Synthesis and characterization of novel type poly (4-chloromethyl styrene-grft-4-vinylpyridine)/TiO2 nanocomposite via nitroxide-mediated radical polymerization

This paper describes the synthesis and characterization of novel type poly (4-chloromethyl styrene-graft-4-vinylpyridine)/TiO₂ nanocomposite. Firstly, poly (4-chloromethyl styrene)/TiO₂ nanocomposite was synthesized by in situ free radical polymerizing of 4-chloromethyl styrene monomers in the presence of 3-(trimethoxysilyl) propylmethacrylate (MPS) modified nano-TiO₂. Thereafter, 1-hydroxy-2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO-OH) was synthesized by the reduction of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO). This functional nitroxyl compound was covalently attached to the poly (4-chloromethyl styrene)/TiO₂ with replacement of chlorine atoms in the poly (4-chloromethyl styrene) chains. The controlled graft copolymerization of 4-vinylpyridine was initiated by poly (4-chloromethyl styrene)/TiO₂ nanocomposite carrying TEMPO groups as a macroinitiators. The coupling of TEMPO with poly (4-chloromethyl styrene)/TiO₂ was verified using ¹H nuclear magnetic resonance (NMR) spectroscopy. The obtained nanocomposites were studied using transmission electron microscopy (TEM), Fourier-transform infrared (FTIR) spectra, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC) and the optical properties of the nanocomposites were studied using ultraviolet-visible (UV-Vis) spectroscopy.     

Stabilization of nano-TiO2 aqueous dispersions with poly(ethylene glycol)-b-poly(4-vinyl pyridine) block copolymer and their incorporation in photocatalytic acrylic varnishes

In this work, TiO₂ nanoparticles were dispersed and stabilized in water using a novel type of dispersant based on tailor-made amphiphilic block copolymers of poly(ethylene glycol)-block-poly(4-vinyl pyridine) (mPEG-b-P4VP) prepared by atom transfer radical polymerization (ATRP). The performance of this new block copolymer as dispersant was compared to a polyelectrolyte dispersant commonly used for TiO₂, sodium salt of polyacrylic acid (Na-PAA). The effect of dispersion technique and type and amount of dispersant on deagglomeration and stability of the TiO₂ aqueous suspensions were studied. After incorporation in a standard waterborne acrylic varnish formulation, dry film transparency, photocatalytic activity, and nanoparticle cluster size were also evaluated. The results show that mPEG-b-P4VP copolymer with appropriate block lengths can have a better performance than Na-PAA in terms of aqueous dispersion stabilization and cluster size reduction in the acrylic matrix. This translates into higher film transparency and photocatalytic performance.     

Low-density polyethylene modified by thermal polymerization of 4-vinylpyridine and methyl methacrylate: Structural studies

The structures of low-density polyethylene (LDPE) modified by in situ sorption and thermal polymerization of 4-vinylpyridine (4VP) and of methyl methacrylate (MMA) were studied. The phase behavior of these materials was investigated by means of X-ray diffraction, scanning electron microscopy (SEM), and by thermal measurements (DSC). The diffraction studies indicated that the polymerization occurs at the amorphous domains of the matrix, except for the case of 4VP (168.0%), in which polymerization at the crystalline domains of LDPE matrix was also observed. These materials showed at least two T_g values, indicating microphase separation. The morphology of LDPE-P4VP was different from that of LDPE-PMMA.     

Modeling and optimization of a new impact-toughened epoxy nanocomposite using response surface methodology

