Modeling of “living” free‐radical polymerization processes. I. Batch,semibatch, and continuous tank reactors

A comprehensive mathematical model is developed for “living” free‐radical polymerization carried out in tank reactors and provides a tool for the study of process development and design issues. The model is validated using experimental data for nitroxide‐mediated styrene polymerization and atom transfer radical copolymerization of styrene and n‐butyl acrylate. Simulations show that the presence of reversible capping reactions between growing and dormant polymer chains should boost initiation efficiency when using free nitroxide in conjunction with conventional initiator and also increase the effectiveness of thermal initiation. A study shows the effects of the value of the capping equilibrium constant and capping reaction rate constants for both nitroxide‐mediated styrene polymerization (using alkoxyamine as polymer chain seeds) and atom transfer radical polymerization of n‐butyl acrylate (using methyl 2‐bromopropionate as chain extension seeds). Also the effect of introducing additional conventional initiator into atom transfer radical polymerization of n‐butyl acrylate is studied. It is found that the characteristics of long chain growth are determined by the fast exchange of radicals between growing and dormant polymer chains. Polymerization results in batch, semibatch, and a series of continuous tank reactors are analyzed. The simulations also show that a semibatch reactor is most flexible for the preparation of polymers with controlled architecture. For continuous tank reactors, the residence time distribution has a significant effect on the development of chain architecture. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1630–1662, 2002     

Thermal characterization of poly(vinyl chloride) samples prepared by living radical polymerization: Comparison with poly(vinyl chloride) prepared by free radical polymerization

Poly(vinyl chloride) (PVC) samples were synthesized by a living radical polymerization (LRP) method and compared with commercial PVC prepared by the conventional free radical polymerization (FRP). The differences were assessed, for the first time, in terms of viscosimetry parameters and thermal analysis. The LRP method used to prepare the PVC‐LRP samples is the only one available to obtain this polymer free of structural defects, being of commercial interest in a view of preparing a new generation of PVC‐based polymer with outstanding performance. The polymerization temperature selected (35°C) to prepare the LRP samples is currently used in the industry to prepare PVC‐FRP grades with moderate to high molecular weight. Since the thermal stability is a direct consequence of the polymer structure, this study is of vital importance to understand the potential of new PVC‐LRP. The thermoanalytical measurements demonstrate an enhanced thermal stability of PVC‐LRP when compared with its FRP counterpart. The PVC‐LRP sample with very low molecular weight reveals a higher thermal stability than the most stable PVC‐FRP sample. It is the first report dealing with thermal analysis of PVC prepared by LRP. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and characterization of poly(vinyl chloride‐co‐vinyl acetate)‐graft‐poly[(meth)acrylates] by atom transfer radical polymerization

The graft polymerization of methyl methacrylate and butyl acrylate onto poly(vinyl chloride‐co‐vinyl acetate) with atom transfer radical polymerization (ATRP) was successfully carried out with copper(I) thiocyanate/N,N,N′,N′,N″‐pentamethyldiethylenetriamine and copper(I) chloride/2,2′‐bipyridine as catalysts in the solvent N,N‐dimethylformamide. For methyl methacrylate, a kinetic plot of ln([M]₀/[M]) (where [M]₀ is the initial monomer concentration and [M] is the monomer concentration) versus time for the graft polymerization was almost linear, and the molecular weight of the graft copolymer increased with increasing conversion, this being typical for ATRP. The formation of the graft polymer was confirmed with gel permeation chromatography, ¹H‐NMR, and Fourier transform infrared spectroscopy. The glass‐transition temperature of the copolymer increased with the concentration of methyl methacrylate. The graft copolymer was hydrolyzed, and its swelling capacity was measured. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 183–189, 2005     

Grafting polymer from poly(ethylene terephthalate) films by surface‐initiated ATRP

