Gel permeation chromatography calibration based on fractal geometry

The previously developed model [Polym Bull 2000, 44, 525] used to characterize the porous gel inside a gel permeation chromatography (GPC) column, has been extended to also include the interstitial space between the macroscopic gel particles. The hydrodynamic dimensions for 12 polystyrene (PS) standards, measured by GPC with differential refractive index (DRI), differential viscometry (VISCO), and multiangle laser light scattering (MALLS) detectors, have been used to determine the fractal parameters of the polystyrene–divinylbenzene gel corresponding to four commercial columns. The new developed model enables to predict the calibration curve for the sets of coupled columns based on the parameters of each column. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 771–777, 2004     

Effect of the chain‐transfer‐agent content on the emulsion polymerization process and adhesive properties of poly(n‐butyl acrylate‐co‐acrylic acid) latexes

The effect of water on regenerated silkworm silk fibers has been studied and compared with that of water on natural silkworm silk fibers. Regenerated fibers are spun from an N‐methylmorpholine‐N‐oxide (NMMO) fibroin solution through a wet‐spinning process, leading to fibers with two distinct tensile behaviors, labeled as brittle and ductile, respectively. Regenerated fibers show a significant contraction when immersed in water. Contraction increases further after drying. In contrast, natural silkworm silk fibers show a negligible contraction when submerged in water. Regenerated fibers tested in water are considerably more compliant than samples tested in air, though their stiffness and tensile strength are significantly reduced. It has been shown that the tensile properties of brittle regenerated fibers can be modified by a wet‐stretching process, which consists of deforming the fiber while immersed in water. Regenerated wet‐stretched fibers always show a ductile behavior independent from their initial tensile behavior. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Evolutionary computing approach for evaluating flory distribution curves in gel permeation chromatography: Study of the poly(1‐octene) system

We carried out deconvolution of the molecular weight distribution curves from gel permeation chromatography for polyolefins into individual active sites considering Flory distribution by an evolutionary‐computing‐based real‐coded genetic algorithm, a nonlinear multivariate optimization algorithm. We applied the deconvolution to homopolymers of 1‐octene synthesized using heterogeneous Ziegler–Natta catalysts with different amounts of hydrogen. The molecular weight distribution was deconvoluted in to five Flory distributions, which showed a sensitivity to hydrogen amounts. With no hydrogen presence, the peaks corresponding to high‐molecular‐weight fractions were intense. As the amount of hydrogen was increased, not only did the intensities of the high‐molecular‐weight peaks decrease, but also peaks corresponding to low‐molecular‐weight fractions were observed. The method allowed us to determine the active site distribution of the polymer molecular weight distribution obtained from gel permeation chromatography. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

4‐chloro‐3‐methylphenyl methacrylate copolymers with 2,4‐dichlorophenyl methacrylate: Synthesis,characterization, and antimicrobial activity

4‐Chloro‐3‐methylphenyl methacrylate (CMPM) and 2,4‐dichlorophenyl methacrylate (2,4‐DMA) were synthesized by reacting methacryloyl chloride with 4‐chloro‐3‐methylphenol (CMP) and 2,4‐dichlorophenol (2,4‐DP), respectively. Homo and copolymers of CMPM and 2,4‐DMA were obtained from different monomer feed ratios, using 2,2′‐azobisisobutyronitrile as initiator in toluene at 70°C. IR‐spectroscopy was employed to characterize the resulting homo and copolymers. Copolymer compositions were determined by ultraviolet (UV) spectroscopy. Fineman–Ross method was used to calculate the reactivity ratios of the monomers. Average molecular weight and polydispersity index were obtained by gel permeation chromatography (GPC). Thermogravimetric analyses (TGA) and differential thermal analysis (DTA) of copolymers were carried out under a nitrogen atmosphere. Antimicrobial effects of the homo and copolymers were also investigated for various microorganisms such as bacteria, fungi, and yeast. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100:439–448, 2006     

