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     

Amphiphilic copolymer grafted "smart surface" enhanced by surface roughness

Polystyrene-poly(acrylic acid) (PS-PAA) block copolymers polymerized by atom transfer radical polymerization were covalently grafted to both smooth and microtextured surfaces. These amphiphilic copolymers were utilized to create smart surfaces, which can be responsive to external stimuli, e.g., pH values or organic solvent. Atom force microscopy, field emission scanning electron microscopy, and contact angle measurements were employed to investigate the physiochemical features of the copolymer brushes. It was found that the wettability of surfaces depended on both the PS/PAA molar ratio and external solvent properties. Hydrophilic surfaces were obtained after treatment with basic solution, as well as a polar solvent, such as ethanol. With treatment with acidic solution or toluene, the surface could be reversibly turned relatively hydrophobic, probably due to the rearrangement or reorganization of polymer chains. Moreover, rougher surfaces, which were microtextured by ZnO nanorods, were incorporated into this adaptive system to enhance the tunable range of wettability.     

Adsorption of trypsin onto styrene-2-hydroxyethyl methacrylate copolymer microspheres and its enzymatic activity

Effects of the surface hydrophilicity of styrene-2-hydroxyethyl methacrylate (S-HEMA) copolymer microspheres on the adsorption immobilization of trypsin and on its enzymatic activity were discussed. In the case of a polystyrene (PS) microsphere, the amount of adsorption was large, whereas the enzymatic activity of the adsorbed trypsin was low. On the other hand, in the case of an S-HEMA copolymer microsphere whose HEMA content was 10 mole %, the maximum specific activity of trypsin adsorbed was nearly equal to that of free trypsin, although the amount of adsorption decreased to about 65 % of that in PS. Accordingly, total activity, which is the product of the amount of adsorption and the specific activity, could be enhanced by controlling the surface hydrophilicity of the microsphere.Part LXXXVII of the series Studies on Suspension and Emulsion.     

The surface characterization of styrene-acrylamide copolymer latex particles and their deposition onto fibers

The surface characteristics of styrene-acrylamide (St-AAm) copolymer latex particles were investigated and their deposition onto polyamide (Nylon 6), polyester (polyethylene terephthalate) and polyacrylonitrile fibers was studied. Conductometric titrations and viscosity measurements of latex dispersions revealed the presence of a water-soluble polymer layer on the particle surface and the thickness of its polymer layer increased with increasing acrylamide fraction in a latex particle. The deposition rates of St-AAm copolymer latices onto Nylon 6 and polyester fibers increased with increasing acrylamide fraction and decreasing pH at a constant ionic strength. These deposition phenomena onto Nylon 6 and polyester fibers agreed qualitatively with prediction based on the electrokinetic data of the latices and the fibers. However, a participation of attractive interaction due to an increase in acrylamide fraction was also suggested.The deposition rate onto polyacrylonitrile fiber decreased with increasing acrylamide fraction in spite of a decrease in electrostatic repulsive interaction, and it was found that a specific large repulsive interaction acts between polyacrylonitrile fiber and St-AAm copolymer latex particles.This paper is part VIII in a series on Interfacial electrical studies on the deposition of polymer latexes onto fabrics and the removal of these deposited latexes. Part VII: Tamai H, Kimura I,Suaza T Coll Polym Sci 261: 661 (1983)     

Study on chemical, UV and gamma radiation-induced grafting of 2-hydroxyethyl methacrylate onto chitosan

In the present study, 2-hydroxyethyl methacrylate has been grafted onto chitosan by using either chemical initiation, or photo-induction or gamma radiation-induced polymerisation, all under heterogeneous conditions. The evidence of grafting was provided by Fourier transform infrared spectroscopy and thermal analysis.

The results concerning the effect of initiator concentration, initial monomer concentration and dose rate influencing on the yield of grafting reactions are presented. These suggest that gamma irradiation is the method that leads to higher yields of grafting.     

