Grafting of polyesters onto carbon black. III. Polymerization of β-propiolactone initiated by quaternary ammonium carboxylate groups on the surface of carbon black

By use of carbon black containing quaternary ammonium carboxylate (COO^?N⁺R₄) groups as catalyst, the anionic ring opening polymerization of β-propiolactone (PL) was carried out at 50°C. Although carbon black itself was unable to initiate the polymerization of PL, carbon black containing COO^?N⁺R₄ groups, which was prepared by the reaction of carboxyl groups with corresponding quaternary ammonium hydroxide, was found to be able to initiate the polymerization. The carbon black obtained from the polymerization gave a stable colloidal dispersion in an organic solvent, and it was confirmed that the polyester formed was effectively grafted onto the surface. In addition, the effect of quaternary ammonium countercation on the polymerization was investigated.     

Cationic grafting from carbon black. III. Grafting of polyesters from carbon black by ring-opening polymerization of lactones initiated by CO+ClO groups on carbon black

It was found that the cationic ring-opening polymerization of δ-valerolactone (VL), ε-caprolactone (CL), and β-propiolactone (PL) was initiated by carbon black containing CO⁺ClO groups, which were introduced by the reaction of COCl groups with AgClO₄. The polyester was propagated from CO⁺ClO groups and effectively grafted onto carbon black surface. The polymerizability of these lactones by CO⁺ClO groups decreased in the following order: VL > CL > PL. The increasing temperature of the polymerization caused an increase in the rate of the chain transfer reaction of the growing chains and brought about the decrease of grafting ratio of polyester onto carbon black.     

The free radical polymerization of vinyl monomers in the presence of carbon black

The polymerization of vinyl monomers has been carried out in the presence of furnace blacks using initiators such as 2,2′-azobisisobutyronitrile (AIBN) and benzoyl peroxide (Bz₂O₂) in nitrogen or oxygen atmosphere. The results indicate that free radicals form by the decomposition of initiators reacting with carbon blacks to give active sites on their surface which then capture either the free radicals or the growing polymer radicals. Using the monomers with negative e values, such as styrene and vinyl acetate, a marked retardation was observed in Bz₂O₂-initiated polymerization in the presence of furnace blacks, while a moderate inhibition was found in the polymerization initiated by AIBN. The polymerization reaction using Bz₂O₂ was found to be very sensitive to oxygen in the presence of furnace blacks and the involvement of oxygen was found to promote grafting onto the surface of carbon black by the growing polymer radicals, consequently giving polymer-grafted particles while hindering the formation of homopolymers. Furthermore, the reaction of Bz₂O₂ with the surface of furnace blacks in oxygen atmosphere has been studied in carbon tetrachloride at 45°C. The resulting carbon blacks show an increase in the number of surface quinone groups with an increase in reaction time.     

The polymerization of styrene catalyzed by n-butyllithium in the presence of carbon black

The polymerization of styrene catalyzed by n-butyllithium has been carried out in the presence of carbon black at 0°C in toluene. A large portion of the catalyst was consumed by the reaction with the carbon black surface and thus the growth of polystyrene anions on the surface was hindered to a considerable extent. The typical retardation of conversion of styrene monomer to polymer does not change even in the presence of carbon black pretreated with sodium borohydride solution. The intrinsic viscosities of the homopolymers formed in the presence of carbon black were found to be higher than those of the ones formed in the absence of carbon black. On the other hand, the addition of carbon black during the anionic polymerization of styrene was found to promote grafting the growing polymer anions onto the surface of carbon black, consequently giving polymer-grafted particles, while hindering the conversion of styrene into polymer. However, little grafting was observed when the carbon black pretreated with sodium borohydride solution was used. The phenomena indicate that quinonic groups present on the surface of carbon black may be responsible for the capture of growing polymer anions.     

