Influence of anionic form on thermal degradation of TMAHP–cellulose

Trimethylammoniumhydroxypropyl (TMAHP)–cellulose in 10 anionic forms (F^?, Cl^?, Br^?, I^?, HSO, NO, OH^?, HCO, H₂PO, CH₃COO^?) was prepared, and the influence of each anion on thermal degradation in inert atmosphere was studied. With the help of dynamic and isothermal thermogravimetry (TG) it was found that H₂PO ions had the greatest retarding effect on TMAHP–cellulose degradation. From the values of rate constants it can be seen that all ionic forms of TMAHP–cellulose have the starting rate of thermal degradation greater than unmodified cellulose. The calculated values of activation energy of thermal degradation for different ionic forms are decreasing in following sequence: H₂PO > F^? > NO > I^? > Br^? > HCO > Cl^? > HSO > OH^? > unmodified cellulose > CH₃COO^?. From the results of pyrolyse measurements in combination with gas chromatography and mass spectrometry (Py–GC–MS) it follows that the products of the elimination of quarternary ammonium salts are trimethylamine, 3-hydroxy-2-propanone, and, in the case of OH^? form, water. In all other ionic forms the third product is the corresponding acid.     

Hydrogenation and neutralization of carboxylic styrene–butadiene latex to form thermoplastic elastomer with excellent thermooxidation resistance

Hydrogenation of carboxylic styrene–butadiene rubber latex was carried out using hydrazine and hydrogen peroxide with ferrous sulfate as a catalyst without pressurized hydrogen and an organic solvent. A mixed inhibitor was used during hydrogenation to prevent gel formation. Various hydrogenation conditions were studied. Ferrous sulfate is better than is cupric sulfate as a catalyst. The hydrogenation degree can reach over 90%. The hydrogenated product was characterized by IR and DSC. The hydrogenated products behave as a thermoplastic elastomer with excellent thermooxidation resistance, due to the absence of most double bonds and the presence of crystalline domains of polyethylene segments formed by the hydrogenation of polybutadiene segments. Ionomers were obtained by neutralization of the hydrogenated product with metallic ions and characterized by IR, DSC, and TEM. The ionomers also behave as thermoplastic elastomers with mechanical properties better than those of the hydrogenated product without neutralization, due to the existence of ionic domains besides the crystalline domains. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 1375–1384, 2002     

New aspects in cationization of lignocellulose materials. III. Influence of delignification on reactivity and extractability of TMAHP–hemicelluloses

Beech sawdust samples with different lignin content were alkylated with 3-chloro-2-hydroxypropyltrimethylammoniumchloride (CHMAC). The yields and the degree of subtitution of trimethylammonium-2-hydroxypropyl (TMAHP) samples were similar. Differences were found in extractability of hemicelluloses from this materials both with water and dilute alkali. To obtain the maximum yield of TMAHP–hemicelluloses (ca. 90% of the amount originally present), it is sufficient to remove about 50% of lignin. The lignin component does not influence the reactivity of hemicelluloses. The isolated hemicelluloses differ only in the distribution of functional groups and extractability.     

New aspects in cationization of lignocellulose materials. X. Thermooxidation of TMAHP–sawdust

With the help of dynamic and isothermic thermogravimetry in inert and oxidative atmosphere the thermooxidation of TMAHP–sawdust in individual anionic forms was studied. The values obtained indicate that the most resistant samples against thermooxidation are H₂PO^?₄ and Br^? anionic forms. The most easily thermooxidized sample is the OH^? form. The thermooxidation seems to be a less energy-consuming reaction than thermolysis.     

The mechanism of cellulose alkalization in the isopropyl alcohol–water–sodium hydroxide–cellulose system

The mechanism of cellulose alkalization in isopropyl alcohol (IPA)–water–sodium hydroxide system was studied from the viewpoint of the selective distribution of sodium hydroxide between cellulose and the medium, and of the lattice transition of cellulose. A mixture of IPA, water, and sodium hydroxide spontaneously separates into two layers, i.e., the upper layer solution (ULS) consists of IPA, water, and a small amount of sodium hydroxide and the lower one (LLS) consists of sodium hydroxide, water, and a very small quantity of IPA. The role of the ULS and the LLS was distinctive. The ULS has a function to distribute sodium hydroxide with water in cellulose uniformly according to the distribution equilibrium between ULS and cellulose, and the ULS recovers sodium hydroxide with water from the LLS as the distribution equilibrium shifts in the alkalization of cellulose. The concentration of sodium hydroxide in the LLS and that of IPA in the ULS exerts an influence on the lattice structure of alkali cellulose. During the transformation from cellulose I to alkali cellulose, decrystallization does not occur. Some portion of alkali cellulose reverted to cellulose I by regeneration.     

