In situ preparation and properties of high‐solid‐content and low‐viscosity poly(methyl methacrylate/n‐butyl acrylate/acrylic acid)/poly(styrene/acrylic acid) composite latexes

With monodispersed poly(methyl methacrylate/n‐butyl acrylate/acrylic acid) [P(MMA/BA/AA)] seeded latex with a particle size of 485 nm and a solid content of 50 wt % as a medium, a series of stable P(MMA/BA/AA)/poly(styrene/acrylic acid) composite latexes with a high solid content (70 wt %) and low viscosities (500–1000 mPa · s when the shear rate was 21 s^?1) was prepared in situ via simple two‐step semicontinuous monomer adding technology. The coagulum ratio of polymerization was about 0.05 wt %. The particle size distribution of such latexes was bimodal, in which the large particle was about 589 nm and the small one was about 80 nm. The latexes combined good mechanical properties with good film‐forming properties. Differential scanning calorimetry showed that the corresponding latex film had a two‐phase structure. The morphology of the latex film was characterized with atomic force microscopy and scanning electron microscopy. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1815–1825, 2007     

Preparation and properties of multiwalled carbon nanotube/polycaprolactone nanocomposites

Multiwalled carbon nanotube/polycaprolactone nanocomposites (MWNT/PCL) were prepared by in situ polymerization, whereby as‐received MWNTs (P‐MWNTs) and purified MWNTs (A‐MWNTs) were used as reinforcing materials. The A‐MWNTs were purified by nitric acid treatment, which introduced the carboxyl groups (COOH) on the MWNT. The micrographs of the fractured surfaces of the nanocomposites showed that the A‐MWNTs in A‐MWNT/PCL were better dispersed than P‐MWNTs in PCL matrix (P‐MWNT/PCL). Percolation thresholds of the P‐MWNT/PCL and A‐MWNT/PCL, which were studied by rheological properties, were found at ～2 wt % of the MWNT. The conductivity of the P‐MWNT/PCL was between 10^?1 and 10^?2 S/cm by loading of 2 wt % of MWNT although that of the A‐MWNT/PCL reached ～10^?2 S/cm by loading of 7 wt % of MWNT. The conductivity of the P‐MWNT/PCL was higher than that of the A‐MWNT/PCL at the entire range of the studied MWNT loading, which might be due to the destruction of π‐network of the MWNT by acid treatment, although the A‐MWNT/PCL was better dispersed than the P‐MWNT/PCL. The amount of the MWNT at which the conductivity of the nanocomposite started to increase was strongly correlated with the percolation threshold. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 104: 1957–1963, 2007     

Transparent antifouling coatings via nanoencapsulation of a biocide

Transparent coatings releasing an antifouling agent (AF) can be used to reduce the marine fouling of optical lenses. A variety of water‐borne coatings based on poly(methyl methacrylate‐co‐butyl acrylate) (PMMA‐co‐PBA) were synthesized using a two‐stage miniemulsion process. During this process, the AF, SeaNine 211, was nanoencapsulated in domains small enough not to scatter light. The release rate of SeaNine 211 was studied for the polymers of different T_g, and found to be sufficient to impart AF properties. However, over time, the coatings were found to develop a whitish aspect (blushing) due to water retrodiffusion. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

Synthesis and characterization of new vinyl acetate grafting onto epoxidized linseed oil in aqueous media

Modified poly (vinyl acetate) copolymers with epoxidized linseed oil (ELO) as co‐monomer have been prepared. The polymerization was performed in aqueous medium without any additional protective colloid in the presence of sodium persulfate as catalyst. The effect of vinyl acetate (VAc)/ELO feed ratio, reaction temperature, reaction time, and catalyst amount has been studied. FTIR spectroscopy showed that the reaction between ELO and VAc resulted in slight decrease and shift in ELO characteristic bands of oxirane groups; and new bands were detected in the copolymer spectra attributed to PVAc and ELO functional groups. Moreover, new signals attributable to the copolymer were observed in the ¹H NMR spectra (δ 4.07 and 1.62 ppm) and in the ¹³C NMR spectra (δ 15.29 and 31.0 ppm). Analysis by differential scanning calorimetry (DSC) showed a single T_g for the copolymerization product of VAc and ELO and two T_g for the PVAc/ELO blend, indicating the chemical reaction between VAc and ELO. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42089.     

Specific cationic photoinitiators for near UV and visible LEDs: Iodonium versus ferrocenium structures

Two iodonium salts based on a coumarin chromophore are investigated for polymerization upon light emitting diode irradiations (LEDs). They work as one‐component photoinitiators. They initiate the cationic polymerization of epoxides (under air) and vinylethers (laminate) upon exposure to violet LEDs (385 and 405 nm). Excellent polymerization profiles are recorded. Their efficiency is quite similar to that of a ferrocenium salt. Interpenetrating polymer networks can also be obtained through a concomitant cationic/radical photopolymerization of an epoxy/acrylate blend monomer. The light absorption properties of these new salts as well as the involved photochemical mechanisms are investigated for the first time through electron spin resonance, laser flash photolysis, steady state photolysis experiments. Molecular orbital calculations are also used to shed some light on the initiation mechanisms. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42759.     

