米杂化粒子

以二氧化硅(SiO2)纳米粒子表面键接的二硫代苯甲酸酯作为可逆加成-断裂-链转移(RAFT)聚合反应的链转移剂, 在室温下引发苯乙烯和马来酸酐进行表面RAFT交替共聚反应, 制得了SiO2/苯乙烯-alt-马来酸酐杂化材料. 通过聚氧化乙烯(PEO)的羟基与马来酸酐的酯化反应, 将PEO接枝到SiO2纳米粒子的表面, 增加了硅粒子的生物相容性. 用FTIR, TGA和TEM对杂化材料的结构、组成和形貌进行了表征.     

Immobilization of RAFT agents on silica nanoparticles utilizing an alternative functional group and subsequent surface‐initiated RAFT polymerization

Silica–polystyrene core‐shell particles were successfully prepared by surface‐mediated reversible addition fragmentation chain transfer (RAFT) polymerization of styrene monomer from the surfaces of the silica‐supported RAFT agents. Initially, macro‐RAFT agents were synthesized by RAFT polymerization of γ‐methacryloxypropyltrimethoxysilane (MPS) in the presence of chain transfer agents (CTAs). Immobilization of CTAs onto the silica surfaces was then performed by reacting silica with macro‐RAFT agents via a silane coupling. Grafting of polymer onto silica forms core‐shell nanostructures and shows a sharp contrast between silica core and polymer shell in the phase composition. The thickness of grafted‐polymer shell and the diameter of core‐shell particles increase with the increasing ratio of monomer to silica. A control experiment was carried out by conventional free radical emulsion copolymerization of MPS‐grafted silica and styrene under comparable conditions. The resulting data provide further insight into the chemical composition of grafted‐polymers that are grown from the silica surface through RAFT process. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 467–484, 2009     

Surface modification of polyethylene fiber by graft polymerization

To improve the wettability and adhesion, graft polymerization of acrylamide (AAm) and glycidyl methacrylate (GMA) was performed onto the surface of ultra-high modulus polyethylene (UHMPE) fiber pretreated with Ar plasma. Following the plasma treatment and the subsequent exposure to air to introduce peroxides onto the fiber surface, graft polymerization onto the UHMPE fiber was allowed to proceed from the polymer peroxides either in deaerated monomer solution at an elevated temperature (degassing method), or in aerated monomer solution containing riboflavin at 30°C under UV irradiation (photoinduction method). The monomer solution was prepared from water and dioxane for AAm and GMA, respectively. After rigorous removal of homopolymers, surface analysis of the grafted fibers was performed with ATR-FTIR and XPS, which revealed that PAAm and PGMA chains were grafted in the surface region of fibers. The grafting rate of PAAm by the photoinduction method was much higher than that by the degassing method when compared at the same concentration of the AAm solution. The amount of PGMA grafted was greatly affected by UV irradiation time, but depended on plasma treatment time to an insignificant extent if the treatment was carried out for longer than 30 s. Reaction of propylamine with the PGMA-grafted surface resulted in the appearance of a nitrogen peak in the XPS spectrum, suggesting the presence of epoxy groups on the surface of PGMA grafted fiber. © 1994 John Wiley & Sons, Inc.