This paper reports the development of a high-impact epoxy nanocomposite toughened by the combination of poly(acrylonitrile-co-butadiene-co-styrene) (ABS) as thermoplastic, clay as layered nanofiller, and nano-TiO₂ as particulate nanofiller. Response surface methodology (RSM) was applied for optimization and modeling of the impact strength of epoxy/ABS/clay/TiO₂ quaternary nanocomposite. A second-order mathematical model between the response (impact strength) and variables (ABS, clay and nano-TiO₂ contents) was derived. Analysis of variance (ANOVA) showed a high coefficient of determination value (R ² = 98%). Under optimum conditions, maximum impact strength of 29.2 KJ/m² with 197% increase compared to neat epoxy was experimentally obtained. Also correlation between morphology and impact strength of the nanocomposite was investigated using scanning electron microscopy (SEM) and X-ray diffraction (XRD). A dispersion of exfoliated clay platelets, TiO₂ nanoparticles with low agglomeration and ABS nanoparticles was obtained as morphology of the nanocomposite. A new and more effective method for impact toughening of epoxy was introduced. This study clearly showed that the addition of the combination of layered and particulate nanofillers along with ABS as thermoplastic has a considerable enhancement effect on impact strength of epoxy.     

Synthesis of conductive PSt-g-PANi/TiO2 nanocomposites by metal catalyzed and chemical oxidative polymerization

Well-defined polymer-TiO₂ nanocomposites of core–shell structure were prepared by two-steps, surface-initiated atom transfer radical polymerization (ATRP) of styrene and in situ chemical oxidative polymerization of aniline monomers from the surfaces of the TiO₂ nanoparticles. The methods used include the following: initially, the ATRP initiator was covalently attached to the surface of TiO₂ nanoparticles by esterification of 2-bromo-2-methyl propionic acid with hydroxyl group. The metal-catalyzed radical polymerization of styrene with modified TiO₂ nanoparticles was performed using a copper catalyst system to give the TiO₂-based core hybrids linking PSt segments (TiO₂-PSt hybrids). Next, the TiO₂-PSt reacted with HNO₃/H₂SO₄ to produce a nitro group containing polystyrene to form TiO₂-PSt-NO₂, and obtained TiO₂-PSt-NO₂ was treated with hydrochloric acid/SnCl₂, and converted to an amine group containing polystyrene (TiO₂–PSt-NH₂). Finally, surface oxidative graft copolymerization of aniline, using the –NH₂ moieties of TiO₂/PSt-NH₂ as the anchoring sites. Characterization of these well-defined nanocomposites included FTIR, thermogravimetric analysis, transmission electron microscopy, and X-ray diffraction.     

Double In Situ Approach for the Preparation of Polymer Nanocomposite with Multi-functionality

A novel one-step synthetic route, the double in situ approach, is used to produce both TiO₂ nanoparticles and polymer (PET), and simultaneously forming a nanocomposite with multi-functionality. The method uses the release of water during esterification to hydrolyze titanium (IV) butoxide (Ti(OBu)₄) forming nano-TiO₂ in the polymerization vessel. This new approach is of general significance in the preparation of polymer nanocomposites, and will lead to a new route in the synthesis of multi-functional polymer nanocomposites.     

Fabrication and evaluation of light-curing nanocomposite resins filled with surface-modified TiO2 nanoparticles for dental application

A kind of light-curing nanocomposite resin, which consisted of reactive monomers, surface-modified TiO₂ nanoparticles and a photoinitiation system, has been developed for the application of dental restoration. It may be noted that the conjugation of glycidyl methylmethacrylate (GMA) onto the surface of TiO₂ nanoparticles (nano-TiO₂) contributed to improvement in miscibility between nano-filler and matrix, because the reactive C=C group of GMA participated in curing of the matrix, and hence resulted in the enhancement of mechanical properties. When the content of GMA-modified nano-TiO₂ was 2 wt%, the flexural strength and modulus of the nanocomposite resin reached 147.8 and 2918.3 MPa, respectively, which increased by 21.7 and 30.8 % in contrast to the resin without adding nano-filler. Furthermore, the polymerization shrinkage decreased after incorporating the nano-filler while the degree of monomer conversion and the water sorption for the nanocomposite resins was comparable with those of the resin without nano-filler. In conclusion, this study presented a new method, namely introduction of functional groups onto the nano-filler surface to participate in the reaction of resin monomer, to improve the interfacial adhesion and the resultant miscibility between nano-filler and resin matrix in light-curing dental nanocomposites by chemical linkage mediated with surface-modified specie. Moreover, the enhanced mechanical properties and decreased polymerization shrinkage of nanocomposite resins, which are considered the key to the effects of dental restoration, contributed a great potential as a dental material utilized for caries treatment and prevention.     