Surface‐initiated atom transfer radical polymerization (ATRP) from poly(ethylene terephthalate) (PET) film was studied. Poly(methyl methacrylate) (PMMA), poly (acrylamide) (PAAM), and their diblock copolymer (PMMA/PAAM) on the surface of PET film were successfully prepared by surface‐initiated ATRP. The structures and properties of the modified PET film were characterized by FT‐IR/ATR, X‐ray photoelectron spectroscopy (XPS), measurements of contact angles, and scanning electronic microscopy (SEM). The results indicate that the surface properties of PET film were greatly improved by grafted polymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Fabrication and characterization of tunable wettability surface on copper substrate by poly(ionic liquid) modification via surface‐initiated nitroxide‐mediated radical polymerization

Poly(ionic liquid) surfaces with tunable wettability were successfully prepared on micro/nanoscale CuO/Cu composite substrates by a surface‐initiated nitroxide‐mediated radical polymerization technique. Various characterization techniques including X‐ray photoelectron spectroscopy, cold field emission scanning electron microscopy, and static water contact angle measurement were used to characterize the surfaces for each surface modification step. Kinetic studies revealed that the polymer chain growth from the surface was a controlled/“living” polymerization process. The surface with tunable wettability, reversible switching between hydrophilicity and hydrophobicity can be easily achieved by sequential counteranion exchange. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Internal plasticization of poly(vinyl chloride) by grafting acrylate copolymers via copper-mediated atom transfer radical polymerization

Internal plasticization of poly(vinyl chloride) (PVC) was achieved in one-step using copper-mediated atom transfer radical polymerization to graft different ratios of random n-butyl acrylate and 2–2-(2-ethoxyethoxy)ethyl acrylate copolymers from defect sites on the PVC chain. Five graft polymers were made with different ratios of poly(butyl acrylate) (PBA) and poly(2–2-(2-ethoxyethoxy)ethyl acrylate) (P2EEA); the glass transition temperatures (T_g) of functionalized PVC polymers range from − 25 to − 50°C. Single T_g values were observed for all polymers, indicating good compatibility between PVC and grafted chains, with no evidence of microphase separation. Plasticization efficiency is higher for polyether P2EEA moieties compared with PBA components. The resultant PVC graft copolymers are thermally more stable compared to unmodified PVC. Increasing the reaction scale from 2 to 14 g produces consistent and reproducible results, suggesting this method could be applicable on an industrial scale.     

Controlled radical polymerization catalyzed by CuCl/BDE complex in water medium. I. Polymerization of styrene and synthesis of poly(St‐b‐MMA)

The controlled radical polymerization of styrene in water medium, in the presence of polyoxyethylene nonyl phenyl ether, catalyzed and initiated by CuCl/BDE [bis(N,N′‐dimethylaminoethyl)ether]/R—X was studied. The results show that the molecular weight increased with conversion of the monomer. Using this controlled system, the block copolymer, poly(St‐b‐MMA), was successful synthesized in water medium. In reference to the system of CuCl/BDE/PhCH₂Cl, the polymerization may also occur in the micelle to produce a superhigh molecular mass (M_n = 1,500,000) polymer with monodispersion (MWD, M_w/M_n = 1.03). The Cu(I) and Cu(II) partition ratio in two phases, which may affect the reversible deactivation and debase the catalyst efficiency, was detected. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 75: 802–807, 2000     

Contributions to characterization of poly(vinyl chloride)–lignin blends

The present study evaluates the impact of blending organosolv and kraft lignins, which are natural polymer by‐products in the pulp and paper industry, with plasticized poly(vinyl chloride) (PVC) in flooring formulations. Also examined is the impact of replacing dioctyl phthalate, a PVC industry general‐purpose plasticizer, with diethylene glycol dibenzoate (Benzoflex 2‐45), tricresyl phosphate (Lindol), or alkyl sulfonic phenyl ester (Mesamoll) in these formulations. The influence of the different types of lignins and plasticizers on the processibility, thermal, and mechanical properties of the blends is discussed. These properties demonstrate that partial replacement of PVC (20 parts) with different lignins is feasible for some formulations that can be successfully used as matrices for a high level of calcium carbonate filler in flooring products. In addition, the data demonstrate that the presence of certain plasticizers, which interfere with the intramolecular interactions existing in lignins, may allow the lignin molecules to have more molecular mobility. The morphology and the properties of PVC plasticized lignin blends are strongly influenced by the degree and mode of the lignin plasticization and its dispersion within the PVC matrix. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2732–2748, 2006     