Some investigations on the post radiation grafting of acrylamide onto polyethylene films

A study has been made on the post radiation grafting of aqueous acrylamide onto low density polyethylene film. It was found that the addition of 0.05 wt % Mohr's salt reduced effectively the homopolymerization of acrylamide and the grafting process was successfully achieved. The dependence of the grafting rate on the preirradiation dose and monomer concentration was found to be of 1.43 and 1.4 order, respectively. The overall activation energy for the graft polymerization was found to be 13.5 and 1.95 Kcal/mol below and above 45°C, respectively. Some properties of the graft copolymer such as swelling behaviour, electrical conductivity, and reverse osmosis desalination of saline water (water flux and salt rejection), were also investigated and the possibility of its uses in the practical applications was discussed.     

Imparting antifouling properties of poly(2-hydroxyethyl methacrylate) hydrogels by grafting poly(oligoethylene glycol methyl ether acrylate)

The antifouling properties of poly(2-hydroxyethyl methacrylate- co-methyl methacrylate) hydrogels were improved by the surface grafting of a brush of poly(oligoethylene glycol methyl ether acrylate) [poly(OEGA)]. The atom-transfer radical polymerization (ATRP) of OEGA (degree of polymerization = 8) was initiated from the preactivated surface of the hydrogel under mild conditions, thus in water at 25 degrees C. The catalytic system was optimized on the basis of two ligands [1,1,4,7,10,10-hexamethyl-triethylenetetramine (HMTETA) or tris[2-(dimethylamino)ethyl]amine (Me6TREN)] and two copper salts (CuIBr or CuICl). Faster polymerization was observed for the Me 6TREN/CuIBr combination. The chemical composition and morphology of the coated surface were analyzed by X-ray photoelectron spectroscopy, attenuated total reflectance Fourier transform infrared spectroscopy, contact angle measurements by the water droplet and captive bubble methods, scanning electron microscopy, and environmental scanning electron microscopy. The hydrophilicity of the surface increased with the molar mass of the grafted poly(OEGA) chains, and the surface modifications were reported in parallel. The antifouling properties of the coatings were tested by in vitro protein adsorption and cell adhesion tests, with green fluorescent protein, beta-lactamase, and lens epithelial cells, as model proteins and model cells, respectively. The grafted poly(OEGA) brush decreased the nonspecific protein adsorption and imparted high cell repellency to the hydrogel surface.     

Determination of surface area of copolymer latex particles by surface tension measurements

The surface tension γ of four copolymer latices, of their respective serums, and of aqueous solutions of dispersant alone were measured at various dilutions. By extrapolating the surface excess of dispersant (calculated by the Gibbs adsorption equation) both at the aqueous solution surface and at the serum surfaces to 1/c = 0 (c being the bulk concentration of dispersant) the same limiting site area A_lim per adsorbed molecule was determined. Amounts of dispersant adsorbed by copolymer particles at various dilutions were determined from differences between the known total concentrations of the dispersant in latex and in serum at the same γ. These values were then extrapolated to the maximum adsorption at 1/c = 0 in latex. The surface area of copolymer particles was determined therefrom by using A_lim. The average particle radius calculated this way agrees reasonably well with electron microscope measurements. Thus it appears that the method for determining latex particle surface area by surfactant titration may be calibrated by means of the Gibbs adsorption equation, provided one uses A_lim and not the site area at the critical micelle concentration of dispersant.     

Grafting and patterned grafting of block copolymer nanotubes onto inorganic substrates

Chemical patterning of inorganic substrates by soft lithography has enabled various high-tech applications and cutting-edge fundamental research. In this paper, we report on methods for the grafting and patterned grafting of block copolymer nanotubes onto glass and mica surfaces. Under optimized conditions the density of such grafted nanotubes can be high, and most of the grafted tubes are in a standing position even after solvent evaporation. Surfaces modified with exotic reagents such as block copolymer nanofibers or nanotubes may find applications in biosensing, etc.     

