One‐pot synthesis of a polysaccharide‐based graft copolymer with an efficient redox pair (Fe2+/BrO3−)

A graft copolymer based on a polysaccharide (sodium salt of carboxymethylcellulose) and a vinyl monomer (acrylamide) has been synthesized in a nitrogen atmosphere, and its reaction conditions have been optimized for a better yield with ferrous sulfate and potassium bromate as a redox initiator. The effects of ferrous ion, bromate ion, hydrogen ion, sodium carboxymethylcellulose, and acrylamide along with the reaction time and temperature have been studied through the determination of the grafting parameters: the grafting ratio, add‐on, conversion, efficiency, homopolymer, and rate of grafting. The maximum yield has been found to occur when the acrylamide concentration is 8.0 × 10^?2 mol/dm³, whereas the maximum conversion occurs at a minimum concentration of acrylamide, that is, at 3.0 × 10^?2 mol/dm³. The grafting parameters have been found to increase with an increasing concentration of the redox initiator (Fe²⁺, from 2.0 × 10^?3 to 10.0 × 10^?3 mol/dm³; BrO, from 2.2 × 10^?3 to 4.0 × 10^?3 mol/dm³). The maximum efficiency occurs with a reaction time of 210 min. The rate of grafting has been found to be maximum up to 60 min; after that, it decreases rapidly. In this article, it is shown that the hydrogen ion leads to a very clear decrease in the grafting parameters as its concentration increases from 2.1 × 10^?3 to 11.3 × 10^?3 mol/dm³. Grafted gum and ungrafted gum have been characterized with Fourier transform infrared spectroscopy and thermogravimetric analysis. A probable mechanism has been suggested for graft copolymerization. It has been observed that the graft copolymer is thermally more stable than the parent backbone. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and morphological studies of chemically prepared emeraldine‐base‐form polyaniline powder

In this study, emeraldine base (EB)‐form polyaniline (PANI) powder was chemically prepared in 1M HNO₃ aqueous solution. The thermal characteristics and chemical structures of this powder were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FTIR), and X‐ray diffraction (XRD). A polarizing optical microscope was also used to examine the crystalline morphology of this sample. The results indicated that the EB‐form PANI powder had a discernible moisture content. Moreover, in the first run of DSC thermal analysis, the exothermic peak at 170–340°C was due to the crosslinking reaction occurring among the EB‐form PANI molecular chains. FTIR and XRD examinations further confirmed the chemical crosslinking reaction during thermal treatment. TGA results illustrated that there were two major stages for weight loss of the EB‐form PANI powder sample. The first weight loss, at the lower temperature, resulted from the evaporation of moisture. The second weight loss, at the higher temperature, was due to the chemical structure degradation of the sample. The degradation temperature of the EB‐form PANI powder was around 420–450°C. The degradation temperature of emeraldine salt (ES)‐form PANI powder was lower (around 360–410°C) than that of the EB form (around 420–450°C). From the TGA results, I roughly estimated that 2.74 aniline repeat units, on average, were doped with 1 HNO₃ molecule in the ES‐form PANI. I found a single crystalline morphology of EB‐form PANI, mostly like a conifer leaf. More complex, multilayered dendritic structures were also found. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 2142–2148, 2003     

Photosensitive poly(urethane acylsemicarbazide)s with azobenzene chromophores in the main chain

Poly(urethane acylsemicarbazide)s were synthesized with a two‐step process: (1) the in situ generation of diisocyanate through the thermal decomposition of an azobenzene‐containing precursor diazide and a reaction with ester/ether polyols to form an isocyanate‐terminated prepolymer and (2) chain extension in N,N‐dimethylacetamide with aliphatic or aromatic dihydrazides. Films cast from N,N‐dimethylacetamide solutions were characterized with attenuated total reflection/Fourier transform infrared spectroscopy, and the thermal properties were studied with thermogravimetric analysis and differential scanning calorimetry. The effects of the hard‐segment content and chain extenders on the static and dynamic mechanical properties were investigated. The photoresponsive behavior of the polymers and the effects of variations in the chromophore concentration and chemical composition on the kinetics of photoisomerization were investigated with ultraviolet–visible spectroscopy, which revealed that the rates were independent of the chromophore concentration. The photomechanical behavior, assessed with creep‐recovery measurements, proved that the systems underwent photochemical isomerization upon irradiation with ultraviolet light. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 444–454, 2004     

Alteration of the mechanical and thermal properties of nylon 6/nylon 6,6 blends by nanoclay

