Grafting reaction of living polymer cations with amino groups on chitosan powder

The grafting of polymers having controlled molecular weight and narrow molecular weight distribution onto chitosan powder by the termination of living polymer cation with amino groups on chitosan powder was investigated in heterogeneous system. The amino groups of chitosan powder successfully reacted with living poly(isobutyl vinyl ether) [poly(IBVE)] and poly(2-methyl-2-oxazoline) [poly(MeOZO)] cation with controlled molecular weight and narrow molecular weight distribution to give the corresponding polymer-grafted chitosan powders. The percentage of poly(MeOZO) grafting gradually increased and reached 24.5% after 4 days. The solubility of poly(MeOZO)-grafted chitosan in water increased with an increase in the amount of grafted polymer. It was suggested that grafting reaction of living polymer cation with chitosan powder proceeds from surface amino groups to inner amino groups of the powder with progress of the reaction. The mole number of grafted polymer chain on chitosan powder decreased with an increase in the molecular weight of the living polymer cation because the steric hindrance of functional groups of chitosan powder increased with the increasing molecular weight of living polymer. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1883–1889, 1998     

Effect of initiating groups introduced onto ultrafine silica on the molecular weight polystyrene grafted onto the surface

Summary The effect of initiating groups introduced onto silica surface on the molecular weight of grafted polystyrene chain was investigated. By the treatment of polystyrene-grafted silica with aqueous solution of alkali, surface grafted polystyrene was isolated from the surface. The molecular weight of polystyrene grafted onto the silica obtained from the radical graft polymerization initiated by peroxyester groups introduced onto the surface was found to be much larger than that from the cationic polymerization initiated by acylium perchlorate groups. The number of grafted polystyrene in the radical polymerization, however, was much less than that in the cationic polymerization. Furthermore, the effect of molecular weight of grafted polystyrene on the dispersibility of silica in tetrahydrofuran was examined.     

Graft polymerization of vinyl acetate onto silica

The free‐radical graft polymerization of vinyl acetate onto nonporous silica particles was studied experimentally. The grafting procedure consisted of surface activation with vinyltrimethoxysilane, followed by free‐radical graft polymerization of vinyl acetate in ethyl acetate with 2,2′‐azobis(2,4‐dimethylpentanenitrile) initiator. Initial monomer concentration was varied from 10 to 40% by volume and the reaction was spanned from 50 to 70°C. The resulting grafted polymer, which was stable over a wide range of pH levels, consisted of polymer chains that are terminally and covalently bonded to the silica substrate. The experimental polymerization rate order, with respect to monomer concentration, ranged from 1.61 to 2.00, consistent with the kinetic order for the high polymerization regime. The corresponding rate order for polymer grafting varied from 1.24 to 1.43. The polymer graft yield increased with both initial monomer concentration and reaction temperature, and the polymer‐grafted surface became more hydrophobic with increasing polymer graft yield. The present study suggests that a denser grafted polymer phase of shorter chains was created upon increasing temperature. On the other hand, both polymer chain length and polymer graft density increased with initial monomer concentration. Atomic force microscopy–determined topology of the polymer‐grafted surface revealed a distribution of surface clusters and surface elevations consistent with the expected broad molecular‐weight distribution for free‐radical polymerization. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 87: 300–310, 2003     

Molecular weights of grafted polystyrene onto γ-preirradiated cellulose diacetate

The behavior of molecular weights of grafted polystyrene onto γ-preirradiated cellulose diacetate was studied. The grafting of styrene onto cellulose diacetate was kinetically followed with particular attention paid to the polystyrene molecular weight behavior. The molecular weight was evaluated with the polymer fractions obtained by acid hydrolysis of the grafted copolymer. From the experimental results it appeared that the grafted chain molecular weight is completely controlled by the physical properties of the polymeric matrix either during a “bulk” or a “front” grafting.     