Synthesis, Characterization, and Some Properties of 4-Vinylpyridine-Cr(CO)5 Containing Polymers

The polymerization of 4-vinylpyridine (4VP) and 4-vinylpyridine chromium pentacarbonyl [(4VP)Cr(CO)₅] was performed under N₂ atmosphere at 60–80°C temperature range. Different percent of feed (%PF) of Cr(CO)₅ groups were anchored into poly(4-vinylpyridine) (P4VP) by addition of the intermediate Cr(CO)₅THF, which was generated photochemically from Cr(CO)₆ in THF, to the polymer at ambient temperature. The determined percent of anchoring (%PA) has shown that the maximum anchored Cr(CO)₅ groups was 40% (w/w) with respect to P4VP, and the optimum percent of anchoring was 20% (w/w). The rate of polymerization (R _p ) and the activation energy (E _a ) of 4VP in the absence and in the presence of 16.7% Cr(CO)₅(4VP) were determined. Thermal analysis has shown various changes in the properties of the 4VP polymers after modification of the polymer by Cr(CO)₅ groups. The X-ray diffraction and the melting enthalpy derived from the DSC thermogram revealed that the synthesized poly[(CO)₅Cr(4VP)] has a crystallinity of about 40%, whereas no crystallinity was observed for pure P4VP.     

A novel route for the synthesis of poly(2‐hydroxyethyl methacrylate) grafted TiO2 nanoparticles via surface thiol‐lactam initiated radical polymerization

Hybrid nanocomposites of poly(2‐hydroxyethyl methacrylate) (PHEMA) and TiO₂ nanoparticles were synthesized via surface thiol‐lactam initiated radical polymerization by following the grafting from strategy. Initially, TiO₂ nanoparticles were modified by 3‐mercaptopropyl trimethoxysilane to prepare thiol functionalized TiO₂ nanoparticles (TiO₂? SH). Subsequently, surface initiated polymerization of 2‐hydroxyethyl methacrylate was conducted by using TiO₂? SH and butyrolactam as an initiating system. The anchoring of PHEMA onto the surface of TiO₂ nanoparticles was investigated by FTIR, ¹H‐NMR, XPS, TGA, and XRD analyses. The experimental results indicated a strong interaction between PHEMA and TiO₂ nanoparticles owing to covalent bonding. The TEM and SEM images of PHEMA‐g‐TiO₂ showed that the agglomeration propensity of TiO₂ nanoparticles was significantly reduced upon the PHEMA functionalization. The molecular weight and polydispersity index of the cleaved PHEMA from the surface of TiO₂ nanocomposites were estimated by GPC analysis. An improved thermal property of the nanocomposites was observed from TGA analysis. PHEMA‐g‐TiO₂ nanocomposites were found to be highly dispersible in organic solvents. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Dispersion at Single Unit TiO2 Nanoparticles Reduced Tg,Induced Chain Disentanglement and Reduced Tensile Modulus in Waterborne Acrylic Coatings

Spatially distributed TiO₂ nanoparticles induced an order of magnitude decrease of glass transition temperature, T_g, and chain disentanglement in waterborne acrylic coatings. Acrylic/TiO₂ coatings are synthesized in situ by batch emulsion polymerization. The copolymer is based on butyl acrylate (BA), methyl methacrylate (MMA), and acrylic acid (AA) with composition 56:42:2 mol%, and nano-TiO₂ (ca. 12 nm) is incorporated up to 3 wt% content. Transmission electron microscopy (TEM) showed that TiO₂ is dispersed at nearly single unit throughout the acrylic matrix. The nanoparticle reduced T_g and broadened the temperature range of the glass transition, δT_g. The considerable increase of δT_g suggests gradients of dynamics. Shear rheometry demonstrated that TiO₂ induced chain disentanglement, the rubbery modulus G_e decreased two orders of magnitude with only 1 wt% TiO₂ content thus increasing the packing length p (and the reptation tube diameter as d_t = kp, k > 1). Consequently, the tensile Young's modulus E decreased an order of magnitude, relative to the neat copolymer. The reduction of T_g, the slowdown of macromolecular dynamics, the chain disentanglement and the increase of d_t suggests dynamics modification due to intercalation of the entangled web by the TiO₂ nanoparticles, and these results may be ascribed to a nanoconfinement effect.     