Dissolution of softwood kraft pulps by direct derivatization in lithium chloride/N,N‐dimethylacetamide

A method for the characterization of the molar mass distributions (MMDs) of softwood kraft pulps dissolved in 0.5% lithium chloride (LiCl)/N,N‐dimethylacetamide (DMAc) by size exclusion chromatography is presented. The method is based on derivatization with ethyl isocyanate and the dissolution of samples in 8% LiCl/DMAc. In this study, the derivatization of hardwood kraft pulps did not influence the MMD. In the case of softwood pulps, however, the derivatization decreased the proportion of the high‐molecular‐mass material and increased the proportion of the low‐molecular‐mass material, which resulted in a distribution similar to the MMD of a hardwood kraft pulp. The results suggest that associations between hemicellulose and cellulose in the softwood kraft pulp were ruptured during derivatization. This led to a more correct estimation of the MMD of derivatized softwood kraft pulps than obtained by the dissolution of nonderivatized samples. This new method offers several advantages over derivatization with phenyl isocyanate: a precipitation step is not necessary, it is possible to follow the lignin distribution in the samples, and the method allows very high levels of dissolution of softwood kraft pulps up to a κ number of around 50. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 94: 424–431, 2004     

Synthesis and characterization of biodegradable block copolymers of poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol)

The synthesis of two low molecular weight linear unsaturated oligoester precursors, poly(propylene fumarate‐co‐sebacate) (PPFS) and poly(ethylene fumarate‐co‐sebacate) (PEFS), are described. PPFS, PEFS, and poly(ethylene glycol) are then used to prepare poly(propylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PPFS‐co‐PEG) and poly(ethylene fumarate‐co‐sebacate)‐co‐poly(ethylene glycol) (PEFS‐co‐PEG) block copolymers. The products thus obtained are investigated in terms of the molecular weight, composition, structure, thermal properties, and solubility behavior. A number of design parameters including the molecular weights of PPFS, PEFS, and PEG, the reaction time in the polymer synthesis, and the weight ratio of PEG to PPFS or to PEFS are varied to assess their effects on the product yield and properties. The hydrolytic degradation of PPFS‐co‐PEG and PEFS‐co‐PEG in an isotonic buffer (pH 7.4, 37°C) is investigated, and it is found that the fumarate ester bond cleaves faster than does the sebacate ester bond. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 295–300, 2004     

Development of a fast drying hybrid lacquer in a low‐relative‐humidity environment based on kurome lacquer sap

Hybrid lacquers that dry quickly in a low‐relative‐humidity environment were synthesized with the repeated kurome lacquer process and an organic silicone compound. An investigation by gel permeation chromatography showed that fractions with different molecular weights showed a lower monomer concentration than the pure kurome lacquer. Fourier transform infrared spectra of the hybrid lacquers revealed that absorption due to the ether of the quinone olefin and/or dibenzofuran appeared around 1470 and 1080 cm^?1 and increased with the number of drying days. The gel fractions in the lacquer films increased according to the number of drying days, and this showed that the hybrid lacquers had higher gel fractions than the pure kurome lacquer in the initial stage of dryness. In addition, the drying mechanism of the hybrid lacquers was analyzed with an automatic drying time recorder and rigid‐body pendulum physical property testing measurements. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 1055–1061, 2005     

Flame‐retardant ABS resins from novel phenyl isocyanate blocked novolac phenols and triphenyl phosphate