Rheological behavior and thermal properties of poly(butyl acrylate‐co‐2‐ethylhexyl acrylate)‐grafted vinyl chloride resin

The rheological behavior and thermal properties of a poly(butyl acrylate‐co‐2‐ethylhexyl acrylate) [P(BA‐EHA)]‐grafted vinyl chloride (VC) composite resin [P(BA‐EHA)/poly(vinyl chloride) (PVC)] and its materials were investigated. The rheological behavior, thermal stability, and Vicat softening temperature (VST) of P(BA‐EHA)/PVC were measured with capillary rheometry, thermal analysis, and VST testing, respectively. The effects of the P(BA‐EHA) content and the polymerization temperature of grafted VC on the rheological behavior of the composite resin were examined. The weight loss of the composite resin and its extracted remainder via heating were analyzed. The influence of the content and crosslinking degree of P(BA‐EHA) and the polymerization temperature of the grafted VC on VST of the materials was determined. The results indicated the pseudoplastic‐flow nature of the composite resin. The flow property of the modified PVC resin was improved because of the incorporation of the acrylate polymer. The molecular weight of PVC greatly influenced the flow behavior and VST of the composite resin and its materials. The flowability of the composite resin markedly increased, and the VST of its materials decreased as the polymerization temperature of the grafted VC increased. The initial degradation temperature of the composite resin increased as the P(BA‐EHA) content increased. The VST of the samples was enhanced a little as the content of the crosslinking agent increased in P(BA‐EHA). As expected, the composite resin, with good impact resistance, had better heating stability and flowability than pure PVC, whereas the VST of the material decreased little with increasing P(BA‐EHA) content. Therefore, P(BA‐EHA)/PVC resins prepared by seeded emulsion polymerization have excellent potential for widespread applications. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 419–426, 2005     

Surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) of methyl methacrylate from carbon fibre

Surface modification of carbon fibre (CF) by well‐defined polymer brushes was carried out using the ‘grafting from’ method. Poly(methyl methacrylate)‐grafted carbon fibre (CF‐PMMA) was successfully prepared by surface‐initiated atom‐transfer radical polymerization (SI‐ATRP) of methyl methacrylate (MMA) from the macro‐initiator, bromo‐acetic ester‐modified carbon fibre (CF‐BrA), with the complex of 1,10‐phenanthroline and Cu(I)Br as catalyst. The percentage of grafting (PG%) and the conversion of monomer (C%) increased linearly with increasing of polymerization time, and reached 24.0 % and 6.7 %, respectively, after a polymerization time of 6 h, calculated from the elemental analyses (EA). The structural and surface morphological analyses were conducted with Fourier‐transform infrared (FTIR) spectroscopy, X‐ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Copyright © 2005 Society of Chemical Industry     

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     

Synthesis of chiral stationary phase via surface‐initiated atom transfer radical polymerization of vinylated cellulose 3,5‐dimethylphenylcarbamate

A polysaccharide‐immobilized chiral stationary phase (CSP) was prepared by the surface‐initiated atom transfer radical polymerization (SI‐ATRP), in pyridine, of cellulose 2,3‐bis(3,5‐dimethylphenylcarbamate), having a polymerizable vinyl group, on the surface of SiO₂ support. The successful preparation of the CSP was confirmed via Fourier transform infrared spectroscopy, field‐emission scanning electron microscopy, X‐ray photoelectron spectroscopy, elemental analysis and thermal analysis. The chiral recognition ability of the prepared CSP was evaluated with high‐performance liquid chromatography using 10 racemates with various mobile phases of hexane/alcohol, hexane/tetrahydrofuran and hexane/chloroform. As a result, this CSP prepared using SI‐ATRP can be used in tetrahydrofuran and chloroform solutions as eluents. Copyright © 2011 Society of Chemical Industry     

Poly(ethylene oxide)‐block‐polystyrene copolymers obtained by radical polymerization involving chain‐transfer processes