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     

Surface grafting of polymers onto aramid powder: graft polymerization of vinyl monomers initiated by azo groups introduced onto the surface of aramid powder

The radical graft polymerization of vinyl monomers onto the surface of aramid powder, i.e., poly(p-phenylene terephthalamide) powder, initiated by azo groups introduced onto the surface was investigated. The introduction of azo groups onto the aramid surface was achieved by the reaction of surface acyl chloride groups, which were introduced by the treatment of aramid powder with adipoyl dichloride, with 2,2′-azobis[2-(2-imidazolyn-2-yl)propane] in the presence of pyridine: the amount of azo groups thus introduced onto the surface was determined to be 0.57 mmol/g by elemental analysis. It was found that the polymerizations of methyl methacrylate (MMA) and styrene were successfully initiated by the azo groups on the surface and that the corresponding polymers were grafted onto the surface. The percentage of surface grafting of polystyrene and poly(methyl methacrylate) (PMMA) increased up to 37.6 and 26.5%, respectively. Thermogravimetric analysis of polymer surface-grafted aramid powder confirmed that the grafting of polymers is limited on the surface. The polymerization rate was found to bear a first-order dependence on the concentration of aramid powder having azo groups. This suggests that in graft polymerization, unimolecular termination preferentially proceeds.     

Grafting of polyelectrolytes onto polyacrylamide by reactive processing

Low‐molecular‐weight high‐charge‐density cationic poly diallydimethyl ammonium chloride (polyDADMAC) was grafted onto nonionic polyacrylamide (PAM) using organic peroxide initiators in the molten state carried out in a batch mixer. The graft copolymer can be used as a high performance flocculant. Glycerol was selected as a plasticizer. The grafting reaction was characterized in terms of composition, temperature, degree of grafting, and grafting efficiency. It was found that free radicals on polymer chains were induced by the decomposition of the initiator. Grafting was produced by free radical recombination termination. The degree of grafting increases with an increase of the polyDADMAC/PAM feed ratio. However, the grafting efficiency was lower than 10 wt % in this highly viscous polymer melt system. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1412–1416, 1999     

Grafting of branched polymers onto nano-sized silica surface: Postgrafting of polymers with pendant isocyanate groups of polymer chain grafted onto nano-sized silica surface

To control the surface wettability of nano-sized silica surface, the postgrafting of hydrophilic and hydrophobic polymers to grafted polymer chains on the surface was investigated. Polymers having blocked isocyanate groups were successfully grafted onto nano-sized silica surface by the graft copolymerization of methyl methacrylate (MMA) with 2-(O-[1′-methylpropylideneamino]caboxyamino)ethyl methacrylate (MOIB) initiated by azo groups previously introduced onto the surface. The blocked isocyanate groups of poly(MMA-co-MOIB)-grafted silica were stable in a desiccator, but isocyanate groups were readily regenerated by heating at 150 °C. The hydrophilic polymers, such as poly(ethylene glycol) (PEG) and poly(ethyleneimine) (PEI), were postgrafted onto the poly(MMA-co-MOIB)-grafted silica by the reaction of functional groups of PEG and PEI with pendant isocyanate groups of poly(MMA-co-MOI)-grafted silica to give branched polymer-grafted silica. The percentage of grafting increased with increasing molecular weight of PEG, but the number of postgrafted chain decreased, because of steric hindrance. The hydrophobic polymers, such as poly(dimethylsiloxane) were also postgrafted onto poly(MMA-co-MOI)-grafted silica. It was found that the grafting of hydrophobic polymer and the postgrafting of hydrophilic polymer branches readily controls the wettability of silica surface to water.     

