Photochemical grafting of acrylated azo dyes onto polymeric surfaces. I. Grafting of 4-(N-ethyl,N-2-acryloxyethyl) amino, 4′-nitro,azobenzene onto polyamide and polypropylene fibers

Photochemically induced grafting and graft polymerization of 4-(N-ethyl, N-2-acryloxyethyl) amino, 4′-nitro, azobenzene(I), brought into contact with polyamide and polypropylene fibers by evaporation of solvent from toluene solutions, has been investigated kinetically at 45°C. Two constant-rate periods were observed. The first one was interpreted on the basis of an autosensitized grafting mechanism of monomeric or oligomeric species of (I), photochemically initiated by hydrogen abstraction from the polymer surface. This first step occurred at a rate dependent on the chemical nature of the substrate being faster for polyamide than for polypropylene by a factor of about 1.25; it was followed by a brief induction period, after which a transient autoacceleration led to a second constant rate process, independent of the substrate. This latter step was explained as an autosensitized photochemically induced graft polymerization of (I) on the first grafted layer.     

Effect of ultrasonic irradiation on ceric‐salt‐initiated grafting of methyl methacrylate onto regenerated cellulose film

Effect of ultrasonic irradiation on ceric salt (Ce⁴⁺)‐initiated grafting of methyl methacrylate (MMA) on regenerated cellulose film (thickness = 20 μm) was investigated under an air atmosphere in water solvent at 60°C. The grafting system with the ultrasonic irradiation was characterized by higher percentage of grafting and graft efficiency than the system without the irradiation. Reaction of cellulose with Ce⁴⁺ was also accelerated by the ultrasonic irradiation. No accelerating effect of grafting due to the ultrasonic irradiation was observed for the system under reduced pressure of 5 torr. The effect of the ultrasonic irradiation on the average molecular weight of MMA‐grafted chains was also studied. Moreover, the surface layer of the resulting grafted films was examined by attenuated total reflection–infrared (ATR–IR) measurement and scanning electron microscopy (SEM) observation. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 251–258, 1999     

Graft polymerization of 1,1-dihydroperfluorobutyl acrylate onto cellulose fabric

1,1-Dihydroperfluorobutyl acrylate was prepared and grafted onto cellulose fabric by means of γ-ray preirradiation to produce oil and water repellency. A 2% grafting was sufficient to impart oil and water repellency to cellulose fabric. In the case of 19.1% or 29.4% grafted fabrics, the grafting decreased rapidly with laundering, and the laundered fabric which possessed no oil and water repellency still had about 10% grafting of the perfluoro compound. Thus, the apparent graft polymerization takes place both on the surface and in the inner structure of the cellulose fiber; the polymer grafted onto the surface imparts oil and water repellency and is easily removed by laundering, whereas the polymer grafted onto the inner structure is hardly eliminated but does not impart oil and water repellency to the fabric.     

Grafting of acrylonitrile onto cellulose initiated by ceric ion

Acrylonitrile was grafted onto cellulose with the use of ceric salt as initiator and the grafting was found to be maximum at 0.6N acid concentration. The effect of monomer and initiator concentration on the extent of grafting was studied. A new method for quantitative estimation of extent of grafting on cellulose was developed and its validity was established. The grafted samples with 20% increase in weight were found to be highly resistant to microorganisms.     

电子束预辐照纤维素接枝丙烯酸的研究

研究了高能电子束辐照纤维素棉纱接枝丙烯酸的主要影响因素。讨论了接枝反应机理,认为大分子自由基是电子束预辐照纤维素接枝丙烯酸的主要活性中心。对棉纱接枝物的应用作了探索性的研究。     

Preparation of high PMMA grafted particle SiO2 using surface initiated free radical polymerization

