Grafting polystyrene onto silica nanoparticles via RAFT polymerization

Reversible addition-fragmentation chain transfer (RAFT) polymerization was used to graft polystyrene (PS) onto silica nanoparticles. A novel route was used to prepare the RAFT agent, 2-butyric acid dithiobenzoate (BDB) by substitution of dithiobenzoate magnesium bromide with sodium 2-bromobutyrate under alkali condition in aqueous solution. Epoxy groups were covalently attached to silica nanoparticles by condensation reaction of 3-glycidyloxypropyltrimethoxysilane (GPS) with the hydroxyl on the silica particle surface. RAFT agent functionalized nanoparticles were produced by ring-open reaction of the epoxy group with the carboxyl group of BDB. Then, PS chains with controlled molecular weights and narrow polydispersities (less than 1.1) were grown from the RAFT agent anchored nanoparticle surface. FT-IR, transmission electron microscopy (TEM) and thermogravimetric analysis (TGA) results showed that PS chains grew from silica particles by surface RAFT polymerization.     

超临界二氧化碳介质中苯乙烯-丁二烯-苯乙烯嵌段共聚物与丙烯酸的接枝反应

在超临界二氧化碳介质中进行了丙烯酸(AA)与苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)的接枝反应。接枝率随AA浓度的增加而增加,最高可达15.6%。用扫描电镜观察发现,当接枝率达到3.4%时产物表面出现了皱折,而当接枝率达到9.3%时,产物表面有颗粒出现,而且其数量和直径随接枝率的增加而增加。     

Grafting onto wool

Summary In order to ascertain the role of -SH groups in graft copolymerization of vinyl monomers onto Himachali wool fiber, an attempt has been made to graft copolymerize ethylacrylate (EA) onto reduced wool, in the presence of cerie sulfate (CS) as redox initiator in aqueous medium. Reduction of wool was carried out with thioglycolic acid (TGA) in aqueous solution. Percentage of grafting and percent efficiency were determined as functions of (a) Concentration of initiator (CS), (b) Concentration of monomer (EA), (c) Concentration of Sulfuric acid, (d) Time and (e) Temperature. Reduction of wool does not promote grafting of EA. The unreduced wool during ceric ion-initiated grafting of EA was reported earlier from this laboratory to produce more grafting. In ceric ion-initiated grafting of vinyl monomer onto wool, -SH groups do not play significant role. A plausible mechanism of grafting of EA onto reduced wool in the presence of ceric ion initiator has been suggested.     

Grafting onto wool

Summary In order to study the role of -SH group of wool in graft copolymerization, an attempt has been made to study grafting of acrylic acid (AAc) onto reduced wool in aqueous medium using ceric ammonium nitrate (CAN) as redox initiator. HNO₃ was found to catalyze the graft copolymerization. Reduction of wool was effected with thioglycolic acid (TGA) in aqueous medium. Percentage of grafting was determined as a function of concentration of (i) CAN, (ii) vinyl monomer (AAc), (iii) nitric acid, (iv) time and (v) temperature. Under optimum conditions, poly-(acrylic acid) was grafted to the reduced wool to the extent of 9.14%, the unreduced wool under optimum conditions afforded maximum grafting of poly(AAc) to the extent of 12.24%. Reduction of wool does not promote grafting of AAc in the presence of CAN.     

Grafting of poly(methyl methacrylate) or polyacrylonitrile onto polystyrene using ATRP technique

One of the most useful methods for synthesizing the graft and well‐defined copolymers is the atom transfer radical polymerization (ATRP) method. The polymerization was initiated by polystyrene (PS) carrying chloroacetyl groups as macroinitiator, in the presence of copper chloride (CuCl) and bipyridine (bpy). The macroinitiator (chloroacetylated PS) was prepared by successive chloroacetylation of PS under mild conditions and these reaction conditions overcome the problem of gelation and crosslinking in polymers. Successful graft copolymerizations were performed with methyl methacrylate (MMA) in toluene at 80°C and with acrylonitrile (AN) in tetrahydrofuran/ethylenecarbonate (62.5/37.5 v/v %) mixed solvent at 55°C. The characterization of the copolymers was investigated by ¹H‐NMR and FT‐IR spectroscopices. Gel permeation chromatography measurement indicated an increase of the molecular weight of the graft copolymers, as compared to that of the macroinitiator. This measurement also indicated the monomodal molecular weight distribution. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 2619–2627, 2006     

Plasma induced grafting of PSt onto titanium dioxide powder. II

Grafting of polystyrene (PSt) onto titanium dioxide powder was investigated in this study. The graft polymerization reaction was induced by N₂ plasma treatment of the surfaces of the titanium dioxide powder. IR and XPS results showed that PSt was grafted onto the titanium dioxide powder. The crystal structure of the titanium dioxide powder observed by XRD spectra was unchanged after plasma graft polymerization. In the grafting reaction, the grafting yield increased with the plasma power, the plasma treatment time, and the grafting reaction, but it increased first then decreased after reaching 50°C. The type of monomers also has an effect on the grafting yield. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 2112–2117, 2005     