Nylon 6 [N(6)], nylon 6,6 [N(6,6)], and their blends at different clay loadings were prepared. The mix was melted and injected into strip‐shaped samples. Mechanical and thermal analyses were performed to investigate the effect of blending and the incorporated clay on the mechanical and thermal properties. Enhancements in the Young's modulus and hardness were obtained for all of the nanocomposites, with a 55% increase in Young's modulus after the addition of 6 wt % nanoclay, although the improvement in tensile strength depended on the blend ratio, with greatest effects on the 50% N(6)/50% N(6,6) blend with increases of 44 and 59% for 2 and 4% clay loadings, respectively. Thermogravimetric analysis showed an enhancement in the thermal properties in the 50% N(6)/50% N(6,6) blend at 2% clay loading, and the blend exhibited ductile behavior at this loading. Increases in the crystallization peak temperatures of 10–15° in N(6,6) and the two blends 30% N(6)/70% N(6,6) and 50% N(6)/50% N(6,6) were observed after the addition of the clay. The nanoclay enhanced the γ‐/β‐form crystals in N(6) and N(6,6) neat polymers and also in the blends. Fourier transform infrared spectroscopy FT‐IR revealed the formation of hydrogen bonding and the possible formation of ionic bonds between the polymers and the nanoclay, which resulted in enhancements in the mechanical properties of the blends. The distribution of the nanoclay in the blend was well dispersed, as shown by X‐ray diffraction analysis. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Temperature effect on the infrared absorption of ferroelectric copolymer poly(vinylidene fluoride‐trifluoroethylene)

The intensity of two infrared absorption bands of annealed ferroelectric copolymers [poly(vinylidene fluoride‐trifluoroethylene)] in the mid‐infrared high‐frequency region was found to be strongly related to the annealing temperature. The vibration modes in the amorphous phase of the copolymers were considered to account for these two bands. On the other hand, the temperature dependence of the absorption spectra of the copolymers in the heating and cooling cycle was investigated. In the vicinity of the Curie transition, the absorption bands associated with the CH₂ vibrations exhibited a shift in frequency. Two bands were identified as shifting to a high frequency, and one band shifted to a low frequency with heating. These three bands were restored to their room‐temperature frequency with cooling. In addition, copolymers of a higher vinylidene fluoride content exhibited a more pronounced thermal hysteresis in terms of a shift in frequency. This was consistent with the electrical behavior of the copolymers. The trends of the frequency shifts suggested that dipole–dipole coupling existed between two adjacent chains in the all‐trans conformation, which originated from the interaction of the CH₂ and CF₂ dipoles. The coupling diminished as the copolymers underwent a change in phase above the transition temperature. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 1662–1666, 2005     

Synthesis and characterization of nylons based on hexadecane diacid

A series of nylons with long alkane segments between amide groups were synthesized by using hexadecane diacid and various diamines, and the resulting polyamides were characterized comprehensively. It was shown that the molecular weights of nylons 6 16, 8 16, 10 16, and 12 16 in our studies exceed 1.1 × 10⁴, whereas nylons 2 16 and 4 16 have relatively low molecular weights. In addition, the melting temperatures, the decomposition temperatures, and the glass transition temperatures of the nylons obtained were measured. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2462–2467, 2003     

Preparation and characterization of biodegradable polycaprolactone/multiwalled carbon nanotubes nanocomposites

Blends of the biodegradable polycaprolactone (PCL) and multiwalled carbon nanotubes (MWNTs) were prepared by means of a melt blending method. To conquer the poor compatibility between PCL and MWNTs, the acrylic acid grafted polycaprolactone (PCL‐g‐AA) and the multihydroxyl functionalized MWNTs (MWNTs‐OH) were used as alternatives for the preparation of blends. As the comparison between PCL‐g‐AA/MWNTs‐OH and PCL/MWNTs blends, the former gave much better thermal and mechanical properties than the latter; for examples, 77°C increase in the initial decomposition temperature and 13.3 MPa in the tensile strength at break with the addition of only 5 wt %, due to the formation of ester groups through the reaction between carboxylic acid groups of PCL‐g‐AA and hydroxyl groups of MWNTs‐OH. Finally, the optimal amount of MWNTs‐OH was 5 wt % because excess MWNTs‐OH caused separation of the organic and inorganic phases and lowering their compatibility. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Silicate layer dispersion in copolymer/clay nanocomposites