In this work, a convenient surface-initiated free radical graft-polymerization method, by which polymethacrylic acid (PMAA) with a high grafting density was grafted on silica gel particles, was put forward, and it was feasible and effective. The coupling agent γ-aminopropyltrimethoxysilane (AMPS) was first bound onto the surfaces of silica gel particles, obtaining the modified particles AMPS-SiO₂. So a redox initiation system was constituted with the amino groups on the surfaces of AMPS-SiO₂ particles and ammonium persulphate in the solution. A great deal of primary free radicals on the surfaces of AMPS-SiO₂ particles is produced via the redox initiating reaction, so that the surface-initiated free radical graft- polymerization of methacrylic acid (MAA) on the silica gel particles was realized, giving the grafted particles PMAA/SiO₂ with a high grafting degree (about 30 g/100 g) of PMAA. The effects of the main factors on the surface initiated graft polymerization were examined and the corresponding mechanism was investigated in depth. The experimental results show that for this surface-initiated free radical graft-polymerization of MAA, the suitable temperature is 40 °C. If the temperature is over 40 °C, the graft polymerization will be affected negatively, and the grafting degree of PMAA will decline because of the intense heat decomposition of ammonium persulphate. During the graft polymerization, the grafted polymer layer that has formed is a hindrance to the subsequent graft polymerization. The used amount of initiator and the monomer concentration affect the graft polymerization greatly. The appropriate reaction conditions are as follows: reaction time of 10 h, initiator persulphate amount of 1.1% (it implies the mass percent of the monomer), and monomer MAA concentration of about 5% (it drives at the mass percent of the solution).     

Grafting of poly (methyl acrylate) onto sulfite pulp fibers and its effect on water absorbance

To prepare super water absorbent hydrogels of wood cellulose fibers, poly (methyl acrylate) (PMA) was copolymerized onto softwood sulfite pulp fibers using free radical initiator followed by alkaline hydrolysis. Ceric ammonium nitrate (CAN) was used as the free radical initiator. Effects of various parameters such as fiber concentration, monomer/pulp (M/pulp) ratio, CAN concentration, and reaction time on the grafting yield and on other grafting parameters were investigated. The graft conversion was the same from low to medium fiber concentration. The amount of initiator required was found to be independent of fiber concentration to achieve maximum grafting yield. Different fiber fractions (classified based on their length) have no effect on the grafting yield. The evidence of graft copolymerization was determined by using ATR‐IR spectroscopy. The X‐ray diffraction (XRD) analysis shows that grafting takes place both in amorphous and crystalline regions of cellulose fibers and the decrease in crystallinity of the grafted fibers with an increase in grafting yield was confirmed. The surface morphology of the PMA‐g‐cellulose was characterized by scanning electron microscopy (SEM). The water retention value of the hydrolyzed grafted pulp was determined based on a centrifugation technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Grafting of poly(acrylic acid) onto cellulosic microfibers and continuous cellulose filaments and characterization

Results from the grafting of poly(acrylic acid) (PAA) onto cellulosic microfibers and continuous cellulose filaments are presented. The grafting of PAA onto cellulosic fibers offers the possibility of developing enhanced ion exchange and fluid absorbency on the fibers. The grafting of PAA was carried out with a two‐step procedure. First, vinyl‐terminated ethoxy silane was deposited on the surface of the fiber. This was followed by a grafting polymerization reaction in aqueous media of acrylic acid with different concentrations of potassium persulfate (KPS), which acted as the initiator. The percentage of grafting increased with increasing KPS concentration and reached a maximum value at a concentration of about 0.4 wt % with respect to the weight of the fiber. The grafted copolymer was characterized by Fourier transform infrared spectroscopy. Strong evidence that the grafting reaction was successful was given by the presence of a band, with a maximum at 1732 cm^?1, that was characteristic of carbonyl group absorption and was not initially present in the cellulosic fibers. The water absorption of the cellulosic microfibers grafted with PAA was three times greater than the water absorption of the nongrafted microfibers. The mechanical properties of continuous cellulose filaments did not change drastically with PAA grafting. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 386–393, 2002     

Corona-induced graft polymerization of ethyl acrylate onto cellulose film

Ethyl acrylate was readily grafted from an aqueous solution onto cellophane film previously treated in a corona discharge at atmospheric pressure. The effect was found when the corona treatment was carried out not only in air but also in pure nitrogen. The observed grafting was not promoted but depressed by the presence of ferrous ion, which indicated that peroxide radicals were not initiating the graft. A high grafting efficiency was obtained, and the grafted surface was covered with a smooth uniform layer of polymer.     

