Grafting of vinyl polymers onto VGCF surface and the electric properties of the polymer-grafted VGCF

The graft polymerization of vinyl monomers onto vapor grown carbon fibers (VGCF) initiated by the system consisting of molybdenum hexacarbonyl (Mo(CO)₆) and trichloroacetyl (COCCl₃) groups introduced onto the surface was investigated. The introduction of trichloroacetyl groups onto VGCF surface was successfully achieved by the reaction of carboxyl groups on VGCF surface with trichloroacetyl isocyanate. It was found that the radical graft polymerization of vinyl monomers, such as methyl methacrylate (MMA), styrene, and glycidyl methacrylate (GMA) is successfully initiated by the system consisting of Mo(CO)₆ and COCCl₃ groups introduced onto the surfaces. In the polymerization, the corresponding vinyl polymers were effectively grafted onto the VGCF surface, based on the propagation of polymer from surface radicals formed by the interaction of trichloroacetyl groups and Mo(CO)₆: the percentage of PMMA grafting reached 40%. Polymer-grafted VGCF gave a stable colloidal dispersion in good solvents for grafted polymer. The electric resistance of composite prepared from the polymer-grafted VGCF suddenly increased in organic solvent vapor over 10³ times, and returned to initial resistance when it was transferred into dry air. These results indicate that such composites can be used as novel gas sensors.     

Graft polymerization of vinyl monomers from initiating groups introduced onto polymethylsiloxane-coated titanium dioxide modified with alcoholic hydroxyl groups

The grafting of vinyl polymers onto the surface of polymethylsiloxane-coated titanium dioxide modified with alcoholic hydroxyl groups (Ti/Si–R–OH) were investigated. The introduction of azo and trichloroacetyl groups onto the surface of Ti/Si–R–OH was achieved by the reaction of the surface alcoholic hydroxyl groups with 4,4′-azobis(4-cyanopentanoic acid) and trichloroacetyl isocyanate, respectively. The radical polymerizations of vinyl monomers were successfully initiated by the azo groups introduced onto the surface and by the system consisting of Mo(CO)₆ and Ti/Si–R–COCCl₃. During the polymerization, the corresponding polymers were effectively grafted onto the titanium dioxide surface through propagation from surface radicals formed by the decomposition of azo groups and by the reaction of Mo(CO)₆ with trichloroacetyl groups on the surface. The percentage of grafting and grafting efficiency in the graft polymerization initiated by the system consisting of Ti/Si–R–COCCl₃ and Mo(CO)₆ were much larger than those initiated by azo groups. The polymer-grafted titanium dioxide was found to produce a stable colloidal dispersion in good solvents for the grafted polymer. The dispersibility of poly(N,N-diethylacrylamide)-grafted titanium dioxide in water was controlled by temperature. In addition, the wettability of the surface of titanium dioxide to water was readily controlled by grafting of hydrophilic or hydrophobic polymers.     

Grafting of branched polymers onto the surface of vapor grown carbon fiber and their electric properties

The grafting of branched polymers onto vapor grown carbon fiber (VGCF) surface and their electric properties of the composite prepared from the branched polymer-grafted VGCF were investigated. In the first step, the grafting of copolymers having pendant peroxy groups onto VGCF was achieved by the copolymerization of 1-(t-butylperoxy-i-propyl)-3-i-propenylbenzene (BPPB) with vinyl monomers initiated by the system consisting of Mo(CO)₆ and trichloroacetyl groups previously introduced onto the surface. In the second step, the postpolymerization of vinyl monomers was initiated by pendant peroxy groups of grafted poly(vinyl monomer-co-BPPB) on the surface to give branched vinyl polymer-grafted VGCF. The dispersibility of VGCF in THF was remarkably improved by grafting of branched polymers onto the surface. The electric resistance of composites prepared from the branched polymer-grafted VGCF suddenly increased when the composites were transferred into solvent vapors and suddenly decreased when they were transferred to dry air.     

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 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.     