Preparation of nano-TiO2/polyurethane emulsions via in situ RAFT polymerization

Stable nano-TiO₂/polyurethane (PU) emulsions were prepared via in situ reversible addition-fragmentation chain transfer (RAFT) emulsion polymerization of 2-hydroxyethyl acrylate (HEA)-capped PU macromonomer, using azobisisobutyronitrile (AIBN) as a radical initiator and 2-{[(butylsulfanyl)carbonothioyl]sulfanyl} propanoic acid (BCSPA) anchored onto TiO₂ nanoparticles (TiO₂-BCSPA) as a RAFT agent. When the molar ratio of AIBN to TiO₂-BCSPA was changed from 1:3 to 1:10, the polydispersity index (PDI) of polymers in the emulsions decreased from 1.83 to 1.06, due to more effective RAFT polymerization in the emulsions. The TiO₂ nanofillers were well-dispersed throughout the polymer films. The tensile strengths of the nanocomposite films were significantly enhanced due to coordination bonding between the TiO₂ nanofillers and the –COOH end groups of the polymers, as evidenced by the FT-IR spectral data.     

Synthesis of cross-linked poly(4-vinylpyridine) and its copolymer microgels using supercritical carbon dioxide: Application in the adsorption of copper(II)

Compared with conventional precipitation polymerization method, cross-linked poly(4-vinylpyridine) (P4VP) and its microgels copolymerized with α-methacrylic acid (MAA) were synthesized through a new route of stabilizer-free polymerization in supercritical fluids. The yellow, dry, fine powders were directly obtained from precipitation polymerization of 4-vinylpyridine in supercritical carbon dioxide (scCO₂) at pressures ranging from 70.0 to 230 bar, using N,N′-methylenebisacrylamide as cross-linker. The effects of the reaction pressure, cross-linker ratio, initiator concentration, and reaction time were investigated. The capacity of this microgel for adsorption of copper(II) was also studied. At higher cross-linker concentrations, a high yield of the cross-linked P4VP microgel was generated in scCO₂, and its particle size was less than 300 nm. Polymerization of cross-linked P4VP in scCO₂ was extremely sensitive to the density of the continuous phase. The adsorption followed the Langmuir isotherm. The adsorption capacities of cross-linked P(4VP-co-MAA) and cross-linked P4VP were 47.2 and 26.9 mg g⁻¹, respectively.     

Direct grafting poly(methyl methacrylate) from TiO2 nanoparticles via Cu2+‐amine redox‐initiated radical polymerization: An advantage of monocenter initiation

Cu²⁺ can oxidize amines to generate radicals to initiate radical polymerization of electron‐deficient monomers under mild conditions. Here, CuSO₄‐catalyzed redox‐initiated radical polymerizations of methyl methacrylate from amino‐functionalized TiO₂ nanoparticles (TiO₂‐NH₂ nanoparticles) was performed to prepare TiO₂ nanoparticles grafted with poly(methyl methacrylate) (TiO₂‐g‐PMMA hybrid nanoparticles) in dimethylsulfoxide or N,N‐dimethylformamide at 90°C. Infrared spectroscopy, thermogravimetric analysis, and X‐ray photoelectron spectroscopy confirmed the presence of the grafted PMMA and the grafting yield was about 50 wt%. Microscopy and particle‐size analysis indicated that TiO₂‐g‐PMMA nanoparticles had a good affinity to organic media. Because only aminyl radical (? NH?) on TiO₂ nanoparticles formed in Cu²⁺‐amine redox‐initiation step, there was no free PMMA chains formed during polymerization. Thus, our protocol provides a facile strategy to prepare inorganic/organic hybrid nanoparticles via one‐pot Cu²⁺‐amine redox‐initiated free radical polymerization. POLYM. ENG. SCI., 55:735–744, 2015. © 2014 Society of Plastics Engineers     