In an effort to prepare a novel novolac phenol (NP) based char former with good solubility, the hydroxyl functionalities of NP were blocked with phenyl isocyanate (PI) via a simple urethane‐forming reaction. The chemical structure and properties of the obtained novolac phenol–phenyl isocyanate adduct (NP–PI) were characterized with gel permeation chromatography, Fourier transform infrared spectroscopy, ¹H‐NMR, and differential scanning calorimetry. Adducts of two kinds of NPs (molecular weights = 450 and 800) with PI were used as potential char formers for this study. Thus, a two‐component system using NP–PI as a char former and triphenyl phosphate (TPP) as a phosphorous‐based flame retardant was blended with ABS, and the thermal degradation behavior and flame retardance were examined as a function of the molar mass of NP–PI and the TPP/NP–PI ratio with thermogravimetric analysis and limiting oxygen index (LOI) testing. ABS compositions with no NP–PI were also prepared for comparison. The mixtures showed a synergistic effect between TPP and NP–PI on the flame‐retardance enhancement of ABS. Those containing the higher molar mass NP–PI adduct were the most flame retardant, and a LOI value as high as 41 was obtained. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 721–728, 2006     

Burning‐rate enhancement of a high‐energy rocket composite solid propellant based on ferrocene‐grafted hydroxyl‐terminated polybutadiene binder

Four different samples of ferrocene‐grafted hydroxyl‐terminated polybutadiene (Fc‐HTPB), containing 0.20, 0.52, 0.90, and 1.50 wt % iron, were synthesized by the Friedel–Crafts alkylation of ferrocene with hydroxyl‐terminated polybutadiene (HTPB) in the presence of AlCl₃ as a (Lewis acid) catalyst. The effects of the reaction conditions on the extent of ferrocene substitution were investigated. The Fc‐HTPBs were characterized by IR, ultraviolet–visible, ¹H‐NMR, and ¹³C‐NMR spectra. The iron content and number of hydroxyl groups were estimated, and the properties, including thermal degradation, viscosity, and propellant burning rates (BRs), were also studied. The thermogravimetric data indicated two major weight loss stages around 395 and 500°C. These two weight losses were due to the depolymerization and decomposition of the cyclized product, respectively, with increasing temperature. The Fc‐HTPB was cured with toluene diisocyanate and isophorone diisocyanate separately with butanediol–trimethylolpropane crosslinker to study their mechanical properties. Better mechanical properties were obtained for the gumstock of Fc‐HTPB polyurethanes with higher NCO/OH ratios. The BRs of the ammonium perchlorate (AP)‐based propellant compositions having these Fc‐HTPBs (without dilution) as a binder were much higher (8.66 mm/s) than those achieved with the HTPB/AP propellant (5.4 mm/s). © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Improved methods for evaluating the molar mass distributions of cellulose in kraft pulp

Multi‐angle laser light scattering (MALLS) was used to characterize birch kraft pulps with respect to their absolute molecular mass distributions (MMDs). The pulps were dissolved in lithium chloride/N,N‐dimethylacetamide and separated by size exclusion chromatography (SEC). The weight‐average and number‐average molecular masses of the cellulose fractions of the pulps obtained from the absolute MALLS measurements were compared with the molar masses obtained by direct‐standard‐calibration relative pullulan standards. Discrepancies between the two detection methods were found, and two ways of correlating the relative pullulan molar masses to the absolute molar masses were examined. In the first method, the correlation was made over a large range of molecular masses. The second method correlated the molecular masses of the standards to the molecular masses of samples by the calculation of fictitious, cellulose‐equivalent molar masses of the standards. With the preferred second method, a more correct MMD of kraft pulp samples could, therefore, be obtained from an SEC system calibrated with narrow standards. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1170–1179, 2003     

Surfactant‐free nanoparticles of poly(DL‐lactide‐co‐glycolide) prepared with poly(L‐lactide)/ poly(ethylene glycol)

