Suface grafting of polymers onto nanodiamond by ligand-exchange reaction of ferrocene moieties of polymers with polycondensed aromatic rings of the surface

To improve the dispersibility of nanodiamond (ND) in solvents and polymer matrices, the grafting of copolymers containing vinyl ferrocene (Vf) onto the surface by a ligand-exchange reaction with ferrocene moieties of the copolymer and polycondensed aromatic rings of ND surface was investigated. The copolymer containing Vf was prepared by the radical copolymerization of Vf with vinyl monomers, such as methyl methacrylate (MMA), styrene (St), and N-isopropylacrylamide (NIPAM), using 2, 2′-azobisisobutyronitrile as an initiator. It was found that by heating of ND with poly(Vf-co-MMA), poly(Vf-co-St), and poly(Vf-co-NIPAN) in the presence of AlCl₃ and Al powder as catalysts, the corresponding copolymer was successfully grafted onto the surface. On the contrary, in the absence of AlCl₃, no grafting of these copolymers was observed. The grafting of polymers onto the ND surface was confirmed by FT-IR. These polymer-grafted NDs were found to give stable dispersions in solvents for the grafted polymer. In addition, the dispersibility of poly(Vf-co-NIPAM)-grafted ND uniformly dispersed in water below 32 °C but precipitated above the temperature. Therefore, it was concluded that the dispersibility of ND in water could be controlled by the temperature of water.     

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.     

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.     

Synthesis of vinylferrocene and the ligand-exchange reaction between its copolymer and carbon nanotubes

To improve the dispersibility of carbon nanotubes (CNTs), poly(vinylferrocene-co-styrene) (poly (Vf-co-St)), was grafted onto the surface of CNTs by a ligand-exchange reaction. Poly(Vf-co-St) was obtained by a radical copolymerization reaction using styrene and vinylferrocene as the monomers. The vinylferrocene was synthesized from ferrocene via a Friedel-Crafts acylation. The molecular weight, molecular weight distribution, and amount of Vf in the poly(Vf-co-St) were 1.32 × 10⁴, 1.69 and 17.6% respectively. The degree of grafting of the copolymer onto the CNTs surface was calculated from thermogravimetric analysis and varied from 27.1% to 79.7%. The addition of the poly(Vf-co-St) greatly promoted the dispersibility of the modified CNTs in anhydrous alcohol. The electrical conductivity of composites prepared from the polymer-grafted CNTs and copolymer (acrylonitrile, 1,3-butadiene and styrene, ABS) strongly depended on the degree of grafting. These results show that the amount of polymer grafted onto the surface of CNTs can be controlled and that the electrical properties of composites prepared with these grafted polymers can be tuned.     

Reactive carbon black having acyl imidazole or acid anhydride groups: Preparation and reaction with functional polymers having hydroxyl or amino groups

The introduction of acyl imidazole groups onto a carbon black surface was achieved by the reaction of the carboxyl groups on the surface with N N′-carbonyldiimidazole, the loading of acyl imidazole groups introduced was determined to be 0.28 mmol/g. In addition, reactive carbon black having acid anhydride groups was prepared by the reaction of phenolic hydroxyl groups with trimellitic anhydride chloride; the amount of acid anhydride groups introduced onto the surface was determined to be 0.20 mmol/g. The reaction of acyl imidazole groups on carbon black with commercially available polymers having hydroxyl or amino groups such resulted in polymers that were found to be grafted onto the surface via ester or amide bonds. The percentage of grafting of diol-type poly(propylene glycol) and diamine-type polydimethylsiloxane was increased to 27.2 % and 42.5 %, respectively. Furthermore, acid anhydride groups on carbon black also reacted with functional polymers having hydroxyl or amino groups to give polymer-grafted carbon blacks. The grafting reaction was accelerated by the addition of tertiary amines. These polymer-grafted carbon blacks produced a stable colloidal dispersion in good solvents for the grafted polymer, but readily precipitated in poor solvents.     

Modification of carbon black through grafting multihydroxyl hyperbranched polyether onto its surface

The hydroxy methyl groups were introduced onto the pristine carbon black surface through the reaction between unsaturated hydrogen atoms of the polycondensed aromatic rings of carbon black and formaldehyde in alkali condition. Using the resultant hydroxy methyl groups on the carbon black surface as the growth point, multihydroxyl hyperbranched polyether was grafted onto the carbon black surface by cationic ring‐opening polymerization of 3‐ethyl‐3‐(hydroxymethyl)‐oxetane in the presence of BF₃·OEt₂ to improve its dispersion ability in solvents. It was found that the modified carbon black could be dispersed in polar solvents, such as ethanol, chloroform, and DMF. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2086–2092, 2007     

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 poly(ethylene-block-ethylene oxide) onto a vapor grown carbon fiber surface by γ-ray radiation grafting