Poly(ethylene oxide)‐block‐polystyrene (PEO–PSt) block copolymers were prepared by radical polymerization of styrene in the presence of iodoacetate—terminated PEO (PEO‐I) as a macromolecular chain‐transfer agent. PEO‐I was synthesized by successively converting the OH end‐group of α‐methoxy ω‐hydroxy PEO to chloroacetate and then to the iodoacetate. The chain‐transfer constant of PEO‐I was estimated from the rate of consumption of the transfer agent versus the rate of consumption of the monomer (C_{tr, PEO‐I} = 0.23). Due to the involvement of degenerative transfer, styrene polymerization in the presence of PEO‐I displayed some of the characteristics of a controlled/‘living’ process, namely an increase in the molecular weight and decrease of polydispersity with monomer conversion. However, because of the slow consumption of PEO‐I due to its low chain‐transfer constant, this process was not a fully controlled one, as indicated by the polydispersity being higher than in a controlled polymerization process (1.65 versus < 1.5). The formation of PEO–PSt block copolymers was confirmed by the use of size‐exclusion chromatography and ¹H NMR spectroscopy. Copyright © 2004 Society of Chemical Industry     

Solid‐state characterization and the thermal properties of stereoregular poly(vinyl chloride) prepared by urea clathrate polymerization

The solid‐state characterization of highly stereoregular poly(vinyl chloride) (PVC) prepared by urea clathrate polymerization was carried out by using various instrumental analyses. The structural differences of PVC appeared most remarkably in solubility to organic solvents, IR, WAXD, and solid‐state ¹³C‐NMR spectra. The value of the glass transition temperature (T_g) was about 90°C, not as high as expected, although its detection was quite difficult. The thermal stability was poor, as evidenced by the easy discoloration of this polymer by heat treatment, which was related to the absence of a termination reaction. Dynamic ESR spectra in the solid state clearly indicate that the radical formation occurs at such a low temperature as 160°C in the initial degradation stage. The degradation characteristics of urea clathrate PVC were critically discussed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2820–2825, 1999     

Physical properties of poly(vinyl chloride)–grafted N‐isopropylacrylamide graft copolymers and corresponding polyblends

The physical properties of poly(vinyl chloride) (PVC) and poly(N‐isopropylacrylamide) [poly(NIPAAm)] blend systems, and their corresponding graft copolymers such as PVC‐g‐NIPAAm, were investigated in this work. The compatible range for PVC–poly(NIPAAm) blend systems is less than 15 wt % poly(NIPAAm). The water absorbencies for the grafted films increase with increase in graft percentage. The water absorbencies for the blend systems increase with increase in poly(NIPAAm) content within the compatible range for the blends, but the absorbencies decrease when the amount of poly(NIPAAm) is more than the compatible range in the blend system. The tensile strengths for the graft copolymers are larger than the corresponding blends. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 170–178, 2000     

Hyperbranched copolymers of p‐(chloromethyl)styrene and N‐cyclohexylmaleimide synthesized by atom transfer radical polymerization

The hyperbranched copolymers were obtained by the atom transfer radical copolymerization of p‐(chloromethyl)styrene (CMS) with N‐cyclohexylmaleimide (NCMI) catalyzed by CuCl/2,2′‐bipyridine (bpy) in cyclohexanone (C₆H₁₀O) or anisole (PhOCH₃) with CMS as the inimer. The influences of several factors, such as temperature, solvent, the concentration of CuCl and bpy, and monomer ratio, on the copolymerization were subsequently investigated. The apparent enthalpy of activation for the overall copolymerization was measured to be 37.2 kJ/mol. The fractional orders obtained in the copolymerization were approximately 0.843 and 0.447 for [CuCl]₀ and [bpy]₀, respectively. The monomer reactivity ratios were evaluated to be r_NCMI = 0.107 and r_CMS = 0.136. The glass transition temperature of the resultant hyperbranched copolymer increases with increasing f_NCMI, which indicates that the heat resistance of the copolymer has been improved by increasing NCMI. The prepared hyperbranched CMS/NCMI copolymers were used as macroinitiators for the solution polymerization of styrene to yield star‐shaped poly(CMS‐co‐NCMI)/polystyrene block copolymers by atom transfer radical polymerization. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1992–1997, 2000     

Absorption of trioctyl trimellitate into mass‐polymerization and suspension‐polymerization poly(vinyl chloride)