Surfactant‐free nanoparticles of poly(DL ‐lactide‐co‐glycolide) (PLGA) nanoparticles were prepared with or without poly(L ‐lactide)‐poly(ethylene oxide) (LE) diblock copolymer (abbreviated as PLGA/LE and PLGA nanoparticles) by dialysis method. LE diblock copolymer was used to make PLGA nanoparticles to alternate conventional surfactant. The size of PLGA and PLGA/LE nanoparticles was 295.3 ± 171.3 and 307.6 ± 27.2 nm, respectively, suggesting LE diblock copolymer might be coated onto the surface of nanoparticles. Observation of scanning electron microscope (SEM) showed that PLGA/LE nanoparticles have spherical shapes ranging ～ 200–500 nm. In ¹H‐NMR study, characteristic peaks of the methyl protons of PLGA disappeared in D₂O, whereas characteristic peaks of the methyl proton of both PEG and PLGA were shown in both CDCl₃ and D₂O, indicating that LE diblock copolymer coated on the surface of the PLGA nanoparticles. The higher the initial content of drug, the higher the drug contents and the lower the loading efficiency. PLGA/LE nanoparticles at higher drug contents resulted in slower adriamycin·HCl (ADR) release rate than that of lower drug contents. Also, slower release rate of ADR was achieved by entrapped into the PLGA/LE nanoparticles, whereas LE polymeric micelles showed rapid ADR release. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1116–1123, 2003     

Kinetics of microwave‐assisted polymerization of ϵ‐caprolactone

The kinetics of polymerization of ?‐caprolactone (CL) in bulk was studied by irradiating with microwave of 350 W and frequency of 2.45 GHz with different cycle‐heating periods (30–50 s). The molecular weight distributions were determined as a function of reaction time by gel permeation chromatography. Because the temperature of the system continuously varied with reaction time, a model based on continuous distribution kinetics with time/temperature‐dependent rate coefficients was proposed. To quantify the effect of microwave on polymerization, experiments were conducted under thermal heating. The polymerization was also investigated with thermal and microwave heating in the presence of zinc catalyst. The activation energies determined from temperature‐dependent rate coefficients for pure thermal heating, thermally aided catalytic polymerization, and microwave‐aided catalytic polymerization were 24.3, 13.4, and 5.7 kcal/mol, respectively. This indicates that microwaves increase the polymerization rate by lowering the activation energy. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 1450–1456, 2004     

High molecular weight hydrophilic functional copolymers by free‐radical copolymerization of acrylamide and of N‐acryloylmorpholine with N‐acryloxysuccinimide: Application to the synthesis of a graft copolymer

Free‐radical solution copolymerization of acrylamide (AAm) and of a disubstituted acrylamide derivative, N‐acryloylmorpholine (NAM), with N‐acryloxysuccinimide (NAS) was investigated with the aim to obtain a copolymer of at least 100,000 g mol^?1. Different polymerization conditions likely to increase the molecular weight were studied such as monomer and initiator concentrations, temperature, and nature of the solvent. The molecular weights were determined by SEC using a light‐scattering detector. The grafting of end‐functionalized polysaccharide chains onto such high molecular weight poly(NAM‐co‐NAS) was performed and a graft copolymer bearing a high number of saccharidic branches was obtained. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1808–1816, 2003     

Toughening of epoxy resins by hydroxy‐terminated,silicon‐modified polyurethane oligomers

Epoxy resins are among the most versatile engineering structural materials. A wide variety of epoxy resins are commercially available, but most are brittle. Several approaches have been used to improve the toughness of epoxy resins, including the addition of fillers, rubber particles, thermoplastics, and their hybrids, as well as interpenetrating polymer networks (IPNs) of acrylic, polyurethane, and flexibilizers such as polyols. This last approach has not received much attention; none of them have been able to suitably increase resin toughness with out sacrificing tensile properties. Therefore, in an attempt to fill this gap, we experimented with newly synthesized hydroxy‐terminated silicon‐modified polyurethane (SiMPU) oligomers as toughening agents for epoxy resins. SiMPU oligomers were synthesized from dimethyl dichlorosilane, poly(ethylene glycol) (weight‐average molecular weight ～ 200), and toluene 2,4‐diisocyanate and characterized with IR, ¹H‐NMR and ¹³C‐NMR, and gel permeation chromatography. The synthesized SiMPU oligomers, with different concentrations, formed IPNs within the epoxy resins (diglycidyl ether of bisphenol A). The resultant IPN products were cured with diaminodiphenyl sulfone, diaminodiphenyl ether, and a Ciba–Geigy hardener under various curing conditions. Various mechanical properties, including the lap‐shear, peel, and impact strength, were evaluated. The results showed that 15 phr SiMPU led to better impact strength of epoxy resins than the others without the deterioration of the tensile properties. The impact strength increased continuously and reached a maximum value (five times greater than that of the virgin resin) at a critical modifier concentration (20 phr). The critical stress intensity factor reached 3.0 MPa m^1/2 (it was only 0.95 MPa m^1/2 for the virgin resin). © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1497–1506, 2003     