To modify the surface of vapor grown carbon fiber (VGCF), poly(ethylene-block-ethylene oxide) (PE-b-PEO, M_n=1400, PEO content=50 wt%) was successfully grafted onto the surface by using γ-ray irradiation of the PE-b-PEO-adsorbed VGCF in solvent-free system. It is found that the percentage of polymer grafting reached 15.0% when the PE-b-PEO-adsorbed VGCF was irradiated by γ-ray over 40 kGy dose at 110 °C, but at the lower irradiation temperature of 75 °C, the grafting reaction scarcely proceeded. This indicates that polymer radicals formed by γ-ray irradiation were successfully trapped by VGCF surface above melting point of PE-b-PEO. On the other hand, when the dispersion of VGCF in THF solution of PE-b-PEO was irradiated, the percentage of PE-b-PEO grafting was less than 4.0%. It was confirmed by a field-emission scanning electron microscope (FE-SEM) that the surface of the VGCF was uniformly covered by grafted PE-b-PEO. In addition, the surface free energy of ungrafted and PE-b-PEO-grafted VGCF was determined.     

Preparation of nano-ZnO/PMMA composite particles via grafting of the copolymer onto the surface of zinc oxide nanoparticles

The grafting of polymers onto the surface of zinc oxide nanoparticles and radical copolymerization of methyl methacrylate (MMA) and methacrylic acid (MAA) were investigated. The copolymer chains encapsulating nanoparticles were anchored onto the surface of nano-ZnO through reactions of carboxyl groups with ZnO. Grafting percentage and grafting efficiency of composite particles were investigated by employing thermogravimetric analysis (TGA). FT-IR and ¹³C NMR showed that there existed a strong interaction at the interface of nano-ZnO and copolymer, which implied that the copolymer chains were grafted onto the surface of ZnO nanoparticles. Nano-ZnO being encapsulated by copolymer was confirmed by using transmission electron microscopy (TEM). Additionally, TGA plots showed that the presence of ZnO nanoparticles improved the thermal stability of copolymer to a certain extent. Another important finding is the copolymerization and grafting reaction did not alter the crystalline structure of the ZnO nanoparticles according to the X-ray diffraction patterns. It can also be seen from scanning electron microscope (SEM) that grafted polymer chains on nanoparticles interfere with the aggregation of ZnO nanoparticles in polymer matrix and improve their compatibility with the polymeric matrix.     

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.     

Solvothermal preparation and characterization of maleic anhydride grafting high density polyethylene copolymer

In this article, the grafting copolymerization of maleic anhydride (MAH) onto high density polyethylene (HDPE) was carried out through solvothermal process. Infrared spectra (IR) revealed that MAH had been successfully grafted onto the HDPE backbone. The influences of the reaction parameters on the grafting copolymerization, e.g., the concentration of the initiator, MAH and HDPE content, reaction time, reaction temperature, comonomer, and different solvents were also studied. Further studies found that MAH could be grafted onto HDPE in both good solvents and poor solvents, which was much different from the traditional solution grafting method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Surface modification of acrylonitrile copolymer membranes by grafting acrylamide. I. Initiation by ceric ions

Surface modification of membranes of an acrylonitrile copolymer (PAN) containing 5.5% methyl methacrylate (MMA) and 4.0% sodium methylpropylenesulfonate by grafting acrylamide (AAm) with cetric ammonium nitrate as initiator in the aqueous medium has been studied. Results showed that the extent of grafting was varied with some parameters, such as dimethyl formamide and Tween-20 amount in the reaction solution, concentration of AAm, and reaction time. The grafted copolymer was verified by infrared spectra and X-ray photoelectron spectroscopy. Both of these methods also showed that the ester group of MMA unit on the surface of PAN membranes may be partially hydrolyzed into carboxyl group in the copolymerization condition. Surface and pore structures of PAN membranes after grafting were viewed under a scanning electron microscope (SEM). From SEM photos we know that AAm homopolymer branches were grafted onto the surface of the membrane and the morphology of membrane did not change. Results of contact angle of isooctane on the membrane under water showed that the wettability of the modified membrane was improved. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 66: 1521–1529, 1997     

A novel gas sensor from crystalline polymer-grafted carbon black: responsibility of electric resistance of composite from crystalline polymer-grafted carbon black against solvent vapor

Summary Crystalline polymers, such as poly(ɛ-caprolactone) (PCL), poly(ethylene adipate) (PEA), and polyethylene (PE), were successfully grafted onto carbon black surface by direct condensation of terminal groups of these polymers with carboxyl groups on the surface using N,N'-dicyclohexylcarbodiimide as a condensing agent. The electric resistance of a composite prepared from these crystalline polymer-grafted carbon black drastically increased to 10⁴–10⁵ times of initial resistance in good solvent vapor of grafted polymer and returned to initial resistance when it was transferred into dry air. However, the change of electric resistance of the composite hardly observed in poor solvent vapor. These results suggest that these composite can be applied as a novel gas sensor. Received: 18 February 1999/Accepted: 25 March 1999     

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.     