Poly(vinyl chloride) (PVC) slush powder has been widely used; we prepared it by dry blending. We found that the absorption of plasticizer by the PVC resins was the most important factor in the dry‐blending process and, further, that different types of PVC resin had different absorption rates. This results of this study provide new information about the relationship of absorption to PVC and other parameters. Haake rheomix testing and the quantity of plasticizers absorbed by the PVC resins were used to characterize the absorption process. Suspension‐polymerization poly(vinyl chloride) (SPVC) and mass‐polymerization poly(vinyl chloride) (MPVC) in different sizes were used for the test. The results showed that the MPVC absorbed the plasticizer more quickly than SPVC, especially at a higher temperature. However, for the same PVC resin type, the absorbing speeds were nearly independent of particle size. The studies that used a scanning electric microscope and specific surface area revealed that the morphology of the two types of particles was different. The surfaces of the individual particles of SPVC were smoother than those of MPVC. There was a “skin” covering the SPVC particles, whereas with the MPVC particles, the primary polymer was exposed directly on the surface. This difference in morphology was shown to be a significant factor in the different rates of absorption of the plasticizers for the different PVC resins. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2369–2374, 2004     

Biodegradable poly(vinyl alcohol)‐graft‐ poly(ε‐caprolactone) comb‐like polyester: Microwave synthesis and its characterization

Poly(vinyl alcohol)‐initiated microwave‐assisted ring opening polymerization of ε‐caprolactone in bulk was investigated, and a series of poly(vinyl alcohol)‐graft‐poly(ε‐caprolactone) (PVA‐g‐PCL) copolymers were prepared, with the degree of polymerization (DP) of PCL side chains and the degree of substitution (DS) of PVA by PCL being in the range of 3–24 and 0.35–0.89, respectively. The resultant comb‐like PVA‐g‐PCL copolymers were confirmed by means of FTIR, ¹H NMR, and viscometry measurement. The introduction of hydrophilic backbone resulted in the decrease in both melting point and crystallization property of the PVA‐g‐PCL copolymers comparing with linear PCL. With higher microwave power, the DP of PCL side chains and DS of PVA backbone were higher, and the polymerization reaction proceeded more rapidly. Both the DP and monomer conversion increased with irradiation time, while the DS increased first and then remained constant. With initiator in low concentration, the DP and DS were higher, while the monomer was converted more slowly. Microwaves dramatically improved the polymerization reaction in comparison of conventional heating method. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104, 3973–3979, 2007     

Removal of chromium (VI) from aqueous solutions using poly(4‐vinyl pyridine) beads

Sorption of hexavalent chromium ions from aqueous solution by poly 4‐vinyl pyridine [Poly(4‐VP)] was studied. The batch method was applied for adsorption processes. The effects of initial ion concentration, time, pH and temperature on adsorption were investigated. A treatment time of 60 min was found to be sufficient to reach equilibrium. pH 3.0 was found as the optimum pH value for the process. The maximum adsorption performance was achieved at 86.7 mg g^?1 using 500 mg L^?1 Cr (VI) solutions. The process of adsorption of Cr (VI) was explained by Langmuir isotherm. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 2865–2870, 2006     

Polymerization of methyl methacrylate with a thermal iniferter: Diethyl 2,3‐dicyano‐2,3‐di(p‐tolyl)succinate

A hexa‐substituted ethane type compound, diethyl‐2,3‐dicyano‐2,3‐di(p‐tolyl)succinate (DCDTS), was successfully synthesized and used for initiation of methyl methacrylate (MMA) polymerization. The reaction demonstrated the characteristics of a “living” polymerization; i.e., both the yield and the molecular weight of the resulting polymers increased linearly with increasing reaction time, the molecular‐weight distribution of PMMA obtained was ～1.60 and almost unaffected by the conversion, and the resultant polymer can be chain extended by adding fresh MMA. End group analysis of the resultant PMMA confirmed that DCDTS behaves as a thermal iniferter for MMA polymerization. A block copolymer was prepared from the resultant PMMA, which contains a hexa‐substituted C? C bond functional end group. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 2566–2572, 2001