Characterization of enzyme‐deproteinized skim rubber

Skim natural rubber latex is a protein‐rich byproduct obtained during the centrifugal concentration of natural rubber latex. Skim latex has a very low dry rubber content (4–8%), and the rubber particles are smaller in size. It has a higher proportion of nonrubber solids, which are mostly proteinaceous in nature. It is difficult to coagulate, and it takes more processing time. The proteins in skim latex can be decomposed by proteolytic enzymes. This article discusses the use of stabilized liquid papain from the papaya plant (Carica papaya) for deproteinization followed by creaming for quick and easy coagulation of skim latex. The technological properties and aging characteristics of the deproteinized skim rubber are compared with those of conventionally prepared skim rubber and block rubber. The deproteinized skim rubber showed enhanced quality parameters. Particle size analysis revealed that deproteinization and creaming of the skim latex did not markedly change the particle size. Gel permeation chromatography showed a reduction in the quantity of fatty acids after deproteinization and creaming, which was reflected in the improvement of the aging characteristics in comparison with the control sample. Vulcanizates prepared with the deproteinized skim rubber had higher resilience, lower heat buildup, lower compression set, and good tensile strength and elongation at break in comparison with conventionally prepared skim rubber, and the properties were almost comparable to those of block rubber. The improvement in the mechanical properties and aging characteristics could be attributed to the reduction of the protein content, the partial removal of unsaturated fatty acids, and the removal of metal ions that were pro‐oxidants during the deproteinization and creaming process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Reverse atom transfer radical polymerization of stearyl methacrylate using 2,2′‐azobisisobutyronitrile as the initiator

The living/controlled radical polymerization of stearyl methacrylate was carried out with a conventional radical initiator (2,2′‐azobisisobutyronitrile) in N,N‐dimethylformamide in the presence of a 2,2′‐bipyridine complex of hexakis(N,N‐dimethylformamide)iron(III) perchlorate. The polymerization mechanism was thought to proceed through a reverse atom transfer radical polymerization. The molecular weights of resulting poly(stearyl methacrylate) increased with conversion, and the resulting molecular weight distributions were quite narrow. The rates of polymerization exhibited first‐order kinetics with respect to the monomer. A probable reaction mechanism for the polymerization system is postulated to explain the observed results. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1236–1245, 2002     

Synthesis of cationic hemicellulosic derivatives with a low degree of substitution in dimethyl sulfoxide media

A series of water‐soluble cationic 2‐hydroxylpropyltrimethylammonium hemicellulosic derivatives with low average degrees of substitution (DS's) were prepared by the incorporation of the cationic moiety 2,3‐epoxypropyltrimethylammonium chloride (ETA) onto the backbone of hemicelluloses in the presence of NaOH as a nucleophilic catalyst in homogeneous dimethyl sulfoxide (DMSO) media. The dependence of the homogeneous reaction on the different affecting factors was investigated. The average DS was calculated from the N/C ratio in the products and from the weight gain. The degree of substitution determined by the nitrogen content (DS_N) values up to 0.25 in a one‐step synthesis of the etherified hemicelluloses could be controlled by the adjustment of the amount of solvent used and the molar ratio of NaOH or ETA to the anhydromonomer units in the hemicelluloses. The structure of the cationic hemicellulosic derivatives formed was determined by Fourier transform infrared spectroscopy and further confirmed with solution‐state ¹³C‐NMR spectroscopy. In comparison, no significant degradation of the hemicellulosic derivatives occurred during the etherification of the polymers in the homogeneous DMSO system. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation,characteristics, and flocculation behavior of modified palygorskite–polyacrylamide ionic hybrids