Graft polymerization of vinyl monomers initiated by peroxycarbonate groups introduced onto silica surface by Michael addition

The introduction of peroxycarbonate groups onto a silica surface and the graft polymerization of vinyl monomers initiated by peroxycarbonate groups introduced onto a silica surface were investigated. The introduction of peroxycarbonate groups onto a silica surface was achieved by Michael addition of amino groups introduced onto the silica surface to t‐butylperoxy‐2‐methacryloyloxyethylcarbonate (HEPO). The amount of peroxycarbonate groups was determined to be 0.17 mmol/g. The graft polymerization of various vinyl monomers such as styrene (St), N‐vinyl‐2‐pyrrolidinone (NVPD), and 2‐hydroxyethyl methacrylate (HEMA) was initiated by peroxycarbonate groups introduced onto the silica surface to give the corresponding polymer‐grafted silicas. The percentage of poly(St)‐grafting reached about 120% after 5 h. This means that 1.20 g of poly(St) is grafted onto 1.0 g of silica. The surface of poly(St)‐grafted silica shows a hydrophobic nature, but the surfaces of poly(NVPD) and poly(HEMA)‐grafted silica show a hydrophilic nature. Furthermore, the poly(St)‐grafted silica was found to give a stable colloidal dispersion in a good solvent for the grafted polymer. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1491–1497, 1999     

Surface grafting of polymers onto ultrafine silica: cationic polymerization initiated by benzylium perchlorate groups introduced onto ultrafine silica surface

Summary The cationic graft polymerization initiated by benzylium perchlorate groups introduced onto ultrafine silica surface was investigated. The introduction of benzylium perchlorate groups onto the surface was achieved by the reaction of silver perchlorate with surface benzyl chloride groups, which were introduced by the treatment of silica with 4-(chloromethyl)phenyltrimethoxysilane. The cationic graft polymerization of styrene and cationic ring-opening polymerization of -caprolactone were found to be initiated by the surface benzylium perchlorate groups and the corresponding polymers were grafted onto the surface. The percentage of grafting onto silica surface decreased with increasing polymerization temperature, because chain transfer reaction of growing polymer cation is accelerated with increasing polymerization temperature.     

Grafting and phosphonic acid functionalization of hyperbranched polyamidoamine polymer onto ultrafine silica

In this study, grafting of hyperbranched polyamidoamine (PAMAM) polymer onto ultrafine silica followed by functionalization via the introduction of phosphonic acid groups into the branch ends was performed. First, an initiating site was incorporated into the silica surface by reacting the silica silanol group with 3‐aminopropyltriethoxysilane, producing amino‐functionalized silica. The free amine group content was altered by varying the ratio of methanol to water in the hydrolysis step of the silanization reaction. Grafting of PAMAM was attained by three rounds of sequential Michael addition of silica amino groups to methyl acrylate and amidation of the resulting terminal methyl ester groups with ethylenediamine. Completion of the grafting reaction in each step was clearly confirmed using FTIR analysis. Excessive ethylenediamine and unattached hyperbranched PAMAM present in the reaction product were removed by dialysis with a molecular weight cutoff of 6000–7000 Daltons. However, the amino group content determined in each step was found to be significantly lower than theoretically expected, perhaps indicative of side reactions and, in later stages, steric hindrance. The resultant hyperbranched PAMAM‐grafted onto silica was functionalized by phosphorylation of the terminal amino groups by a Mannich type reaction, producing the phosphorylated hyperbranched PAMAM‐grafted silica. Then its application on cotton fabric to produce fire‐retardant cellulose was tentatively investigated. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preirradiation‐induced emulsion graft polymerization of glycidyl methacrylate onto poly(vinylidene fluoride) powder

An epoxy‐group‐containing monomer, glycidyl methacrylate (GMA), was grafted onto poly(vinylidene fluoride) powder via preirradiation‐induced emulsion graft polymerization. The existence of graft chains was proven by chemical structure characterization with Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy analysis. The degree of grafting was calculated by means of fluorine content analysis. A kinetic study indicated that, with the emulsion graft polymerization system, the GMA conversion rate was high, exceeding 80%. The variation in the molecular weight of the grafted polymer was measured by gel permeation chromatography, and its crystallinity was investigated with differential scanning calorimetry. The epoxy groups in graft chains were found to be suitable for further chemical modification. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation,characterization, and properties of cellulose–polyacrylamide graft copolymers