Synthesis and blend morphology of BA/BC-type binary graft copolymers composed of polyelectrolyte trunks

Poly(α-methylstyrene) (PMS) macromonomer having one vinylbenzyl group per polymer chain was prepared by the couplings of living PMS with p-chloromethylstyrene (CMS). Subsequently, well-defined poly[acrylic acid (AA)-g-α-methylstyrene (MS)] and poly[4-vinylpyridine (4VP)-g-MS] graft copolymers composed of polyelectrolyte trunks were prepared by radical copolymerization of PMS macromonomer with AA and 4VP monomers, respectively. Binary poly(AA-g-MS)/poly(4VP-g-MS) or poly[AA · triethyl amine (Et₃N) salt-g-MS)/poly(4VP-g-MS) graft copolymer blend films were cast from a benzene/methanol mixture. The morphological results of binary graft copolymer blends are discussed with respect to three-phase separated structures.     

PANI-chitosan-TiO2 ternary nanocomposite and its effectiveness on antibacterial and antistatic behavior of epoxy coating

A straightforward approach has been developed for fabricating antibacterial and antistatic epoxy coatings by using polyaniline-chitosan modified TiO₂ ternary nanocomposite. This nanocomposite was synthesized through the following steps. First, chitosan was grafted onto the TiO₂ nanoparticles and then final nanocomposite was prepared via solution polymerization of aniline. Electrical conductivity measurement revealed that nanocomposite with 7.5 wt % of the modified TiO₂ nanoparticles has noticeably higher conductivity compared to polyaniline. Evaluating the coatings' antibacterial property indicated epoxy coatings with the content of ternary nanocomposite show significant bactericidal activity against Gram-positive bacteria and have acceptable antibacterial action against Gram-negative ones. Also, obtained results showed that the ternary nanocomposite would greatly decrease coatings' surface resistivity and when nanocomposite content is about 2 wt % surface resistivity is about 3 × 10⁷ Ω sq⁻¹. On the contrary, the coating with nanocomposite loading exhibits improved thermal and mechanical performance compared to the coating made of neat epoxy. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47629.     

Chemical modification of TiO2 nanoparticles as an effective way for encapsulation in polyacrylic shell via emulsion polymerization

Encapsulation of inorganic nanoparticles by polymers is one of the interesting research topics that lead to the synthesis of nanocomposites. These nanocomposite materials comprise the properties of both organic polymer and inorganic nanoparticles. Here, hybrid latex particles with core–shell nanostructure were prepared via semi-batch emulsion polymerization. Copolymers of (methyl methacrylate-butyl acrylate) and (dimethylaminoethyl methacrylate-butyl acrylate-acrylic acid) were formed as the inner and outer layers, respectively on the surface of modified TiO₂ nanoparticles as the core. In order to create compatibility between inorganic and polymeric phases, modification of TiO₂ nanoparticles was performed with glycidyl methacrylate with an optimized procedure for the first time and then emulsion polymerization was carried out. The products of each step were fully characterized. The results of dynamic light scattering, TEM and SEM analyses proved the formation of encapsulated hybrid latex particles. DLS and SEM data revealed that the sizes of nanocomposite particles vary between 85 and 120 nm for 0–5 wt% of the modified TiO₂ nanoparticles. Physico-mechanical properties of the obtained nanocomposite films were studied by DMTA. It was found that using only 3 wt% of modified TiO₂ improved those properties of resulting films remarkably.     