A novel inorganic–organic hybrid with modified palygorskite (MPGS) and acrylamide was prepared with a heterogeneous redox initiator system composed of a reductive agent (MPGS) together with an oxidant (Ce⁴⁺). The MPGS–polyacrylamide (PAM) hybrids were characterized by X‐ray diffraction, ¹H‐NMR, Fourier transform infrared spectroscopy, conductometry, viscometry, and size exclusion chromatography. The MPGS–PAM hybrid could be a starlike and ionic bond hybrid. The ionization behavior of the MPGS–PAM hybrid in deionized water depended strongly on its coil dimension and the palygorskite content in the hybrid. The flocculation performance of the MPGS–PAM hybrid in a kaolin suspension was also related to its intrinsic viscosity and the palygorskite content and was better than that of PAM, except for that of the MPGS–PAM hybrid with a high palygorskite content. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1494–1500, 2006     

New fluorous bipyridine ligands for copper‐catalyzed atom transfer radical polymerization of methyl methacrylate in the thermomorphic mode

The atom transfer radical polymerization (ATRP) of methyl methacrylate (MMA) is often carried out under homogeneous conditions, so the residual metal catalyst in the polymer often influences the quality of the polymer and causes environmental pollution in the long run. Novel CuBr/4,4′‐bis(R_fCH₂OCH₂)‐2,2′‐bpy complexes (R_f = n‐C₉F₁₉, n‐C₁₀F₂₁, or n‐C₁₁F₂₃; 2,2′‐bpy = 2,2′‐bipyridine) are insoluble in toluene at room temperature yet readily dissolve in toluene at elevated temperatures to form homogeneous phases for use as catalysts in the ATRP reaction, and the Cu complexes precipitate again upon cooling. The CuBr/4,4′‐bis(n‐C₉F₁₉CH₂OCH₂)‐2,2′‐bpy system produced the best results (e.g., polydispersity index by gel permeation chromatography = 1.26–1.41), in that the residual Cu content in the polymer was as low as 19.3 ppm when the ATRP of MMA was carried out in the thermomorphic mode. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthesis and properties of fluoroalkyl end‐capped sulfobetaine polymers

A variety of fluoroalkyl end‐capped 3‐[N‐(3‐acrylamido)propyl‐N,N‐dimethylammonio]propanesulfonate polymers [R_F–(APDAPS)_n–R_F] were prepared by the reactions of fluoroalkanoyl peroxides with the corresponding monomer under very mild conditions. Similarly, fluoroalkyl end‐capped 2‐vinylpyridinio propane sulfonate polymer was obtained by the use of fluoroalkanoyl peroxide. These fluoroalkyl end‐capped sulfobetaine polymers exhibited a good solubility in water; however, these polymers have a poor solubility in other solvents. In particular, R_F–(APDAPS)_n–R_F polymers caused gelation in methanol, although R_F–(VPPA)_n–R_F polymer showed no gelation in methanol. R_F–(APDAPS)_n–R_F polymers were found to form the self‐assembled molecular aggregates with the aggregations of the end‐capped fluoroalkyl segments and the ionic interactions between sulfobetaine segments in aqueous solutions. On the other hand, it was suggested that R_F–2‐vinylpyridinio propane sulfonate (VPPS)_n–R_F polymer is not likely to form the self‐assemblies in aqueous solutions because of the steric hindrance of pyridiniopropyl betaine units in polymer. We also studied the surfactant properties of R_F–(APDAPS)_n–R_F and R_F–(VPPS)_n–R_F polymers compared with those of other fluoroalkyl end‐capped betaine‐type polymers such as 2‐acrylamido‐2‐methylpropanesulfonic acid polymers and 2‐(3‐acrylamidopropyldimethylammonio) ethanoate polymers. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1144–1153, 2004