Graft copolymers of acrylamide on cellulose materials (α‐cellulose 55.8%, DP 287.3) obtained from Terminalia superba wood meal and its carboxymethylated derivative (DS 0.438) were prepared using a ceric ion initiator and batch polymerization and modified batch polymerization processes. The extent of graft polymer formation was measured in graft level, grafting efficiency, molecular weight of grafted polymer chains, frequency of grafting as a function of the polymerization medium, and initiator and monomer concentrations. It was found that the modified batch polymerization process yielded greater graft polymer formation and that graft copolymerization in aqueous alcohol medium resulted in enhanced levels of grafting and formation of many short grafted polymer chains. Viscosity measurements in aqueous solutions of carboxymethyl cellulose‐g‐polyacrylamide copolymer samples showed that interpositioning of polyacrylamide chains markedly increased the specific viscosity and resistance to biodegradation of the graft copolymers. The flocculation characteristics of the graft copolymers were determined with kaolin suspension. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 913–923, 2003     

Grafting of selected presynthesized macromonomers onto various dispersions of silica particles

A new process was developed which enables one to obtain surface‐modified silica with a high heavy metal ion complexing ability. The synthetic approach is based on grafting of vinyl‐terminated macromonomers onto silica via covalent bonding. A proper selection of the macromonomer structure, molecular weight, and molecular weight distribution allows materials to be obtained with a range of desirable properties. The process has been tested on various dispersions (ranging from 35 and 200 μm) of silica particles and two structurally related macromonomers. Native silica and the resulting mixed organic–inorganic products were fully characterized by IR spectroscopy, SEM, yield of grafting (elemental analysis and calcination), density (helium pycnometry), specific surface area (BET method), and pore size (gas adsorption and mercury porosimetry) measurements. It was found that the corresponding polymers are effectively grafted onto the surface; the density, surface area, and pore size of the silica particles decrease with polymer grafting. Preliminary results on metal‐ion uptake indicate that polymer‐grafted silica exhibits an excellent complexing ability. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1287–1296, 2002     

ICAR ATRP of methyl methacrylate catalyzed by FeCl3·6H2O/succinic acid

In this work, methyl methacrylate (MMA) was polymerized by initiator for continuous activator regeneration (ICAR) atom transfer radical polymerization (ATRP) method to obtain low molecular weight living polymers. The ATRP initiator was ethyl 2‐bromoisobutyrate, the catalyst ligand complex system was FeCl₃·6H₂O/succinic acid, and the conventional radical initiator 2,2′‐azobisisobutyronitrile was used as a thermal radical initiator. Polymers with controlled molecular weight were obtained with ppm level of Fe catalyst complex at 90°C in N,N‐dimethylformamide. The polymer was characterized by nuclear magnetic resonance (NMR). The molecular weight and molecular weight distribution of the obtained poly (methyl methacrylate) were measured by gel permeation chromatography method. The kinetics results indicated that ICAR ATRP of MMA was a “living”/controlled polymerization, corresponding to a linear increase of molecular weights with the increasing of monomer conversion and a relatively narrow polydispersities index. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

炭黑表面的接枝聚合改性方法

通过接枝高聚物对炭黑表面改性，可显著提高炭黑与基质的相容性，本文介绍了带有可反应端基的聚合物和可分解自由基官能团的聚合物与炭黑间的接枝反应，这种接枝方法可控制接枝链分子量及其分布。     