Radiation-induced graft copolymerization of mixtures of styrene and acrylamide onto cellulose acetate. IV. Studies on some physical properties and structural characterization by means of scanning electron microscopy

Binary mixtures of monomers, e.g., styrene and acrylamide in 1:1 methanol:water solution, were grafted onto cellulose acetate film by taking recourse to preirradiation grafting procedure. The surface modification of the films due to grafting was examined by means of scanning electron microscopy. The mechanical properties, e.g., tensile strength elongation at break, and elasticity as well as water vapor permeability of the grafted films, were investigated. In the case of ungrafted films or when acrylamide was grafted to a low extent, the film surfaces were smooth and hence were not modified to any significant extent. But when acrylamide was grafted appreciably, or when styrene was grafted singly or in binary mixture with acrylamide, the surfaces were found to be covered with fibrils. The pattern of the surface modification also changes with the increase of the extent of grafting. The observed properties of the grafted films were explained on the basis of the electron microscopic results.     

Role of nanoclay in determining microfibrillar morphology development in PP/PBT blend nanocomposite fibers

In this work, a new and highly efficient method of surface-initiated free radical graft-polymerizations on the surfaces of silica gel particles was put forward, and the graft-polymerization of methacrylic acid (MAA) was conducted. This method was convenient, feasible and highly effective. Coupling agent ??-mercaptopropyltrimethoxysilane(MPTS) was first bonded onto the surfaces of silica gel particles, obtaining the modified particles MPTS-SiO₂, onto which mercapto groups were chemically attached, so a redox initiation system of graft-polymerization was constituted by the mercapto group on the surfaces of MPTS-SiO₂ particles and the cerium (IV) salt in the solution. And then the surface-initiated free radical graft-polymerization of MAA on the surfaces of silica gel particles was carried out, resulting in the grafted particles PMAA/SiO₂ with a very high grafting density (35?g/100?g) of PMAA. The grafted particles PMAA/SiO₂ were characterized by infrared spectrum (FTIR), scanning electron microscope (SEM) and thermogravimetric analysis (TGA). The effects of the main factors on the new surface-initiated graft polymerization were emphatically examined, and the corresponding mechanism of the graft-polymerization was investigated in depth. The experimental results show that the mercapto group-cerium salt system analogous to the hydroxyl group-cerium salt system, can also effectively initiate vinyl monomers to be graft-polymerized on the surfaces of solid particles, and furthermore, it is a highly effective surface-initiated graft-polymerization method. In this graft-polymerization system, several factors such as sulfuric acid concentration, the used amount of cerium salt and the reaction temperature affect the grafting density greatly. For the graft-polymerization of MAA, the appropriate reaction conditions are as follows: reaction time of 3?h, reaction temperature of 50?°C, cerium concentration of 5.0?×?10^?3?M, acid (H⁺ ion) concentration of 0.15?M and MAA concentration of 0.5?M.     

Graft copolymerization of methyl acrylate onto cellulose initiated by potassium ditelluratoargentate(III)

A novel redox system, potassium ditelluratoargentate(III) (DTA)–cellulose, was employed to initiate the graft copolymerization of methyl acrylate onto cellulose in alkali aqueous solution. Grafting parameters, such as total conversion, grafting efficiency and grafting yield, were evaluated comparatively. The dependence of these parameters on temperature, reaction time, initiator concentration and ratio of monomer to cellulose was also investigated. Graft copolymers with high grafting parameters were obtained, which indicated that the DTA–cellulose redox pair is an efficient initiator for cellulose grafting. The proof of grafting was obtained from gravimetric analysis and infrared spectra. A tentative mechanism involving a two‐step single‐electron‐transfer process of DTA is proposed to explain the generation of radicals and initiation. Thermogravimetry, X‐ray diffraction and scanning electron microscopy were also carried out to study the thermal stability, crystallinity and morphology of the grafted copolymers. Copyright © 2004 Society of Chemical Industry     

The graft polymerization of acrylamide onto paper preirradiated with high energy electrons

The graft polymerization of acrylamide onto filter paper preirradiated in air with electrons from a 200-keV accelerator has been shown to lead to weight increases of up to 210%. The degree of grafting depends on the radiation dose, the moisture content of the paper, and the time interval between irradiation and grafting, but is independent of the radiation dose rate. The degree of grafting increases with the monomer concentration of the reaction medium, and increases as the grafting temperature is reduced. Irradiations in the presence of O₂ or N₂ and the effect of ferrous ions in the grafting solution indicated that peroxides derived from cellulose do not contribute significantly to the initiation reactions up to 60°C. The results are consistent with the degree of grafting depending primarily on the concentration of trapped radicals present in the paper at the time of copolymerization. The cellulose in the grafted material was degraded and the grafted acrylamide was isolated and its molecular weight measured and compared with a calculated value. The moisture regain characteristics of the grafted material are reported.     