Grafting onto polyformaldehyde fibers

Acrylic acid (AA), acrylonitrile (AN), and acrylamide (AM) were grafted onto polyformaldehyde (PF) fibers employing γ-ray irradiation as well as benzoyl peroxide initiation. The nature of the graft copolymer obtained from a given monomer was dependent on the type of method used for the grafting reactions. This was reflected in the various characteristics of the grafted PF fibers such as moisture regain and dyeability to disperse, direct, basic, and acid dyes. The extent of grafting was dependent on time, concentration of the initiator, concentration of monomer, and irradiation dose. The grafting reaction with all the three monomers and both methods of grafting studied followed first-order kinetics. The rate constant values for grafting with AA, AN, and AM were 0.493, 0.576, and 0.420 hr^?1, respectively for the irradiation method and 0.385, 0.385, and 0.346 hr^?1, respectively, for the benzoyl peroxide initiation technique. The increase in the moisture regain was directly proportional to the amount of graft in the fiber. Acrylic acid grafted PF fibers were rendered hydrophilic to the highest extent (7.9% M.R. for 42% graft), while AM-grafted fibers were rendered so to the lowest extent (7.23% M.R. for 76.5% graft). Considerable improvement in dyeability of PF fibers was observed as a result of grafting. In general, dyeability was proportional to the amount of graft introduced in the fibers. The AA-grafted PF fibers gave a six-to sevenfold increase in disperse dye content when the irradiation method was followed and a four-to fivefold improvement when the chemical method was used during the grafting reaction. The AA-grafted and AM-grafted PF fibers show considerable affinity toward direct cotton dyes. The two substrates could also be dyed with fiber-reactive dyes in deep fast shades, the AM-grafted PF fibers giving deeper shades as a result of higher reactivity imparted to the substrate by the NH₂ group of the graft copolymer. The AA- and AN-grafted PF fibers could be dyed in intense deep shades with cationic dyes. Similarly, AM-grafted substrates gave bright deep shades with acid dyes. Infrared studies, used to analyze the grafted PF fibers, indicated the presence of ? COOH, ? CN, and ? NH₂ groups introduced in the fiber structure as a result of grafting with AA, AN, and AM.     

Preparation and characterization of porous titanium dioxide sulfonated polystyrene composite microspheres with amphiphilicity

Porous particles with amphiphilicity were prepared by a nonpolymeric pore‐formation process with the sulfonation of polystyrene microspheres. Nano titanium dioxide (TiO₂) particles were then grafted onto the surface via a sol–gel method to finally form the composite particles. The effects of the mass ratio of ethanol (EtOH) to water, temperature, and solubility parameter on the pore‐formation process is discussed in detail. The morphology, porous structure, and wetting properties of the particles were studied by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared (FTIR) spectroscopy, and contact angle measurement. The results show that porous sulfonated polystyrene (SP) microspheres could be fabricated at 60°C with a 1 : 1 mass ratio of EtOH–water and a solubility parameter of 29.69 MPa^1/2. The TiO₂ particles were determined to be grafted onto the SP microspheres by physical‐bond interaction on the basis of FTIR analysis. The contact angles for both water (aqueous‐phase) and various organic solvent (oil‐phase) droplets with different polarities on the surface of compressed tablets of TiO₂–SP powder were all lower than 30°; this indicated excellent amphiphilicity in the composite particles. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Study of polystyrene/titanium dioxide nanocomposites via melt compounding for optical applications

This article presents the study of melt compounding of polystyrene (PS) with various types of titanium dioxide (TiO₂) nanoparticles and surfactants, using a corotating twin screw extruder with multiple screw element configurations. It was found that a properly designed high shear screw configuration and the copolymer of silicone, ethylene oxide, and propylene oxide‐based surfactant produced the greatest degree of nanoparticle dispersion in PS/TiO₂ nanocomposites, whereas a silane‐based surfactant and silicon dioxide (SiO₂) or aluminum oxide (Al₂O₃) coated TiO₂ nanoparticles yielded nanocomposites with the least photocatalytic degradation effects and the best retention of tensile and impact properties. POLYM. COMPOS., 28:241–250, 2007. © 2007 Society of Plastic Engineers     

Grafting biodegradable polyesters onto cellulose

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

Methylmethacrylate Grafting onto Cotton Stalk Pulp

Grafting of cotton stalk pulp with methylmethacrylate monomer using a ceric salt redox system is carried out. The effect of different variables—for example, monomer dose, reaction time, reaction temperature, acid concentration, initiator concentration, and liquor ratio—are studied. The effect of the presence of different amounts of residual lignin in cotton stalks pulp on the grafting process is demonstrated. Residual lignin percentage in the pulp plays an important role in determining the grafting rate. A sharp decrease in the grafting rate is observed by increasing the residual lignin percent in pulp from 1.64% to 4.96%. As the residual lignin percentage in the pulp is increased to 12% in pulp, the grafting reaction is nearly stopped. Optimization of the grafting conditions is clarified.     