Grafting of cotton fiber by water‐soluble cyclodextrin‐based polymer

β‐cyclodextrin (CD)‐based linear water‐soluble polymers were synthesized in a controlled manner by a one‐pot synthesis method. The synthesized water‐soluble polymer was covalently fixed onto cotton surfaces by a polycondensation reaction at controlled conditions. Grafting on cotton fibers transfers the cyclodextrin properties onto its surface. The grafting occurred through the formation of a crosslink between hydroxyl groups of cotton and CD polymer. This was confirmed using FTIR spectroscopy, DSC, tensile strength, computer color matching, and solvent fastness analysis. The tensile strength of modified fiber samples was unchanged as compared to that of unmodified fiber samples. The percentage of grafting depended on a number of parameters and specifically on (i) temperature, (ii) time, and (iii) pH of the reaction medium. Similarly, under optimum conditions the weight increase on cotton fabric due to the grafting reaction could reach 10–15 wt % The grafted cotton fabric shows good dyeability and solvent fastness properties. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Grafting of polystyrene and poly(p‐chlorostyrene) from the surface of ramie fiber via RAFT polymerization

Reversible addition‐fragmentation chain transfer (RAFT) radical polymerization was used for controlled grafting of styrene and p‐chlorostyrene from the surface of ramie fiber. The hydroxyl groups in ramie fiber were first converted to thiocarbonylthio groups as the RAFT chain transfer agent then used to mediate the RAFT polymerization of styrene, and p‐chlorostyrene in tetrahydrofuran using azobis (isobutyronitrile) as initiator at 60°C. The grafted copolymers were analyzed by Fourier transform infrared spectroscopy, scanning electron microscopy, thermogravimetry, and contact angle measurements. The results confirmed that grafting occurred on the surface of the ramie fiber, substantially increasing the water contact angle from 75.31° to 147° for polystyrene grafted ramie fiber (cell‐PS) and 135° for poly(p‐chlorostyrene) (cell‐PSCl), and improving the hydrophobicity of the grafted fiber. The homopolymers formed in the polymerization were analyzed by size exclusion chromatography to estimate the molecular weights and polydispersity indices (PDIs) of chains grafted from the surface of the ramie fiber, as well as showed narrow chain length distributions with a PDI of 1.32–1.70. These materials possess potential applications in many advanced technologies. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Hydrophobic cellulose fibers via ATRP and their performance in the removal of pyrene from water

In the present work, cellulose fibers were modified by grafting with poly(lauryl acrylate) and poly(octadecyl acrylate). The grafted materials were prepared by polymerization of the corresponding monomers via surface initiated atom transfer radical polymerization, starting from cellulose papers previously modified with 2‐bromoisobutyryl groups. The polymerizations were carried out in the presence of ethyl‐2‐bromoisobutyrate, as a sacrificial initiator, added to control the molecular weight of the anchored segments, and polymerization kinetics. The grafting of both polymers was confirmed by infrared spectroscopy and elemental analysis. The effect of grafting these polymers on the thermal stability, morphology, and surface properties of cellulose fibers was studied using thermogravimetric analysis, scanning electron microscopy, and measuring water contact angle, respectively. The results reveal that grafting poly(lauryl acrylate) and poly(octadecyl acrylate) to cellulose confers the filter paper a hydrophobic character, and increases its affinity with pyrene, allowing the removal of this pollutant from water. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44482.     

Surface graft copolymerization of poly(methyl methacrylate) onto waste tire rubber powder through ozonization

Grinding of tires offers a promising opportunity for recycling waste rubber because fine waste tire rubber particle may be used as fillers and property modifiers in thermoplastic, elastomer, and thermoset blends. However, due to the lack of reactive sites on the WTR surface, the adhesion between WTR powder and matrix is poor. In this article, ozonization of waste tire rubber (WTR) powder was performed to produce some “immobile” reactive points (hydroperoxide groups) on the WTR surface. The free radical generated by the decomposition of hydroperoxide groups on WTR surface, was used to initiate graft polymerization of methyl methacrylate (MMA) onto the surface of WTR powder. The experimental results showed that MMA was successfully grafted onto the surface of WTR. The hydrophilicity of the MMA grafted WTR (MMA‐g‐WTR) was improved. The concentration of hydroperoxide groups and the graft degree were both increased with ozonization time. With increasing of polymerization time and polymerization temperature, the grafting degree increased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011