Phase‐transfer‐agent‐aided polymerization and graft copolymerization of acrylamide

The use of phase‐transfer catalysts, with water‐insoluble initiators, for polymerization and graft copolymerization reactions was explored. The polymerization of a water‐soluble vinyl monomer, acrylamide (AAm), and the graft copolymerization of AAm onto a water‐insoluble polymer backbone, isotactic polypropylene (IPP), with a water‐insoluble initiator, benzoyl peroxide (BPO), and a phase‐transfer catalyst, tetrabutyl ammonium bromide (Bu₄N⁺Br^?), were carried out in a water/xylene binary solvent system. The conversion percentage of AAm into polyacrylamide (PAAm) and the percentage of grafting of AAm onto IPP were determined as functions of various reaction parameters, such as the BPO, AAm, and phase‐transfer‐catalyst concentrations, the amounts of water and xylene in the water/xylene mixture, the time, and the temperature. The graft copolymer, IPP‐g‐PAAm, was characterized with IR spectroscopy and thermogravimetric analysis. By a comparison of the results of the phase‐transfer‐catalyzed graft copolymerization of AAm onto IPP and the preirradiation method, it was observed that the optimum reaction conditions were milder for the phase‐transfer‐catalyst‐aided graft copolymerization. Milder reaction conditions, including the temperature, the time of reaction, and a moderate initiator (BPO), in comparison with high‐energy γ‐rays, led to better quality products, and the reaction proceeded smoothly with high productivity. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2364–2375, 2004     

Surface modification of carbon black to facilitate suspension polymerization of styrene and carbon black

To carry out suspension polymerization of styrene in the presence of carbon black, an effective method was introduced to modify carbon black using nitric acid for oxygen treatment. The surface modification of carbon black with oxidation was confirmed by Fourier transform infrared spectroscopy, thermogravimetric analysis, and scanning electron microscopy (SEM), which demonstrated that the chemical structure of carbon black has clearly changed. Compared with pristine carbon black (CB), SEM illustrates that the aggregation phenomenon of modified carbon black (MCB) was clearly weakened. After modification, the aggregation and inhibition effects of MCB on the polymerization of polystyrene/modified CB (PS/MCB) composite particles are obviously weakened. The lipophilicity of CB after modification was also increased during the synthesis of PS/MCB. The oxidized CB was successfully dispersed by polystyrene using in situ suspension polymerization. The dispersion and dosage of MCB in PS/MCB composite particles was greatly improved over that of CB in PS/CB composite particles. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46387.     

Vinyl polymerization by carbon black,VI. Physico-chemical characteristics of poly(N-vinylcarbazole) prepared by modified and unmodified carbon black

The polymerization initiating activity of carbon black N220, unmodified as well as modified by pretreatment with various protonic and aprotonic acids has been examined in regards to N-vinylcarbazole polymerization. The physico-chemical characteristics of the polymer obtained by these catalyst systems have been investigated by I.R., X-ray, ¹H-NMR, ¹³C-NMR, gel permeation chromatography and thermal analysis measurements. Under certain conditions the resultant polymer shows some partial insolubility in methylethylketone. Contrary to the usual belief, this is not due to any stereochemical difference between the polymeric entities as observed by ¹³C-NMR spectrum analysis of the methylethylketone insoluble fraction of the polymer.     

Grafting onto carbon black by the reaction of reactive carbon black having acyl chloride group with several polymers

Summary Acyl chloride group introduced onto carbon black rapidly lost its activity by the moisture in air. However, the decrease of acyl chloride group content in vacuum was negligibly small. By the reaction of the acyl chloride group with several polymers having hydroxyl or amino group, such as polyethylene glycol (PEG), poly(vinyl alcohol)(PVA), and polyethyleneimine (PEI), these polymers were found to be effectively grafted onto carbon black; for instance, the grafting ratio of PEG (Mn=8.2×10³), PVA (Mn=2.2×10⁴), and PEI (Mn=2.0×10⁴) was 18.5%, 32.9%, and 45.8%, respectively. The number of polymer grafted onto carbon black decreased with an increase of its molecular weight.     