Grafting of glycidyl methacrylate onto gelatin

Gelatin was graft copolymerized with poly(glycidyl methacrylate) using potassium peroxydisulfate in aqueous medium. Effect of temperature, time, initiator, monomer, and backbone concentrations were studied. The percent grafting was found to increase initially and then decrease in all the cases except with variation of monomer concentration. The rate of grafting, grafting efficiency, and percent of grafting were calculated. The grafting results have been discussed in the light of the rate of grafting. Mechanical properties, FT IR spectra, percent swelling, and percent dye uptake were carried out on the graft copolymerization and the results discussed.     

Grafting of acryloyl cyanoacetohydrazide onto chitosan

Chitosan was grafted with a novel monomer namely Acryloyl cyanoacetohydrazide (ACAH) which contains carbonyl and cyano groups. The graft copolymerization was conducted in heterogeneous phase using potassium persulfate (K₂S₂O₈) and sodium bisulfite (NaHSO₃) as redox initiators. The effect of monomer concentration, initiator concentration and ratio, time and temperature on the extent of grafting (G%) and the efficiency of grafting were studied. Homopolymer formation has not been observed under all the investigated conditions. The grafted samples were characterized by FTIR spectroscopy, X-ray diffraction and thermogravimetric analysis. The crystallinity of the used chitosan was reduced by grafting. Dye uptake of the grafted samples towards the different types of dyes (acidic, and basic) was investigated and was found to improve profoundly over the native chitosan with a higher uptake for the acidic dye. The grafted samples showed an increased swelling in water, which increased further upon quaternization of the graft copolymers. The extent of swelling is higher in acidic and basic media more than in neutral pH. The quaternized graft copolymer was found to be soluble in water. The fungicidal activity of the quaternized graft copolymers towards three soil-borne sugar beets pathogens was investigated in vitro. The effect on the micro organisms is proportional to the amount of ACAH in the graft copolymer.     

Identification and characterisation of high impact polystyrene — Part I: Microscopic identification of high impact polystyrene filled with titanium dioxide

Phase contrast microscopy cannot be applied for the identification and characterisation of high impact polystyrenes if the final product is filled with titanium dioxide. In such cases, coupling the solution of high impact polystyrene in a mixture of chloroform and ether with a diazonium salt of p-nitroaniline results specifically in the coloration of the elastomeric particles, which can be viewed clearly under the microscope. It has been observed that the shape, size and dispersion of the elastomeric particles remain undisturbed during the coupling reaction.     

聚烯烃弹性体与马来酸酐的熔融接枝

以双螺杆挤出机作为反应器，比较了聚烯烃弹性体（POE），线性低密度聚乙烯（LLDPE）与马来酸酐（MAH）的熔融接枝反应。尽这两种树脂具有相近的支化度，但由于POE树脂的大支链对大分子自由基之间的偶合反应具有抑制作用，所以，POE/MAH接枝体系的接枝率明显高于LLDPE／MAH接枝体系，而且接枝产物保持了较好的流动性；酸酐在POE树脂上的接枝率随过氧化物和接枝单体用量的增加而增大。接枝树脂可以明显提高PE与铝之间的粘接强度。     

Grafting of polyesters onto carbon whisker surface

Summary Polymerization of N-(p-aminobenzoyl)-caprolactam (PAC) in melts of polyols such as dihydroxy-terminated oligo(oxytetramethylene) with M_n=2000 g/mol at 200°C afforded stable dispersions of poly(p-phenylenebenzamide) whiskers in polyol. In spite of the low molecular weight of the polyaramide, which was isolated by solvent extraction, the microparticles are efficient reinforcing agents of polyurethanes because of the excellent interfacial adhesion resulting from covalent attachment of the polyols onto the microparticle surfaces. The role of the competing formation of p-aminobenzoate-terminated polyols via esterification of PAC was investigated. Morphological and mechanical properties of polyurethane microcomposites, prepared from poly(p-phenylenebenzamide)/poly(oxytetramethylene)diol dispersions and 4,4-diisocyanatodiphenylmethane, were determined as a function of the microparticle content. When compared to conventional polyurethanes, containing equivalent amounts of spherical organic and inorganic fillers, the microcomposites give higher Young's modulus, tensile strength without sacrificing high elongation at break.