Factors of silicate layer dispersions in polymers have been studied with copolymers. The influence of the copolymerization ratio of copolymers and the alkyl chain lengths of organomodified reagents of organophilic clay has been examined. The dispersion of silicate layers in copolymers is dependent on the copolymerization ratios of the functional groups, that is, the polarity of the polymer matrix. The alkyl chain lengths of organomodified reagents also have an important influence on silicate layer dispersions. From a comprehensive viewpoint, the polarity matching between polymers and organophilic clay is an important factor for silicate layer dispersions in polymers. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1554–1557, 2005     

Enhancement of the high‐temperature utility of a polystyrene‐b‐poly(ethylene‐co‐butylene)‐b‐polystyrene block copolymer by friedel–crafts naphthoylation

A procedure was developed for the Friedel–Crafts naphthoylation of the polystyrene segments of a polystyrene‐b‐poly(ethylene‐co‐butene)‐b‐polystyrene (SEBS) triblock copolymer. It was possible to obtain up to 72% 1‐naphthoylation or 100% 2‐naphthoylation of the polystyrene segments in the copolymer. Naphthoylation could also be accomplished using trifluoromethanesulfonic acid as a catalyst. The naphthoylated products were characterized by ¹H‐NMR spectroscopy, size‐exclusion chromatography, and dynamic mechanical thermal analysis. The mechanical properties of the original and naphthoylated polymers were measured from 25 to 125°C. The results obtained indicate that naphthoylation enhances the tensile properties of the polymers at elevated temperatures. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1289–1295, 2003     

Novel high-temperature-resistant Y2SiO5 aerogel with ultralow thermal conductivity

A novel Y₂SiO₅ ternary aerogel was prepared from tetraethoxysilane and yttrium chloride hexahydrate via the sol-gel method followed by high-temperature calcination. The effects of different calcination temperatures on the microstructure, mechanical and thermal stability of the Y₂SiO₅ aerogels were investigated. The aerogels exhibited low densities of 0.33-0.62 g/cm³, low thermal conductivities of 0.029-0.05 W/(m·K), and a relatively high strength of 0.16-56.47 MPa. Moreover, compared with the Al₂O₃–SiO₂ aerogel, the Y₂SiO₅ aerogel has higher thermal stability and more excellent high-temperature insulation, which has potential applications as a thermal protection material in hypersonic vehicles.     

Polymerization-induced self-assembly of block copolymer nanoparticles via RAFT non-aqueous dispersion polymerization

There is considerable current interest in polymerization-induced self-assembly (PISA) via reversible addition–fragmentation chain transfer (RAFT) polymerization as a versatile and efficient route to various types of block copolymer nano-objects. Many successful PISA syntheses have been conducted in water using either RAFT aqueous dispersion polymerization or RAFT aqueous emulsion polymerization. In contrast, this review article is focused on the growing number of RAFT PISA formulations developed for non-aqueous media. A wide range of monomers have been utilized for both the stabilizer and core-forming blocks to produce diblock copolymer nanoparticles in either polar or non-polar media (including supercritical CO₂ and ionic liquids) via RAFT dispersion polymerization. Such nanoparticles possess spherical, worm-like or vesicular morphologies, often with controllable size and functionality. Detailed characterization of such sterically stabilized diblock copolymer dispersions provides important insights into the various morphological transformations that can occur both during the PISA synthesis and also on subsequent exposure to a suitable external stimulus (e.g. temperature).     

Synthesis and thermomechanical characterization of polyurethane elastomers extended with α,ω‐alkane diols

A series of polyurethane (PU) elastomers was prepared by the reaction of poly(?‐caprolactone) and 4,4′‐diphenylmethane diisocyanate, which was extended with a series of chain extenders (CEs) having 2–10 methylene units in their structure. The completion of the reaction was confirmed by Fourier transform infrared spectroscopy. The chemical structures of the synthesized PU samples were characterized with Fourier transform infrared, ¹H‐NMR, and ¹³C‐NMR spectroscopy, and the thermal properties were determined by thermogravimetric analysis, DSC, and dynamic mechanical thermal analysis techniques. The mechanical properties were also studied and are discussed. The thermogravimetric analysis and DSC analysis showed that CE length had a considerable effect on the thermal properties of the prepared samples. The dynamic mechanical thermal analysis and damping peaks were also affected by the number of methylene units in the CE length. The elastomer extended with 1,2‐ethane diol exhibited optimum thermal properties, whereas the elastomer based on 1,10‐decane diol displayed the worst thermal properties. Tensile strength and elongation at break decreased with increasing CE length, whereas hardness showed the opposite trend. The glass‐transition temperature moved toward lower temperatures with increasing CE length. The decrease in the glass‐transition temperature and tensile properties were interpreted in terms of decreasing hard segments and increasing chain flexibility. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Characterization of polyurethane foams prepared from non‐pretreated liquefied corn stover with PAPI