Photochemical reactions of high polymers. XIII. Photografting of methyl methacrylate onto the polymers bearing thiosulfate groups

Polymers bearing pendent thiosulfate groups, that is, sodium poly(vinyl benzyl thiosulfate) (PVBB) and the sodium salt of poly(vinyl hydrothiosulfatoacetate)(PV AcB), were prepared. The photograft polymerization of methyl methacrylate onto these polymers was carried out. The relationships between irradiation time and conversion, degree of grafting, and grafting efficiency were investigated in the photograft polymerization. It was ascertained that the pendent thiosulfate groups acted as effective initiators for the graft polymerization. From the number of endgroups in the homopolymer formed along with the graft polymer, the mechanism of the graft polymerization was discussed and it was verified that the graft polymerization was initiated by the thiyl radical formed by scission of the sulfur–sulfur bond of the pendent thiosulfate group. An unusually high degree of grafting and extremely rapid polymerization rate observed in the graft polymerization suggested the dual functions of thiosulfate-bearing polymer as initiator and emulsifier. It was found that addition of FeCl₂ to this polymerization system increased the rate of polymerization and the degree of grafting but decreased the grafting efficiency. The effect of FeCl₂ was interpreted by assumption of a photo-redox reaction between thiosulfate group and Fe²⁺.     

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 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.     

Synthesis of hyperbranched polymers via a facile self-condensing vinyl polymerization system - Glycidyl methacrylate/Cp2TiCl2/Zn

A facile self-condensing vinyl polymerization (SCVP) system, the combination of glycidyl methacrylate, Cp₂TiCl₂ and Zn, has been firstly used to prepare novel hyperbranched polymers, consisting of vinyl polymers as the backbone, and cyclic ester polymers (poly(?-caprolactone) or poly(l-lactide)) as the side chains. The polymerizations are initiated by the epoxide radical ring-opening catalyzed by Cp₂Ti(III)Cl which is generated in situ via the reaction of Cp₂TiCl₂ with Zn. The key to success is that the polymerizations can proceed concurrently via two dissimilar chemistries possessing the opposite active initiating species, including ring-opening polymerization (ROP) and controlled/living radical polymerization (CRP). We have demonstrated that this facile one-step polymerization technique can be applied successfully to prepare highly branched polymers with a multiplicity of end reactive functionalities including Ti alkoxide, hydroxyl and vinyl functional groups.     

Preparation and dispersibility of poly(L‐lactide)‐grafted silica nanoparticle

To improve dispersibility of silica nanoparticle in organic solvents, the grafting of poly(L ‐lactide) (PLLA) onto silica nanoparticle surface by ring‐opening polymerization of L‐lactide (LA) was investigated in the presence of an amidine base catalyst. The ring‐opening polymerization of LA successfully initiated in the presence of silica having amino groups (silica‐NH₂) and an amidine base catalyst to give PLLA‐grafted silica, but not in the presence of untreated silica (silica‐OH). In the absence of the amidine base catalyst no ring‐opening polymerization of LA even in the presence of silica‐NH₂ and no grafting of PLLA onto silica were observed. It became apparent that the amidine base catalyst acts as an effective catalyst for the ring‐opening graft polymerization of LA from the surface of silica‐NH₂. In addition, it was found that the percentage of PLLA grafting onto silica could be controlled according to the reaction conditions. The average particle size of PLLA‐grafted silica was smaller than that of silica‐NH₂. Therefore, it was considered that the aggregation structure of silica nanoparticles was considerably destroyed by grafting of PLLA onto the surface. The PLLA‐grafted silica gave a stable dispersion in polar solvents, which are good solvents for PLLA. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Grafting of hyperbranched aromatic polyamide onto silica nanoparticles

Hyperbranched aromatic polyamide grafted nano-silica particles were successfully prepared via “one-pot” melt polycondensation. The particles were firstly treated with a silane coupling agent to introduce amine groups as the growth points, and then grafting of the hyperbranched polymers started from the modified surface. The percentage grafting can be as high as 32.8%. The key reaction conditions, including feeding ratio, reaction temperature and time, were carefully investigated to determine a set of optimal grafting parameters. It was found that the significant steric hindrance between the hyperbranched polymers during graft polymerization played a key role in controlling molecular structure of the grafted polymers, while adsorption of grafting monomer onto SiO₂ particles prior to the reaction facilitated higher degree of branching and apparent molecular weight of ungrafted polymers.     

Synthesis, characterization and UV curing kinetics of hyperbranched polysiloxysilanes from A2 and CB2 type monomers

A controllable approach to synthesize UV curable hyperbranched polysiloxysilanes from A₂ (1,1,3,3-tetramethyldisiloxane) and CB₂ type monomers (methyl(vinyl)silanediylbis(oxy)bis(ethane-2,1-diyl) diacrylate and methyl(vinyl) silanediylbis(oxy)bis(ethane-2,1-diyl)bis(2-methylacrylate)) was developed in the presented paper. The polymerization was monitored using FTIR, where a two-step polyaddition mode was observed. Vinyl silane group preferentially reacted with hydride silane, resulting in the formation of AB₂ type intermediates containing one hydride silane and two acrylate (or methacrylate) groups, at the same time, there may be low quantity of B₄ type intermediates. The intermediates further polymerized to form hyperbranched polymers. The UV curing kinetics of the hyperbranched polymers, especially the effects of atmosphere, content of photoinitiator and light intensity on UV curing behavior were studied in detail. The results indicated that the hyperbranched polymers could be cured rapidly under UV irradiation. The curing rates increased with the enhancement of light intensity, and the inhibition effect of oxygen could be restrained by increasing light intensity.     

