Influence of two-step process and of different stoichiometric ratios on morphologies generated in castor oil epoxy resins

Phase separation during polymerization was studied in a model system consisting of a diepoxide based on diglycidyl ether of bisphenol A (DGEBA), variable amounts of ethylenediamine (EDA) and the mass of castor oil (CO) necessary to obtain a mass fraction equal to 0-15 in a final system where the stoichiometric ratio of amine to epoxy equivalents, r, was equal to 1. A two-step polymerization process was performed by curing first a system with r = 0-5, during variable times before phase separation, and then carrying the system to r = 1. Thermodynamic analysis of samples with different r values led to a linear relationship between the Flory-Huggins interaction parameter and r. The concentration (P) and average size (D?) of dispersed-phase particles followed opposite trends, i.e. P increased while D? decreased, when either r was increased or the time of curing in the first step of a two-step process was decreased. This was explained by assuming that the competition between nucleation and growth was determined by the viscosity at the cloud point, η_cp. Low values of η_cp favoured growth over nucleation and led to fewer but larger particles.     

Phase separation studies in RIM polyurethanes catalyst and hard segment crystallinity effects

Polyurethanes were prepared from pure 4,4′-diphenylmethane diisocyanate (MDI), 1,4-butane diol (BDO) or 1,2-ethane diol (EDO) and α,ω-hydroxyl poly(propylene oxide) (PPO) by reaction injection moulding (RIM). Hard segment (MDI + BDO or EDO) level was 45–50 wt%. The PPO had about 20% ethylene oxide copolymerized in at the chain ends to provide 80% primary OH end groups. M_n was varied from 2000 to 4000. Dibutyl tin dilaurate catalyst and mould temperature were varied. Dynamic mechanical, wide-angle X-ray, differential scanning calorimeter, molecular weight and tensile elongation measurements were made on the RIM polyurethanes. At low reaction rates (low catalyst or temperature) highly crystalline, well phase separated but low molecular weight polymers were produced. At high catalyst or temperature levels more poorly phase separated but high molecular weight, tough polymers resulted. Higher M_n PPO gave better phase separation and EDO gave higher melting temperatures. Preventing hard segment crystallinity by substituting asymmetric MDI or glycols resulted in phase compatibility.     

Surface tailoring of an ethylene propylene diene elastomeric terpolymer via plasma‐polymerized coating of tetramethyldisiloxane

In the research presented here, we explore the use of a low‐energy plasma to deposit thin silicone polymer films using tetramethyldisiloxane (TMDSO) (H(CH₃)₂? Si? O? Si? (CH₃)₂H) on the surface of an ethylene propylene diene elastomeric terpolymer (EPDM) in order to enhance the surface hydrophobicity, lower the surface energy and improve the degradation/wear characteristics. The processing conditions were varied over a wide range of treatment times and discharge powers to control the physical characteristics, thickness, morphology and chemical structure of the plasma polymer films. Scanning electron microscopy (SEM) shows that pore‐free homogeneous plasma polymer thin films of granular microstructure composed of small grains are formed and that the morphology of the granular structure depends on the plasma processing conditions, such as plasma power and time of deposition. The thicknesses of the coatings were determined using SEM, which confirmed that the thicknesses of the deposited plasma‐polymer films could be precisely controlled by the plasma parameters. The kinetics of plasma‐polymer film deposition were also evaluated. Contact angle measurements of different solvent droplets on the coatings were used to calculate the surface energies of the coatings. These coatings appeared to be hydrophobic and had low surface energies. X‐ray photoelectron spectroscopy (XPS) and photoacoustic Fourier‐transform infrared (PA‐FT‐IR) spectroscopy were used to investigate the detailed chemical structures of the deposited films. The optimum plasma processing conditions to achieve the desired thin plasma polymer coatings are discussed in the light of the chemistry that takes place at the interfaces. Copyright © 2004 Society of Chemical Industry     

Cationic ring-opening polymerization of hexamethylcyclodisilazane: General aspects and tentative mechanisms

The ring-opening polymerization of hexamethylcyclodisilazane (D_2NMe), initiated by methyl triflate in 1,2-dichloroethane, forms in the first, fast kinetic step both linear polymer and cyclic dimer (D_4NMe). Subsequently a slow depolymerization process occurs leading to exclusively cyclotrisilazane (D_3NMe). On the basis of kinetic measurements carried out using an adiabatic calorimetric technique and complementary experiments, mechanisms of both propagation, cyclization and back-biting reactions are proposed. The influence of the reaction temperature was also studied; it is demonstrated that, at low temperature, polymerization does not lead to cyclic oligomer formation. In such conditions, the polymerization presents a ‘living’ character.     