Polyurethane foams were prepared through co‐polymerization of non‐pretreated liquefied corn stover (LCS) and polymethylene polyphenylisocyanate (PAPI). The effects of [NCO]/[OH] ratio on the chemical structure and the thermal properties were studied by means of Fourier transform infrared spectroscopy (FT‐IR), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). The urethane linkages and the free isocyanate groups in co‐polymerization were detected from FT‐IR analysis. Thermal decomposition of polyurethane foams occurred in four main successive stages. With the increasing [NCO]/[OH] ratio, the glass transition temperature (T_g) and the initial decomposition temperature increased from −36.12 and 52.18 to 1.20 and 73.30°C, respectively. And the range of T_g expanded from 26.39 to 57.12°C.     

Optimized conditions for the grafting reaction of poly(methyl methacrylate) onto oil‐palm empty fruit bunch fibers

This article describes the graft copolymerization of poly(methyl methacrylate) (PMMA) onto oil‐palm empty fruit bunches (OPEFBs) with a fiber length of less than 75 μm. The graft copolymerization was carried out under a nitrogen atmosphere by a free‐radical initiation technique in an aqueous medium. Hydrogen peroxide and ferrous ions were used as a redox initiator/cocatalyst system. The PMMA homopolymer that formed during the reaction was removed from the grafted copolymers by Soxhlet extraction. Determining the effects of the reaction period, reaction temperature, and monomer concentration on the grafting percentage was the main objective, and they were investigated systematically. The optimum reaction period, reaction temperature, monomer concentration, and initiator concentration were 60 min, 50°C, 47.15 × 10^?3 mol, and 3.92 × 10^?3 mol, respectively. The maximum percentage of grafting achieved under these optimum conditions was 173%. The presence of PMMA functional groups on OPEFB and the enormous reduction of the hydroxyl‐group absorption band in PMMA‐g‐OPEFB spectra provided evidence of the successful grafting reaction. The improvement of the thermal stability of PMMA‐g‐OPEFB also showed the optimal achievement of the grafting reaction of PMMA onto OPEFB. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Thermal and shape memory properties of cyanate/polybutadiene epoxy/polysebacic polyanhydride copolymer

A novel thermal‐induced shape memory polymer was synthesized by copolymerization of a new kind of epoxy resin‐polybutadiene epoxy (PBEP), bisphenol A‐type cyanate ester (BACE), and polysebacic polyanhydride (PSPA) with different mass ratios. Fourier transform infrared spectroscopy (FTIR), bending test, dynamic mechanical analysis (DMA), and shape memory property were investigated systematically. It was found that the PSPA significantly enhanced the bending strength and flexural modulus. The DMA results showed that the glass transition temperature reduced with increasing content of PSPA. Furthermore, the shape memory tests proved that the copolymer possessed excellent shape memory properties. The shape recovery time decreased with increasing content of PSPA and temperature. The shape memory rate increased as the PSPA content increased. The shape recovery ratio decreased with increasing cycle times. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42045.     

Durable antimicrobial treatment of cotton fabrics using N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride and polycarboxylic acids

N‐(2‐hydroxy)propyl‐3‐trimethylammonium chitosan chloride (HTCC), a water‐soluble chitosan quaternary ammonium derivative, was used as an antimicrobial agent for cotton fabrics. HTCC has a lower minimum inhibition concentration (MIC) against Staphylococcus aureus, Klebsiella pneumoniae, and Escherichia coli compared to that of chitosan; however, the imparted antimicrobial activity is lost on laundering. Thus crosslinking agents were utilized to obtain a durable antimicrobial treatment by immobilizing HTCC. Several crosslinkers such as dimethyloldihydroxyethylene urea (DMDHEU), butanetetracarboxylic acid (BTCA), and citric acid (CA) were used with HTCC to improve the laundering durability of HTCC treatment by covalent bond formation between the crosslinker, HTCC and cellulose. The polycarboxylic acid treatment was superior to the DMDHEU treatment in terms of prolonged antimicrobial activity of the treated cotton after successive laundering. Also, the cotton treated with HTCC and BTCA showed improved durable press properties without excessive deterioration in mechanical strength or whiteness when compared to the citric acid treatment. With the addition of only 0.1% HTCC to BTCA solutions, the treated fabrics showed durable antimicrobial activity up to 20 laundering cycles. The wrinkle recovery angle and strength retention of the treated fabrics were not adversely affected with the addition of HTCC. Therefore, BTCA can be used with HTCC in one bath to impart durability of antimicrobial activity along with durable press properties to cotton fabric. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1567–1572, 2003     