Cationic Graft Polymerization onto Silica Nanoparticle Surface in a Solvent-Free Dry-System

For the purpose of the prevention of the environmental pollution and the simplification of reaction process, the scale-up synthesis of polymer-grafted silica nanoparticle by surface initiated cationic ring-opening graft polymerization of 2-methyl-2-oxazoline (MeOZO) in a solvent-free dry-system was investigated. The introduction of iodopropyl groups onto the silica surface as initiating group was carried out by the reaction of silanol groups with 3-iodopropyl- trimethoxysilane in a solvent-free dry-system. The graft polymerization of MeOZO onto silica nanoparticle surface in a solvent-free dry-system was initiated by spraying the monomer onto the surface having iodopropyl groups and the polymerization was conducted in powder fluid system under nitrogen. After the polymerization, unreacted MeOZO was readily removed under high vacuum. It was found that the cationic ring-opening polymerization of MeOZO was successfully initiated in the solvent-free dry-system to give polyMeOZO-grafted silica nanoparticles. The maximum grafting of polyMeOZO obtained from the polymerization initiated by iodopropyl groups on the surface reached 47.7 %. The percentage of grafting and grafting efficiency during the cationic ring-opening graft polymerization in the solvent-free dry-system were considerably larger than those in solution system. This suggests that chain transfer reaction from surface growing cation to monomer was effectively inhibited in the solvent-free dry-system.     

Surface grafting of polymer onto carbon thin film

The surface grafting of polymers onto carbon thin film deposited on a glass plate was achieved by two methods: the graft polymerization initiated by initiating groups introduced onto the surface; and the trapping of polymer radicals by surface aromatic rings of the thin film. It was found that the radical and cationic graft polymerization of vinyl monomers are initiated by azo and acylium perchlorate groups introduced onto the surface, respectively, and the corresponding polymers are grafted onto the surface: the surface grafting of polymers were confirmed by the contact angle of the surface with water. In addition, the anionic ring-opening alternating copolymerization of epoxides with cyclic acid anhydrides was found to be initiated by potassium carboxylate groups on the carbon thin film to give the corresponding polyester-grafted carbon thin film. On the other hand, polymer radicals formed by the decomposition of azo polymer, such as poly(polydimethylsiloxane-azobiscyanopentanoate) and poly(polyoxyethylene-azobiscyanopentanoate), were successfully trapped by the surface aromatic rings of carbon thin film and polydimethylsiloxane and polyoxyethylene were grafted onto the surface. © 1995 John Wiley & Sons, Inc.     

Graft polymerization of methyl methacrylate onto wool initiated by ferric acetylacetonate/dichloroacetic acid system

The graft polymerization of methyl methacrylate (MMA) initiated by ferric acetyl acetonate/dichloroacetic acid [Fe(acac)₃–Cl₂CHCOOH] system onto wool has been investigated in a mixture of water and dioxane. No grafting occurred in organic solvent; water was essential to the grafting. Both the total conversion and the percentage of grafting showed maxima when the mole ratio of Fe(acac)₃ and Cl₂CHCOOH was ¼. Increasing wool content increased the percentage of grafting, while homopolymer conversion was independent of wool content. The rate of grafting was not proportional to MMA concentration. The grafting mechanism was discussed from these results.     

Surface grafting of polymers onto ultrafine silica: Cationic polymerization initiated by oxoaminium perchlorate groups introduced onto ultrafine silica surface

Summary The cationic polymerization initiated by oxoaminium perchlorate groups introduced onto ultrafine silica surface was investigated. The oxoaminium perchlorate groups were successfully introduced by treatment of nitroxyl radicals on silica surface with perchloric acid. The introduction of the nitroxyl radicals was achieved by reaction of 4-hydroxy-2,2,6,6-tetramethyl-piperidinyloxy radical with acid anhydride groups on the surface. The cationic polymerization of isobutyl vinyl ether, N-vinylcarbazole, 2,3-dihydrofuran, and -butyrolactone was initiated by oxoaminium perchlorate groups introduced onto the surface and the corresponding polymers were grafted onto the surface through the propagation of grafted polymer chain from the surface oxoaminium perchlorate groups.     