Grafting onto wool. I. Ceric ion-initiated grafting of poly(methyl acrylate) onto wool

Poly(methyl acrylate) has been grafted onto wool by using ceric ion as redox initiator in an aqueous medium. Initiation by ceric ammonium nitrate (CAN) was carried out in the presence of nitric acid of varying concentration at 35, 45, and 50°C for a period of 1.5 or 3 hr. Percent grafting was found to be dependent on concentrations of acid and monomer, reaction time, and temperature. Above 45°C, a considerable amount of homopolymer was formed; at 35°C, very little grafting of poly(methyl acrylate) was observed. Nitric acid catalyzed the reaction and a concentration of 0.17–0.19M HNO₃ was found suitable.     

Polymerization of acrylates by atom transfer radical polymerization. Homopolymerization of 2-hydroxyethyl acrylate

The application of atom transfer radical polymerization (ATRP) to the homopolymerization of 2-hydroxyethyl acrylate, a functional monomer, is reported. The polymerizations exhibit first-order kinetics, and molecular weights increase linearly with conversion. Polydispersities remain low throughout the polymerization (M_w/M_n ≈ 1.2). Reactions were conducted in bulk and in 1 : 1 (by volume) aqueous solution; the latter demonstrates the resilience of ATRP to protic media. Analysis of poly(2-hydroxyethyl acrylate) by MALDI-MS and ¹H-NMR shows M_n,exp to be much closer to M_n,th than those observed by SEC using polystyrene standards. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1417–1424, 1998     

Stimuli-responsive membranes through peroxidation radiation-induced grafting of 2-hydroxyethyl methacrylate (2-HEMA) onto isotactic polypropylene film (IPP)

Stimuli-responsive membranes were prepared by peroxidation radiation-induced grafting of 2-hydroxyethyl methacrylate (2-HEMA) onto IPP. The radioactive isotope ⁶⁰Co was used as the source of gamma radiation. A plausible mechanism of grafting has been proposed. Using this method, the degree of grafting and morphology could be controlled through the variation of reaction parameters such as total dose, inhibitor concentration, monomer concentration, reaction time, reaction temperature and solvents. Maximum percentage of grafting (210?%) was obtained at total radiation dose of 20?kGy. The graft copolymerization reaction was carried out for 3?h with 20?v/v% of the monomer (2-HEMA) in methanol at 85?°C using 0.06?wt% of FeCl₃ as inhibitor. The chemical structures of grafted membranes were characterized by Fourier transform infrared spectroscopy (FTIR) which indicates that HEMA has been grafted onto IPP. The atomic force microscopy (AFM), scanning electron microscopy (SEM) techniques were used to assess the morphological characterization of the membranes, revealing the roughness of the surface. These membranes were investigated for their swelling behavior. pH-sensitivity and the dyeability of the grafted and ungrafted membranes have also been studied.     

Quantitative determination of the surface composition of acrylate copolymer latex films by XPS (ESCA)

The interaction of copolymer latex particles with emulsifiers is governed to a great extent by the monomer composition of the particle surface. In this article it is demonstrated that for methylmethacrylate butylacrylate copolymer latexes this quantity, within certain limits, may be determined by XPS (ESCA) by a detailed analysis of the C(1s) line. It is shown that in this analysis secondary shifts in binding energy caused by the two carboxyl-oxygen atoms have to be taken into account, a fact that has been neglected in the literature so far.     

水溶性聚合物和两亲聚合物:14.丙烯酰胺/2-丙烯酰胺基十六烷磺酸铵无规共聚物

水溶液中用硫酸亚铁-异丙苯过氧化氢氧化还原引发体系合成了丙烯酰胺(AM)/2-丙烯酰胺基十六烷磺酸铵(AMC_(16)SNH_4)无规共聚物。用元素分析、IR、~(13)C-NMR和~1H-NMR对其进行了表征。对水溶液性质的研究结果表明,与部分水解聚丙烯酰胺相比,这种新型共聚物有着优异的耐盐性、耐温性和贮存稳定性。     

Modification of the surface properties of porous nanometric zirconia particles by covalent grafting