Monitoring the grafting of epoxidized natural rubber by size‐exclusion chromatography coupled to FTIR spectroscopy

The evaluation of heterogeneous polymeric species by a selective, dual detector size‐exclusion chromatography setup can provide accurate results on the incorporation of specific functional groups in copolymers as a function of the molar mass distribution. However, when non‐UV‐absorbing species are used in copolymerization reactions, the dual detector method becomes less reliable. By interfacing a Fourier transform infrared (FTIR) spectrometer with size‐exclusion chromatography (SEC), the problem can be overcome, making it possible to map non‐UV‐absorbing species as a function of the molar mass distribution. Coupling takes place via a solvent‐evaporation stage, which delivers the mobile phase as a dry, solvent‐free polymeric film onto a germanium disk. In this article, styrene and methyl methacrylate were grafted onto epoxidized natural rubber (ENR50) and analyzed by SEC. The accuracy of FTIR as a suitable detector was evaluated by comparing results from a dual detector SEC setup and FTIR coupled to SEC. FTIR proved to be a successful detector for the analysis of non‐UV‐absorbing species. This was consequently followed by the characterization of methyl methacrylate‐grafted ENR50. From the relevant data, Gram–Schmidt and contour plots could be made to indicate the incorporation of methyl methacrylate into the grafted epoxidized natural rubber as a function of the molar mass distribution. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 2539–2549, 2003     

Polysiloxaneurethanes: new polymers for potential coating applications

Polysiloxaneurethanes (PSUR) are block copolymers containing polysiloxane and urethane (or polyurethane) segments and showing very interesting mechanical, dielectric and surface related properties. Brief reviews of investigations that have been carried out so far on PSUR are presented with special reference to coating applications of them. The properties of the novel moisture-curable PSUR (MCPSUR), tested before and after moisture curing, are discussed in connection with their chemistry and structure. The properties of aqueous dispersions of PSUR (ADPSUR) synthesised in ICRI are also reviewed. The preliminary results of some coating tests made for MCPSUR and ADPSUR are presented.     

Characterisation of block copolymer self‐assemblies by thermal field‐flow fractionation

The ability of block copolymers to self‐assemble into various nanostructures (such as micelles) has attracted significant attention over the years as these block copolymers provide a versatile platform that can readily be modified for a wide range of applications. As such, the solution behaviour of block copolymers has been at the forefront of the modern nanotechnology revolution. However, these novel block copolymer‐based self‐assemblies lack suitable characterisation techniques to determine size, molar mass and compositional distributions simultaneously. This mini‐review gives a short background on the current techniques used to determine important micelle properties as well as their limitations for characterising complex samples. Current column‐based fractionation techniques used for determining property distributions are addressed. As a result of the limitations of column‐based fractionations, a multidetector thermal field‐flow fractionation (ThFFF) approach is put forward as a powerful alternative for determining not only size and molar mass distributions, but also other micelle properties as a function of temperature. More importantly, ThFFF is highlighted as the only current characterisation platform capable of addressing the analytical challenges associated with compositional distributions of polymer self‐assemblies. © 2017 Society of Chemical Industry     

Formation of silver nanoparticles created in situ in an amphiphilic block copolymer film

In this work, silver nanoparticles were synthesized with an amphiphilic diblock copolymer, polystyrene‐block‐poly(1‐vinyl‐2‐pyrrolidone) (PS‐b‐PVP), as a template film. First, microphase‐separated amphiphilic PS‐b‐PVP (70 : 30 wt %) was synthesized through atom transfer radical polymerization. The self‐assembled block copolymer film was used to template the growth of silver nanoparticles by the introduction of a silver trifluoromethanesulfonate precursor and an ultraviolet irradiation process. The in situ formation of silver nanoparticles with an average size of 4–6 nm within the block copolymer template film was confirmed with transmission electron microscopy, ultraviolet–visible spectroscopy, and wide‐angle X‐ray scattering. Fourier transform infrared spectroscopy also demonstrated the selective incorporation and in situ formation of silver nanoparticles within the hydrophilic poly(1‐vinyl‐2‐pyrrolidone) domains, which were mostly due to the stronger interaction strength of the silver with the carbonyl oxygens of poly(1‐vinyl‐2‐pyrrolidone) in the block copolymer. This work provides a simple route for the in situ synthesis of silver nanoparticles within a polymer film. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008