Preparation of acrylate polymer/silica nanocomposite particles with high silica encapsulation efficiency via miniemulsion polymerization

Acrylate polymer/silica nanocomposite particles were prepared through miniemulsion polymerization by using methyl methacrylate/butyl acrylate mixture containing the well-dispersed nano-sized silica particles coupling treated with 3-(trimethoxysilyl)propyl methacrylate (MPS). The encapsulation efficiency of silica particles was determined through the elution and hydrofluoride acid etching experiments, and the size distribution and the morphology of the composite latex particles were characterized by dynamic light scattering and transmission electron microscopy. The coupling treatment of silica with MPS can improve the encapsulation efficiency of silica and the degree of grafting of polymer onto silica. When 0.10 g MPS/g silica was used to modify silica, the encapsulation efficiency of silica was greater than 95%, and the degree of grafting of acrylate polymer onto silica was about 60%. Although the average size and the size distribution index of the composite latex particles increased as the weight fraction of silica increased, the stable latex containing the ‘guava-like’ composite particles was obtained. The grafting of polymer onto silica particles improved the dispersion of silica particles in the solvents for acrylate polymer and in the polymer matrix.     

Preparation and characterization of hydrophilic and antibacterial silver decorated silica-grafted-poly(vinylpyrrolidone) (Ag-SiO2-PVP) nanoparticles for polymeric nanocomposites

Hydrophilic antibacterial silver decorated silica-grafted-poly(vinylpyrrolidone) (Ag-SiO₂-PVP) nanoparticles were successfully synthesized in multiple steps. In this regard, silanization of the silica nanoparticles was performed with different concentrations of vinyltrimethoxysilane (VTS) to generate vinyl groups onto the nanoparticles surface. Obtained results showed that by increasing the VTS concentration the amount of vinyl groups on the surface of the silica nanoparticles increased while nanoparticles agglomeration did not occur. Then, poly(vinylpyrrolidone) PVP brushes were grafted onto the silanized silica nanoparticles (SiO₂-VTS) via grafting-through polymerization method to obtain PVP-grafted silica nanoparticles (SiO₂-PVP). Fourier transform infrared spectroscopy, thermal gravimetric analysis, and dynamic light scattering confirmed the successful generation of the vinyl groups and PVP brushes onto the silica nanoparticles. Finally, Ag-SiO₂-PVP nanoparticles were prepared by synthesizing silver nanoparticles onto the SiO₂-PVP nanoparticles to render them antibacterial. Energy dispersive X-ray spectroscopy showed that highest grafting of silver nanoparticles onto the SiO₂-PVP nanoparticles was obtained for the nanoparticles with highest content of vinyl groups. X-ray photoelectron spectroscopy was used to identify the elements and their chemical structure for the synthesized nanoparticles. Plate colony counting method was applied to assess the antibacterial effects of the Ag-SiO₂-PVP nanoparticles which revealed outstanding bactericidal properties of them.     

Vinyl Polymerization. 218. Polymerization of Methyl Methacrylate in the Presence of Nylon-6 Fiber and Water

The polymerization of methyl methacrylate in the presence of nylon-6 fibers and water was carried out. It was found that the conversion in the absence of water was the same as that of thermal polymerization, but in the presence of water the conversion was much higher. When methyl methacrylate and water existed sufficiently in the polymerization system, the rate of polymerization (R_p) was given by the following equation; R_p = k (Nylon)^1,0 (Methyl methacrylate)⁰ (Water)⁰. The over-all activation energy of the polymerization was found to be 13 kcal/mole. The polymerization of styrene, acrylonitrile, vinyl acetate, and methyl acrylate could not be initiated by the system of nylon and water. Apparent grafting efficiency of polymethyl methacrylate onto nylon was calculated from the amount of polymer which was not extracted with acetone. The efficiency was independent on the reaction time and the amount of water, and increased with the amount of nylon, while it decreased with the amount of methyl methacrylate and with reaction temperature. From the fact that a major part of the polymethyl methacrylate could not be extracted, it was concluded that the polymerization of methyl methacrylate in the presence of nylon and water occured predominantly inside the fiber. The degree of the polymerization of polymethyl methacrylate formed inside the nylon fiber was considerably higher than that of homopolymethyl methacrylate formed outside the fiber. It was qualitatively recognized that the major part of the polymethyl methacrylate generated in the fiber was not grafted onto nylon, but existed as homopolymer.