Radiation‐induced grafting of pentamethyl hindered amine light stabilizer 1,2,2,6,6‐pentamethyl‐4‐piperidinyl methacrylate onto polypropylene

The γ‐radiation‐induced grafting of 1,2,2,6,6‐pentamethyl‐4‐piperidinyl methacrylate (PMPM) onto polypropylene (PP) was investigated with a simultaneous irradiation technique. The effects of the solvent, dose, monomer concentration, and photoinitiator on the grafting were investigated. The grafting was easier in a benzene solution than in chloroform and acetone solutions. The grafting percentage first increased almost linearly with the irradiation dose until 20 kGy and then increased slowly or remained constant. The grafting percentage increased with the monomer concentration until 1.1 mol/L. The grafting percentage was higher when the proper amount of benzophenone was added. The grafted samples were characterized with Fourier transform infrared spectroscopy and thermogravimetric analysis. Carbonyl groups were found on grafted PP samples, and the carbonyl index increased with the grafting percentage. Thermogravimetric analyses proved the existence of grafted materials on PP, and grafted PMPM thermally decomposed at a lower temperature than PP. The radiation resistance of PP with grafted PMPM was better than that of pristine PP. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 2157–2164, 2005     

Grafting of partially hydrolysed poly(methyl methacrylate) onto mesylated cellulose acetate

A new synthetic route to cellulose graft polymers by nucleophilic displacement of mesylate groups from mesyl cellulose acetate (MCA) by the polystyrylcarboxylate anion has been recently reported by us. This approach to cellulosic graft polymers overcomes the drawbacks of the radical polymerization methods and allows for precise control of parameters such as the molecular weight and molecular weight distribution of the grafted side chains, higher degree of substitution on the cellulose backbone, the number and nature of grafted side chains and overall better control and reproducibility of the grafting process. In this report, partially hydrolysed poly(methyl methacrylate) was successfully grafted on to mesylated cellulose acetate in excellent yields by nucleophilic displacement of mesylate groups in less than 60 min at 75°C.     

Graft copolymerization of vinyl monomers onto modified cottons. XII. Grafting of 1,1-dihydroperfluoroheptyl acrylate onto cellulose carbamate using hydrogen peroxide as initiator

Cellulose carbamate having 1.4% N was grafted with 1,1-dihydroperfluoroheptyl acrylate (DHPFHA) using H₂O₂ as initiator under a variety of conditions. The technique used involved padding the fabric in H₂O₂ solution at room temperature followed by impregnating it in an aqueous emulsion of DHPFHA. The graft yield, expressed as fluorine percent, was found to depend upon monomer and initiator concentration, temperature, and reaction time and pH of the polymerization medium as well as upon the carbamate content of the modified cotton. Increasing the monomer concentration up to 5% caused a considerable enhancement in grafting. The same holds true for initiator concentration up to a certain limit after which the grafting decreases. Raising the reaction temperature up to 100°C was accompanied by an increment in the magnitude of grafting reaction. The latter was characterized by an initial fast rate followed by a slower rate. Slightly acidic media (pH 5–6) proved to be the best for performing grafting. The graft yields were quite poor when grafting was carried out in acidic (pH 2–4) or alkaline (pH 8–12) media. The presence of a relatively smaller amount of carbamate groups in the cellulose molecules decreases its susceptibility to grafting. The opposite holds true for larger amounts. Incorporation of FeSO₄ at low concentration in the monomer emulsion had no effect on the graft yield. However, the latter decreases at higher FeSO₄ concentration. Grafted cellulose carbamate having ca. 15% fluorine showed very good oil and water repellency. The grafted product retained ca. 85% of the strength of cellulose carbamate.     