Effect of fluoropolymer antidripping agent on the microstructure and properties of polyesters

Poly(ethylene terephthalate) (PET) is of excellent mechanical properties and melt processability and is widely used as raw material for textile fibers. However, the flame retardant properties of PET were rather poor, and both reactive and additive phosphorus- and halogen-containing compounds have been employed to enhance the reaction-to-fire properties while the meltdripping behaviour during burning hasn’t been handled properly with the flame retardants. In this work, fluoropolymer was blended with both pure PET (pPET) and reactive phosphorus-containing flame retarded copolyester (fPET), and the flame retardance and char formation and mechanical properties of the resulted pPET and fPET blends were investigated. The tensile strengths of modified pPET samples were worsen whereas those of modified fPET samples were improved at low concentrations. The initial thermal degradation in nitrogen was accelerated remarkably for the two polyesters with fluoropolymer. The oxygen indices of the all modified samples were reduced while char formation and meltdripping suppression were encouraged. The apparent melt viscosity and elasticity for the two polyesters were gained much with antidripping agent. Therefore, fluoropolymer improved char formation of the two polyesters based on the gaseous phase mechanism while the partial suppression of meltdripping behavior and the decrease of mechanical properties mainly originated from the increase of melt viscosity via fibrillation for pPET.     

Surface modification of starch nanocrystals through ring‐opening polymerization of ε‐caprolactone and investigation of their microstructures

Bionanoparticles of starch obtained by submitting native potato starch granules to acid hydrolysis conditions. The resulted starch nanoparticles were used as core or macro initiator for polymerization of ε‐caprolactone (CL). Starch nanoparticle‐g‐polycaprolactone was synthesized through ring‐opening polymerization (ROP) of CL in the presence of Sn(Oct)₂ as initiator. The detailed microstructure of the resulted copolymer was characterized with NMR spectroscopy. Thermal characteristic of the copolymer was investigated using DSC and TGA. By introducing PCL, the range of melting temperature for starch was increased and degradation of copolymer occurred in a broader region. X‐ray diffraction and TEM micrographs confirmed that there was no alteration of starch crystalline structure and morphology of nanoparticles, respectively. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Restraining the associations of anthracene fluorophore by chemically linking to poly(methyl methacrylate)

Associations (dimer or aggregate) of anthracene (An) fluorophores tend to interrupt the monomer emission and reduce the quantum yield (Φ_PL); therefore, poly(methyl methacrylate) (PMMA) chain was used in this study to chemically link to anthracene and to block the mutual associations among the anthracene fluorophores. With this aim, the target polymers were prepared by anionic polymerizations with 9,10‐dibromoanthracene/s‐butyllithium as initiating system to proceed polymerizations of methyl methacrylate (MMA) directly or in the presence of 1,1‐diphenylethylene (DPE). Use of DPE before addition of MMA produces stable initiating anionic species and avoids potential side reactions during polymerization; however, it also introduces four β‐phenylene rings around the central anthracene ring, which interfere with the corresponding emission pattern and reduce the Φ_PL (32%) value due to potential interactions between phenylene rings and anthracene. On the contrast, polymerization without participation of DPE results in polymer with central anthracene ring directly connected to two PMMA chains, which gives clean vibronic emission pattern with limited association emissions and enhanced Φ_PL (52%) value. Physical blending of anthracene by PMMA is less efficient to restrain the associations and results in a film of lower Φ_PL (20%). © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of branched polyacrylonitrile through self‐condensing vinyl copolymerization

Branched polyacrylonitrile (PAN) was prepared through a self‐condensing vinyl copolymerization of acrylonitrile and 2‐(2‐bromopropionyloxy)ethyl acrylate (BPEA). The branched architecture of the product was confirmed by NMR spectra and the average degree of branching (DB ) was estimated. Through a comparison of the intrinsic viscosity of the product with that of its linear analogue, the contraction factor g′ was calculated. It was found that the viscosity of the branched PAN was obviously lower that that of linear PAN. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effects of three crosslinkers on colored pH‐responsive core–shell latexes

Environmentally responsive hydrogels have become attractive research subjects for many applications. In this work, a series of pH‐sensitive and color‐changing nanoparticles (nanogels) with core–shell structures were synthesized. The cores were blue latex particles synthesized by a miniemulsion technique with styrene and methacrylic acid as monomers and Neozapon Blue 807 as a dye. The shell was a pH‐sensitive polymer that was precipitation‐polymerized onto the core from 2‐(diethylamino) ethyl methacrylate with N,N′‐methylenebisacrylamide, poly(propylene glycol) diacrylate, and divinylbenzene as crosslinking agents. In the resultant latexes, the color was observed to change from deep blue to pale blue as the pH of the system was changed from a high of 10 to a low of 3. The synthesized latexes and particles (gels) were then characterized with an ultraviolet–visible spectrometer, dynamic light scattering, Fourier transform infrared, and nuclear magnetic resonance. Atomic force microscopy was also used to investigate the different morphologies of the particles after the synthesized latexes were dried at different pH values. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008