We here report on the covalent grafting of various phosphated species (phosphoric acid, phenylphosphonic acid, and octyl phosphate) onto the surface of monoclinic zirconia nanoparticles obtained by hydrothermal treatment of zirconium acetate. The initial particles are 60 nm aggregates of nanometric primary grains and present an inner porosity. Small-angle X-ray scattering shows that the high specific area of the colloidal particles (450 m2 x g(-1)) decreases to 150 m2 x g(-1) upon drying. Therefore, phosphated reactants can access the whole internal surface of the aggregates only before drying. The surface of the particles can be covered with functional groups bound through a variable number of Zr-O-P bonds. Several factors probably enhance the reaction between the particles and the phosphates or phosphonates: the large specific area of the particles, a fully accessible porous network, and a large concentration of surface terminal groups. At the same time, the morphology of the particles is well preserved upon grafting. This is due to the good crystallinity of the primary grains that constitute the particles. In addition, the grafting drastically modifies the surface properties of the colloids. For example, the polarizability of the particles decreases in the sequence -POH > as-prepared ZrO2 > -PC6H5 > -POC8H17. Furthermore, the grafting of octyl phosphate allows exclusion of water from pores of 2 nm radius, up to hydrostatic pressures of 20 MPa.     

Preparation of pH- and thermo-sensitive hydrogel by two-step grafting of acrylamide and acrylic acid onto preirradiated polyethylene film

Two-step grafting reaction of acrylamide (AAm) and acrylic acid (AAc) onto preirradiated polyethylene (PE) film were performed. The effects of irradiation dose, reaction temperature and reaction time on the grafting yield were studied. The effect of reaction time of the first step grafting on the yield of the second step grafting was also evaluated. The original and the irradiated PE films were tested by Fourier transform infrared (FTIR) spectroscopy in the attenuated total reflectance mode (ATR). The AAm and AAc grafted PE film appeared thermo- and pH-sensitive which are similar to the interpenetrating polymer network hydrogel. This revised version was published online in July 2006 with corrections to the Cover Date.     

Polymerization of acrylamide and methylmethacrylate at the surface of submicron polypyrrole particles

This paper presents two methods of encapsulation of polypyrrole latex particles of different sizes by an insulating polymer. The first method concerns the encapsulation by inverse emulsion polymerization of acrylamide with crosslinking agent. That method is effective for the smallest particles (about 100 nm). The second method concerns encapsulation by direct emulsion polymerization of methylmethacrylate. Inhibition of polymerization occurs if potassium persulfate is used as the initiator, whereas no inhibition is observed with 4,4′ azobis 4-cyanopentanoic acid as the initiator. These results are explained in terms of the ion-exchange capacity of conducting polymers. This second method seems to be effective for all the sizes of polypyrrole particles. These encapsulated particles have been characterized by transmission electron microscopy, scanning electron microscopy, quasi elastic light scattering, cyclic voltametry and electrophoresis. Cyclic voltammetry recently developed on aqueous suspensions of polypyrrole particles was revealed to be the best technique because of its simplicity and speed.     

Photoiniferter surface grafting of poly(methyl acrylate) using xanthates

The UV‐induced and catalyst‐free photoiniferter surface grafting using xanthate RAFT agents is studied. First, a novel silane containing a xanthate RAFT agent moiety is synthesized and successfully grafted onto a silicon wafer as confirmed by secondary ion mass spectrometry (SIMS). Next, using only methyl acrylate, solvent and UV light (365 nm) polymer brushes are grafted rapidly from the surface with film thicknesses up to 25 nm reached within half an hour. The obtained polymer films are thoroughly analyzed by X‐ray photoelectron spectroscopy (XPS), ToF‐SIMS, and AFM. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 2002–2007     

Pd/PdO在MCM-41介孔材料孔表面的溶液移植

利用PdCl~2溶液与介孔结构硅酸铝合成原粉反应,把Pd/PdO多用途催化剂移植到MCM-41材料孔表面。产物用XRD,热分析(TG/DTA),TEM,N~2吸附及FT-IR光谱等手段进行表征。结果表明,钯经由Si-O-Pd键负载在硅酸铝骨架及孔表面上。在有序介孔材料外表面沿着孔道方向粘附着直径为10-30nm的Pd/PdO晶粒。研究表明,采用这种液相移植的方法可以有效负载金属催化剂,并防止孔道堵塞。