Emulsifier‐free cationic latexes based on vinylbenzyl chloride and 2‐(dimethylamino)ethyl methacrylate with adjusted hydrophilic–hydrophobic properties

Functional emulsifier‐free cationic latexes based on styrenic monomer vinylbenzyl chloride (VBC) and acrylic monomer 2‐(dimethylamino)ethyl methacrylate (DMA) were successfully prepared with dual quaternary ammonium ions (36–63 mol %) on both monomer moieties in two‐stages. First, [2‐(methacryloyloxy)ethyl]dimethylhexadecylammonium bromide monomer (DMA(C₁₆)), prepared via quaternization of DMA with 1‐bromohexadecane, was utilized as a comonomer (5–20%) as well as a surfactant in the emulsion polymerization of VBC. Next, the quaternization of chloromethyl groups in the VBC moiety in latex particles with trimethylamine and N,N‐dimethylhexadecylamine created a second type of quaternized sites on the latex particles. The percentages of the quaternary ammonium ions of the first‐stage latexes (P[VBC‐DMA(C₁₆‐x)]) and the second‐stage latexes (P[VBC(R)‐DMA(C₁₆‐x)]) were determined using bromide and chloride ion‐selective electrodes. The particles were characterized with a scanning electron microscope, Zetasizer, measuring water contact angles of their pellets. The polymer structure and the alkyl group length in their quaternary ammonium ions played an important role on the sizes, zeta potentials and hydrophilic–hydrophobic balances of the latexes. The water contact angles of the pellets of the latex particles varied from 50.3 to 109.6° depending on both the polymer structure and the alkyl group length. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42775.     

Perfume‐containing polyurea microcapsules with undetectable levels of free isocyanates

Core‐shell polyurea microcapsules with a 40% fragrance load were prepared by interfacial polymerization of guanidine and a technical polyisocyanate prepolymer containing mainly the biuret trimer derived from hexamethylene di‐isocyanate (HDI). Residual free polyisocyanates were still present at a level slightly above 100 mg NCO functional group per kg as determined by liquid chromatography hyphenated with tandem mass spectrometry of HDI and of its biuret trimer. This level was decreased by a factor of about 10 when the polymerization process was allowed to proceed for a longer time and by a factor of about 500 when guanidine or NaOH were added to the microcapsule suspension to act as scavengers. In these cases, polyisocyanate conversion was observed to proceed for about one month when the microcapsules were stored at room temperature before reaching a plateau at a level below 1 mg NCO/kg. Overall, ammonia was the most efficient polyisocyanate scavenger as no residual HDI biuret trimer and only less than 2 μg NCO/kg as HDI were detected at the end of the process, a level which had dropped below the limit of detection of 0.25 μg NCO/kg after about 40 days of aging at room temperature. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Novel aromatic macrocyclic oligomers: intermediates for the preparation of high-performance polymers

Recent studies aimed at the development of macrocyclic oligomers as the intermediates for the preparation of high-performance polymers are reviewed. Efficient methods for the preparation of a range of cyclic oligomers, such as aryl ether ketones, aryl ether phthalazines, aryl ether isoquinolines, aryl ether phthalazinones, and arylene sulfides, have been developed. Cyclization was achieved via a nucleophilic aromatic substitution reaction under high-dilution conditions. The cyclic aryl ether oligomers undergo a facile ring-opening polymerization to form high molecular weight polymer. Cyclic oligomers containing an aromatic sulfide linkage also undergo a facile free-radical ring-opening polymerization to form high molecular weight polymers which can be amorphous or crystalline. Due to their low molecular weights, these cyclic oligomers have very low melt viscosities which makes them attractive intermediates for a variety of applications for which the conventionally prepared high molecular weight polymers would not be suitable.     

Removal of NO from flue gas using UV/S2 process in a novel photochemical impinging stream reactor

A novel photochemical impinging stream reactor was developed for the first time. Removal process of NO from flue gas using sulfate radical ( ·) and hydroxyl radical (·OH) from UV‐light activation of persulfate (UV/S₂ advanced oxidation process) was investigated in the novel reactor. Experiments were conducted to evaluate the effects of S₂ concentration, solution pH, UV power, solution temperature, liquid‐gas ratio, flue gas flow, NO, SO₂,and O₂ concentrations on removal of NO. Mechanism and kinetics of NO removal were also studied. The results show that increasing UV power, solution temperature, S₂ concentration, or solution circulation rate promotes NO removal. Increasing solution pH (1.2–11.9), NO concentration or flue gas flow weakens NO removal. O₂ concentration has no significant effect on NO removal. · and ·OH were the major active species for NO removal. Absorption rate equation and kinetic parameters of NO removal were obtained. © 2017 American Institute of Chemical Engineers AIChE J, 63: 2968–2980, 2017     

Acceleration of kinetic monte carlo simulations of free radical copolymerization: A hybrid approach with scaling

Kinetic Monte Carlo (KMC) has been widely used in the simulation of polymeric reactions. The power of KMC is highlighted by its ability to keep track of the length and sequence of every radical or polymer chain, while it is computationally more expensive than deterministic kinetic models. This paper introduces an acceleration method that significantly reduces the computational cost of KMC simulations, while keeping the same features as the full kinetic Monte Carlo simulations. Case studies are used to demonstrate the general applicability of this method to free radical copolymerization. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4013–4021, 2017