Grafting biodegradable polyesters onto cellulose

To increase the compatibility between cellulose fibers and polyester matrix an original method for grafting hydrophobic oligoesters onto cellulose was proposed. Two kinds of cellulose substrates were employed as cellulose films and microcrystalline cellulose powder. Different oligoesters containing reactive end groups based on poly(DL ‐lactic acid) PDL‐LA, poly(ε‐caprolactone) PCL and poly(3‐hydroxyalkanoate)s PHA were first prepared and characterized by size exclusion chromatography (SEC), nuclear magnetic resonance (NMR), and differential scanning calorimetry (DSC). The carboxylic end groups of the polyesters were activated using thionyl chloride (SOCl₂) to increase the esterification reaction with the hydroxyl groups of the cellulose. The esterification was realized in a heterogenous medium without any catalyst by deposition of chloride oligoesters in solution (2–100 g L⁻¹) onto cellulose film at different temperatures (25–105°C) during 1–12 h. The successful grafting on the various substrates was confirmed on the basis of FTIR spectroscopy, contact angle measurement, X‐ray photoelectron spectroscopy (XPS) and thermogravimetric analysis (TGA). In particular, it is shown that a small quantity of grafted oligoesters led to a significant increase of the hydrophobic character of the cellulose with a contact angle near 130°. The increase of hydrophobicity of cellulose is independent of the nature and length of grafting oligoesters. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Surface grafting of polymers onto glass plate: Polymerization of vinyl monomers initiated by initiating groups introduced onto the surface

The surface grafting of polymers onto a glass plate surface was achieved by the polymerization of vinyl monomers initiated by initiating groups introduced onto the surface. Azo groups were introduced onto the glass plate surface by the reaction of 4,4′-azobis(4-cyanopentanoic acid) with isocyanate groups, which were introduced by the treatment with tolylene-2,4-diisocyanate. The radical polymerization of various vinyl monomers was initiated by azo groups introduced onto the glass plate surface and the corresponding polymers were grafted from the surface: The surface grafting of polymers was confirmed by IR spectra, and the contact angle of surface, with water. The contact angle of the glass plate increased by the grafting of hydrophobic polymers, but decreased by the grafting of hydrophilic polymers. The radical postpolymerization was successfully initiated by the pendant peroxycarbonate groups of grafted polymer on the surface to give branched polymer-grafted glass plate. The cationic polymerization of vinyl monomers was also successfully initiated by benzylium perchlorate groups introduced onto the glass plate surface and the corresponding polymers were grafted onto the surface. The contact angle of the glass plate surface obtained from the cationic polymerization of styrene was larger than that obtained from the radical polymerization. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 65: 2165–2172, 1997     

Reactivity of glycidyl methacrylate grafted cellulose film prepared by grafting under ultrasonic irradiation

Ultrasonic irradiation largely accelerated ceric salt initiated grafting of glycidyl methacrylate (GMA) on regenerated cellulose film (cellophane thickness = 20 μm) at 60°C in air. The grafting under ultrasonic irradiation was characterized by a higher percent of grafting and graft efficiency and a lower density of GMA‐grafted chains in the surface layer of the grafted films compared to the unirradiated system, which was obtained by attenuated total reflectance IR measurements. The grafted films were subjected to amination with ethylenediamine (En) at 70°C for 3 h in N,N‐dimethylformamide. The amount of epoxy groups in the grafted films, which participated in the reaction with En, reached about 50–60 mol % and was slightly lower for the grafted film prepared in the irradiated system than that prepared in the unirradiated one. Adsorption of cupric ions with the aminated samples was performed at pH 5.0 using Clark–Lubs buffer solution and cupric chloride. The adsorption was extremely retarded for the aminated sample prepared using the unirradiated sample compared to that prepared using the irradiated one. The retarded adsorption phenomenon is discussed in terms of a larger formation of crosslinked structures on the surface layer of the former sample during the amination. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2462–2469, 1999     

Grafting of dichlorodimethylsilane onto cellulose acetate as a model system in homogeneous media

Homogeneous graft copolymerization of dichlorodimethylsilane (DCDMS) onto cellulose acetate (CA) was carried out in acetone. The weight conversion, grafting percentage and grafting efficiency were determined as functions of the polymerization temperature and the concentrations of monomer and cellulose acetate. The IR and NMR data of the graft copolymers showed peaks characteristic of grafted chains. The order of the solvents used for increasing the grafting yield values was found as follows: cyclohexanone > ethyl acetate > dioxane, which is in accordance with their dielectric constants. Cellulose acetate previously oxidized by treatment with a mixture of oxalic acid and potassium dichromate when grafted with DCDMS gave low grafting yield values. The rate of copolymerization grafting of DCDMS onto CA was determined (R_p = 1.1 %min⁻¹). The activation energy of the reaction between DCDMS and CA was calculated (1.32 kJ mol⁻¹, 0.32 kcal mol⁻¹). The mechanism of graft copolymerization of DCDMS onto CA is discussed.