Synthesis and properties of polystyrene‐g‐mSiO2 filled polypropylene nanocomposites

Hydrophobically modified nanosilica was prepared from tetraethoxysilane (TEOS) and γ‐methacryloxypropyltrimethoxysilane (MPS) by a two step sol‐gel process. The polystyrene‐grafted‐modified nanosilica (PS‐g‐mSiO₂) hybrid particles were prepared by grafting polystyrene onto the resulting hydrophobically modified nanosilica by dispersion polymerization. The hybrid nanoparticles were subsequently used as the filler to fabricate polypropyrene (PP) nanocomposites. The crystallization kinetics, crystal morphology and crystallization phase component of PS‐g‐mSiO₂/PP nanocomposite were studied using a differential scanning calorimeter (DSC), polarizing optical microscopy (POM) and X‐ray diffraction (XRD). Crystallization half life (t_1/2) decreased, while the Arami exponent (n) of PS‐g‐mSiO₂/PP nanocomposite increased compared with that of virgin PP. A rheological study allowed the unambiguous characterization of the dispersibility of nanosilicas in PS‐g‐mSiO₂/PP nanocomposite. The storage modulus, melt viscosity and the elongation to break of the PS‐g‐mSiO₂/PP nanocomposite were found to be strongly dependent on the grafting of PS on nanosilicas. POLYM. COMPOS., 2010. © 2009 Society of Plastics Engineers     

Synthesis, Characterization, and Some Properties of 4-Vinylpyridine-Cr(CO)5 Containing Polymers

The polymerization of 4-vinylpyridine (4VP) and 4-vinylpyridine chromium pentacarbonyl [(4VP)Cr(CO)₅] was performed under N₂ atmosphere at 60–80°C temperature range. Different percent of feed (%PF) of Cr(CO)₅ groups were anchored into poly(4-vinylpyridine) (P4VP) by addition of the intermediate Cr(CO)₅THF, which was generated photochemically from Cr(CO)₆ in THF, to the polymer at ambient temperature. The determined percent of anchoring (%PA) has shown that the maximum anchored Cr(CO)₅ groups was 40% (w/w) with respect to P4VP, and the optimum percent of anchoring was 20% (w/w). The rate of polymerization (R _p ) and the activation energy (E _a ) of 4VP in the absence and in the presence of 16.7% Cr(CO)₅(4VP) were determined. Thermal analysis has shown various changes in the properties of the 4VP polymers after modification of the polymer by Cr(CO)₅ groups. The X-ray diffraction and the melting enthalpy derived from the DSC thermogram revealed that the synthesized poly[(CO)₅Cr(4VP)] has a crystallinity of about 40%, whereas no crystallinity was observed for pure P4VP.     

A novel route for the synthesis of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) grafted titania nanoparticles via ATRP

A new method is presented for grafting poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) (P(HEMA-co-MMA)) chains from the surface of TiO₂ nanoparticles via atom transfer radical polymerization (ATRP). First, the ATRP initiators were immobilized onto the TiO₂ surface by using 3-aminopropyltriethoxysilane coupling agent and 2-bromoisobutyryl bromide. Then the copolymerization of 2-hydroxyethyl methacrylate with methyl methacrylate was initiated and propagated on the TiO₂ surface by ATRP. The resulting composite nanoparticles were characterized by means of XPS, FT-IR, ¹H NMR, GPC and TGA. The results indicated that the grafting of copolymer chains from the TiO₂ surface was successful. This method opens up new avenues for the preparation of TiO₂-polymer nanocomposites.     

A facile preparative method for gold-containing vesicles from poly(styrene-block-2-vinylpyridine) block copolymer/HAuCl4 complexes

It is found that the complexes of PS-b-P2VP and HAuCl₄ in THF can form a compound vesicle when the THF solution is treated at 40 °C. The compound vesicle is composed of an insoluble wall formed by P2VP/HAuCl₄ complexes and a soluble PS shell. The vesicular character of the aggregates was investigated by dynamic light scattering (DLS) and transmission electron microscope (TEM). The decrease of the solubility of P2VP blocks in THF drives the PS-b-P2VP/HAuCl₄ complexes to aggregate into vesicles, which are stable upon dilution or crosslinking. Based on this study, the vesicles decorated with gold nanoparticles can be produced, which hold potential for the facile organization of the vesicle-supported precious metal catalysts.