Polymerization of allyl methacrylate with wool fabric using different initiators

Polymerization of allyl methacrylate (AMA) with wool fabrics using different initiators, namely, potassium persulphate, Fe²⁺? H₂O₂, benzoyl peroxide, ceric ammonium nitrate, and vanadium pentanitrate, was investigated. The percent of polymer add-on depends upon the type and concentration of the initiator. Addition of metallic salts such as Fe³⁺ to the polymerization system enhances polymerization significantly when benzoyl peroxide and potassium persulphate are used independently as initiator. The opposite holds true for ceric ammonium nitrate and vanadium pentanitrate. With Fe²⁺? H₂O₂, on the other hand, the enhancement is marginal. Also studied was the incorporation of Li⁺, Cu⁺⁺, and Fe³⁺ at different concentrations in AMA—wool–benzoyl peroxide polymerization systems. Determination of the polymer add-on on the basis of double bond analysis revealed that the remained double bond is governed by the magnitude of the polymer add-on as well as by the type of initiator.     

Radical polymerization of vinyl monomers in the presence of carbon black initiated by 2,2'‐azobisisobutyronitrile and benzoyl peroxide in ionic liquid

The radical polymerization behavior of vinyl monomers, such as styrene, methyl methacrylate (MMA), and vinyl acetate (VAc), in the presence of carbon black initiated by benzoyl peroxide (BPO) and 2,2'‐azobisisobutyronitrile (AIBN) in ionic liquid (IL) was compared with those in toluene. 1‐Butyl‐3‐methylimidazolium hexafluorophosphate was used as IL. The radical polymerization of vinyl monomers initiated by BPO and AIBN in the presence of carbon black was remarkably retarded in toluene. On the contrary, the retardation of the polymerization by carbon black was considerably reduced in IL. During the radical polymerization in the presence of carbon black, a part of polymer formed was grafted onto carbon black surface based on the termination reaction of the growing polymer radicals with carbon black surface. The percentage of grafting and molecular weight of polymer in IL were much higher than those in toluene. This may be due to the fact that lifetime of the growing polymer radical is prolonged because of high viscosity of IL. Therefore, the growing polymer radicals with higher molecular weight were trapped by carbon black surface, because of stabilization of polymer radicals. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Alkaline hydrolysis of alkylated acidic groups on carbon black

Potentiometric pH-stat titration was performed on alkylated carbon black dispersed in aqueous solution at pH 9.0, 10.0 and 11.0 and alkaline hydrolysis rate constant of the alkylated functional groups on the carbon black was obtained therefrom. Carbon black treated with C₁-C₈n-alcohols in vapor or liquid phase was used in this experiment. Hydrolysis proceeded more rapidly for carbon black treated with lower alcohols. For each alkylated carbon black, the hydrolysis rate constant decreased with time and, after the hydrolysis rate diminished, a hydrolysis resistant fraction of alkylated groups remained. For example, the hydrolysis rate constants at 25°C were 24.33, 17.50 and 4.501 · mol^?1 · sec^?1 at 15 min and 6.00, 6.00 and 3.671 · mol^?1 · sec^?1 at 45 min after the start of hydrolysis at pH 9.0 for carbon black treated with C₂, C₃ and C₄ alcohols respectively.     

Raman spectra of Graphon carbon black

The Raman spectrum of Graphon carbon black has been recorded using rotating cell techniques. Angular dependence of scattering at 1360, 1580 and 2700 cm^?1 are reported and these data suggest that the 1360 cm^?1 line is associated with non-planar microstructure distortions. The excitation frequency dependence of the intensity ratio of the bands at 1360 (D) and 1580 cm^?1 (G) is interpreted in terms of resonance (vibronic) interaction. This dependence is primarily the result of an increase in the intensity of the 1360 cm ^?1 line. The disorder-associated line (D) exhibits a significant excitation-dependent shift from 1378 cm^i?1 (457.9 nm Ar⁺) to 1330 cm^?1 (647.1 nm Kr⁺). The “graphite” (G) line position is less sensitive to changes in excitation frequency. The spectral features are discussed in terms of factor group, C_6v⁴, and layer site symmetry, C_3v. Also the possible role of localized alkene-like structure in zones of structural distortion is considered.     