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     

Maleic anhydride/styrene melt grafting and crosslinking onto ethylene‐octene copolymer

Melt grafting of the multimonomer system of maleic anhydride (MAH)/styrene (St) onto ethylene‐octene copolymer (POE) was performed by a twin‐screw extruder. The effects of St and initiator contents as well as MAH/St on the grafting reaction were investigated. The structure and properties of the grafted POE were characterized by the Fourier transform infrared spectroscopy, melt flow index, dynamic rheological behaviors, and thermogravimetric analysis. It is shown that the addition of St can significantly enhance MAH grafting degree onto POE. MFI values of grafted POE are affected not only by MAH/St copolymer concentration, but also by initiator concentration. These data indicate that the interaction and reaction between MAH and St monomers plays an important role in the grafting reaction. St improves the grafting reactivity of MAH and reacts with MAH before the two monomers graft onto POE. And high grafting degree can be obtained while the gel content is still low. Compared with neat POE, grafted POE shows different dynamic rheological behaviors and high thermal stability. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

1,3-Bisdiphenylphosphinoferrocenes: the unexpected 2,5,-dilithiation of dibromoferrocene towards a new area of ferrocene-ligand chemistry

The synthesis and characterization of 1,3-bis-diphenylphosphinoferrocene is described for the first time. The ligand is obtained as a byproduct of the ortho-lithiation of 1,1′-dibromoferrocene, as a consequence of the dilithiation of one of the cyclopentadienyl rings. The intermediate compound 1,1′-dibromo-2,5-bis-(diphenylphosphino)ferrocene which is the precursor compound to the new ligand has been structurally characterized. Further reaction of 1,1′-dibromo-2,5-bis-(diphenylphosphino)ferrocene with n-butyllithium followed by quenching with chlorodiphenylphosphine affords the new 1,2,3,1′-tetrakis(diphenylphosphino)ferrocene, while the similar reaction of 1,1′-dibromo,2,2′-bis(diphenylphosphino)ferrocene gives 1,1′,2,2′-tetrakis(diphenylphosphino)ferrocene.     

Synthesis and characterization of a poly(acrylic acid)‐graft‐methoxy poly(ethylene oxide) comblike copolymer

A methoxy poly(ethylene oxide) (MPEO) grafted poly(acrylic acid) (PAA) comblike copolymer was synthesized by the direct condensation of MPEO onto the PAA backbone in the presence of dicyclohexyl dimethylcarbodiimide (DCC) and 4‐dimethylaminopyridine (DMAP). Its chemical structure was characterized by Fourier transform infrared and ¹H‐NMR spectroscopies. The effects of different catalysts, solvents, reaction temperatures, and reaction times on the grafting degree of the PAA‐g‐MPEO comblike copolymer were investigated. Compared to p‐toluene sulfonic acid, DMAP/DCC as a catalyst markedly increased the grafting degree. The optimum reaction conditions were a tetrahydrofuran/water mixture solvent, a reaction temperature of 50°C, and a reaction time of 168 h. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Grafting modification of Kevlar fiber using horseradish peroxidase

Summary Horseradish peroxidase catalyzed grafting of acrylamide (AM) onto Kevlar fibers in mixed solvents of dioxane and water was studied. The factors affecting the grafting reaction, such as solvents composition, reaction time, temperature, pH of reaction media, concentration of acrylamide and hydrogen peroxide were examined. The modified fiber was characterized with IR, scanning electron microscopy (SEM), elemental analysis, XPS, contact angle measurement and the grafting yield. The O/C ratio and N/C ratio on the surface increased after treatment and the surface of the Kevlar fiber became rougher. The contact angle decreased from 80 to 45 after grafting, indicating the wettability of the fiber increased after modification. All the results suggested that AM have been grafted onto the Kevlar surface through HRP-mediated radical initiated grafting reaction. And the probably mechanism of HRP catalyzed grafting of AM onto Kevlar surface was proposed.     

Synthesis of phenoxymethyl ethylene carbonate using quaternary ammonium salt catalysts grafted onto styrene-vinylbenzylchloride-montmorillonite support

The synthesis of phenoxymethyl ethylene carbonate (PMEC) from carbon dioxide and phenyl glycidyl ether (PGE) was investigated using styrene-vinylbenzylchloride-montmorillonite supported quaternary ammonium salt catalysts. The catalysts were prepared by grafting the copolymer of styrene (ST) and vinylbenzyl chloride (VBC) onto montmorillonite (MMT) interlayers, followed by the quaternization using trialkylamines. The influence of VBC concentration, the structure of trialkylamine, and the type of support on the catalytic activity was discussed. Quaternary ammonium salt grafted onto organophilic ST-VBC-MMT intercalates showed higher conversion of PGE than that grafted onto montmorillonite interlayers since the former exhibits greater affinity for organic solvents than the latter does.