Oxidation processes on conducting carbon additives for lithium-ion batteries

The oxidation processes at the interface between different types of typical carbon additives for lithium-ion batteries and carbonates electrolyte above 5?V versus Li/Li⁺ were investigated. Depending on the nature and surface area of the carbon additive, the irreversible capacity during galvanostatic cycling between 2.75 and 5.25?V versus Li/Li⁺ could be as high as 700?mAh?g^?1 (of carbon). In the potential region below 5?V versus Li/Li⁺, high surface carbon additives also showed irreversible plateaus at about 4.1?C4.2 and 4.6?V versus Li/Li⁺. These plateaus disappeared after thermal treatments at or above 150?°C in inert gas. The influence of the irreversible capacity of carbon additives on the overall performances of positive electrodes was discussed.     

A temperature-responsive carbon black nanoparticle prepared by surface-induced reversible addition-fragmentation chain transfer polymerization

A reversible addition-fragmentation chain transfer (RAFT) agent, 2-{[(dodecylsulfanyl)carbonothioyl]sulfanyl}propanoic acid (DSCTSP), was immobilized on the hydroxyl-functionalized carbon black (CB) surface via a direct condensation reaction, producing CB-DSCTSP. Then, RAFT polymerizations were carried out on carbon black surface using the CB-DSCTSP as a chain transfer agent. Poly(N-isopropylacrylamide) (PNIPAAm) chains were grown from the carbon black surface by a surface-induced reversible addition-fragmentation chain transfer (SI-RAFT) polymerization. FT-IR, ¹H NMR, TGA, TEM, and dynamic light scattering were used to characterize the carbon black grafted with poly(N-isopropylacrylamide) (CB-g-PNIPAAm). Dispersion experiment showed that CB-g-PNIPAAm had a good solubility in water. ¹H NMR, AFM and dynamic light scattering measurements showed that CB-g-PNIPAAm behaved a reversible temperature-responsive property in water.     

Theoretical confirmation of in situ monitoring of monomer conversion during acrylamide polymerization via pyranine flouroprobe

In this study, a new approach for in situ monitoring of the monomer conversion based on the chemical interaction of a fluoroprobe, pyranine (8‐hydroxypyrene‐1,3,6‐trisulfonic acid, trisodium salt), with polymer chains during the free radical crosslinking copolymerization of acrylamide/bisacrylamide system (AAm/Bis) has been developed. Recently, we have shown that the pyranine fluoroprobes added to the prepolymerization solution in trace amounts bind covalently to the vinyl groups of the growing polymer chains via OH group by radical addition when the free radical polymerization of acrylamide (AAm) is initiated. This covalent binding results in a considerable blue shift in the emission spectrum of the pyranine, from 515 to ～ 420 nm. In this study 0.5, 0.7, and 1.0 mol L^?1 linear and crosslinked polymers including trace amounts of pyranine were synthesized. The change in the emission spectra of pyranine during polymerization and gelation were monitored as function of time. Here, we showed that both by theoretically and by comparing the fluorescence data with gravimetric measurements, the fluorescence intensity of pyranine monitored during the polymerization process can be used for in situ monitoring of the monomer conversion with great sensitivity. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Reactions of carbon black. Part I. Nonthixotropic carbon black compositions

The solution polymerization of butyl acrylate in the presence of a furnace black was found to produce a stable dispersion of carbon black which showed Newtonian flow, while the mixture prepared by mixing the same carbon black into a solution of poly(butyl acrylate) homopolymer had a large degree of thixotropy. A marked change in the viscosity of the reaction mixture was also observed at an early stage of polymerization when the initial mixture which was a moist mass with no fluidity, turned to a fluid easily stirred. The change in viscosity and the transition in flow behavior were carefully followed with a rotary cylinder type viscometer. The non-Newtonian initial mixture was found to turn to a Newtonian fluid at low conversion of the monomer. Beside the adsorption of the homopolymer onto the surface of carbon black particles, which would occur also in mechanical mixing, the change in the flow behavior was estimated to be caused by the change in the shape and the size of the dispersed carbon black particles due to the change in the condition of the surface of the particles by which growing polymer radicals, as well as initiator radicals, were captured.     

Rheology of copolymers containing carbon black

The rheological response of random copolymers of styrene and butyl methacrylate containing carbon black simulates the behavior of toner in the electrophotographic process. Both the relative viscosity and the dependence of viscosity on shear rate were increased by raising the temperature and raising the concentration and surface area of carbon black. For high concentrations and surface areas of carbon black and at elevated temperatures, a well-defined yield stress varied from 2.5 × 10² to 1.6 × 10⁴ Pa, depending on the concentration and nature of the carbon black but independent of the type of polymer and temperature, implying the formation of a carbon black network. Plasticization by carbon black was favored at low surface area and concentration of carbon black and at elevated temperatures.     

Novel comb‐structured‐polymer‐grafted carbon black by surface‐initiated atom transfer radical polymerization and ring‐opening polymerization

Novel comb‐structured‐polymer‐grafted carbon black (CB) was synthesized with a combination of surface‐initiated atom transfer radical polymerization and ring‐opening polymerization. First, poly(2‐hydroxyethyl methacrylate) (PHEMA) was grafted onto the CB surface by surface‐initiated atom transfer radical polymerization. The prepared CB‐g‐PHEMA contained 35.6–71.8% PHEMA, with the percentage depending on the molar ratio of the reagents and the reaction temperature. Then, with PHEMA in CB‐g‐PHEMA as the macroinitiator, poly(?‐caprolactone) (PCL) was grown from the CB‐g‐PHEMA surface by ring‐opening polymerization in the presence of stannous octoate. CB‐g‐PHEMA and CB‐g‐(PHEMA‐g‐PCL) were characterized with Fourier transform infrared, ¹H‐NMR, thermogravimetric analysis, dynamic light scattering, and transmission electron microscopy. The resultant grafted CB had a shell of PHEMA‐g‐PCL. On the whole, the CB nanoparticles were oriented in dendritic lamellae formed by these shells. This hopefully will result in applications in gas sensor materials and nanoparticle patterns. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Preparation and kinetic analysis of PS‐b‐PBA block copolymer by 4‐oxo‐TEMPO capped polystyrene macroinitiators

Polystyrene‐block‐poly(n‐butyl acrylate) block copolymers were prepared from 4‐oxo‐2,2,6,6‐tetramethylpiperidinooxy (4‐oxo‐TEMPO) capped polystyrene macroinitiators at a high temperature, 165°C. It was found that the number‐average molecular weight of PBA chains in block copolymers could reach above 10,000 rapidly at early stage of polymerization with a narrow polydispersity index of 1.2–1.4, but after that, the polymerization seemed to be retarded. Furthermore, according to the kinetic analysis, the concentration of 4‐oxo‐TEMPO was increased mainly by the hydrogen transfer reaction of hydroxylamine (4‐oxo‐TEMPOH) to growing radicals during polymerization. This increase in 4‐oxo‐TEMPO concentration could retard the growth of polymer chains. The rate constant of the hydrogen transfer reaction of 4‐oxo‐TEMPOH to growing radicals, k_H, estimated by the kinetic model is about 9.33 × 10⁴M^‐1s^?1 at 165°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

The effect of carbon black and colloidal silica fillers on interfacial adhesion at polystyrene interfaces

We have shown that the addition of small amounts of carbon black can drastically reduce the interfacial fracture toughness between polymers. This is interpreted as being due to strong interactions between the filler particles and the polymer chains which hinder interfacial adhesion. The effect is less severe when graphitic carbon black particles are used. The fracture toughness was found to increase with time as t ^{1 / 2}, regardless of filler concentration, indicating that interface formation was diffusion limited. A distinct minimum with filler concentration in the fracture toughness of interfaces annealed for times longer than 5 min was found. This feature could be explained as a balance between the increase in modulus and the decrease in polymer chain dynamics as a function of carbon black concentration. The addition of colloidal silica, where the surface interactions are screened, was found to reinforce the interface, as predicted by the Guth–Gold relationship. Mixing small quantities (<2%) of inert fillers with interfacially active ones restored the fracture toughness. This observation has practical importance since one can now obtain optimum adhesion without compromising the mechanical integrity provided by the reactive filler.