Influence of coupling agents and treatments on the mechanical properties of cellulose fiber–polystyrene composites

Wood fibers of aspen in the form of chemithermomechanical pulp (CTMP) and Tembec 6816 have been used as reinforcing fillers in different varieties of polystyrene. The tensile strength, elongation, and energy at maximum point, as well as tensile modulus at 0.1% strain is reported. Also revealed is the optimum condition of compression molding. The influence of different coupling agents, such as poly[methylene(polyphenyl isocyanate)], silanes (A-172, A-174, A-1100), and grating on the mechanical properties of composites is discussed. The extent of increase in mechanical properties depends on the weight percentage of fibers, the concentration of coupling agents, and the grafting level (add-on %). Coating followed by an isocyanate treatment appears to be the best treatment. In addition, the isocyanate treatment and grafting are superior to the silane treatment. Experimental results are explained on the basis of possible interactions among cellulose fiber-coupling agent-polymer in the interfacial area.     

Viscosity–temperature relationships for cellulose acetate–acetone solutions

Viscosity measurements were made for dilute solutions of three grades of cellulose acetate (acetyl content 39.8%, molecular weight M?_v 30270 to 46250) in acetone in the temperature t range of 10° to 35°C. The data satisfied the Mark-Houwink equation, [η] = KM?, where [η] = limiting viscosity number and K and α are Mark-Houwink constants. The values of [η] and α decreased with increase in temperature, and straight-line correlations were obtained for ?d[η]/dt versus M?_v and log η versus 1/T (absolute temperature). The results are discussed in terms of solution properties of cellulose acetate in acetone and their possible relevance to reverse osmosis membrane science.     

Structure–process–yield interrelations in nanocrystalline cellulose extraction

In order to improve the extraction of nanocrystalline cellulose (NCC) from sulfuric acid hydrolysis of chemical pulps, we have studied the effect of hydrolysis conditions on the degree of polymerization (DP), the extent of sulfation, morphological, and solid‐state characteristics of the extracted materials vis‐à‐vis yield. Our results demonstrate that sulfation plays a significant role in (i) determining the yield of, and (ii) imparting the unique solid‐state characteristics to, the extracted, H₂O‐insoluble cellulose nanomaterial from sulfuric acid hydrolysis. The hydrolysis process is itself proven to be highly reproducible, and NCC with high crystallinity (>80%) and a yield between 21% and 38% could be extracted from a fully bleached, commercial softwood kraft pulp using 64 wt.% sulfuric acid at 45–65°C after freeze drying. The NCC aggregates, with iridescent patterns typical of chiral nematic materials, are parallelepiped rod‐like structures which possess cross‐sections in the nanometer range and lengths orders of magnitude larger, resulting in high aspect ratios. The Ruland–Rietveld analysis was employed to precisely resolve X‐ray diffraction patterns and obtain information on crystallite size, crystalline and amorphous areas, and crystallinity of the extracted materials.     

Styrene–butadiene–styrene/montmorillonite nanocomposites synthesized by anionic polymerization

We successfully synthesized an exfoliated styrene–butadiene–styrene triblock copolymer (SBS)/montmorillonite nanocomposite by anionic polymerization. Gel permeation chromatography showed that the introduction of organophilic montmorillonite (OMMT) resulted in a small high‐molecular‐weight fraction of SBS in the composites, leading to a slight increase in the weight‐average and number‐average molecular weights as well as the polydispersity index. The results from ¹H‐NMR revealed that the introduction of OMMT almost did not affect the microstructure of the copolymer when the OMMT concentration was lower than 4 wt %. Transmission electron microscopy and X‐ray diffraction showed a completely exfoliated nanocomposite, in which both polystyrene and polybutadiene blocks entered the OMMT galleries, leading to the dispersion of OMMT layers on a nanoscale. The exfoliated nanocomposite exhibited higher thermal stability, glass‐transition temperature, elongation at break, and storage modulus than pure SBS. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci, 2006     

Hydroxypropylmethylcellulose–anionic surfactant interactions in aqueous systems

The increase in the viscosity of an aqueous solution or gel of hydroxypropylmethylcellulose (HPMC) in the presence of an anionic surfactant is attributed to a two-step process: (a) the surfactant undergoes ion–dipole interaction with the ethereal oxygen in HPMC, in the absence or presence of water, and (b) hydrocarbon moieties in the now pendant surfactant molecules undergo hydrophobic bonding, in the presence of water, resulting in an apparent increase in the molecular weight of the HPMC. DSC of dry blends and dried gels or films confirmed HPMC–sodium lauryl sulfate interaction. Work-to-break measurements on films cast from aqueous solutions of HPMC, in the absence or presence of anionic surfactants, indicated an apparent increase in the molecular weight of HPMC in the presence of surfactants.     

Homogeneous graft copolymerization of styrene onto cellulose in a sulfur dioxide–diethylamine–dimethyl sulfoxide cellulose solvent

Graft copolymerization of styrene onto cellulose was studied in a homogeneous system (SO₂–DEA–DMSO medium) by γ-ray mutual irradiation technique. At the same time, homopolymerization of styrene was also examined separately in DMSO, SO₂–DMSO, DEA–DMSO, and SO₂–DEA–DMSO media by the same technique. Polymerization of styrene hardly occurs on concentrations above 10 mole SO₂–DEA complex per mole glucose unit. Maximum percent grafting was obtained in concentrations of 4 mole, after which it decreased rapidly. Total conversion and percent grafting increased with the irradiation time. The value (=0.55) of the slope of the total conversion rate plotted against the dose was only a little higher than the 1/2 which was expected from normal kinetics. No retardation in homopolymerization of styrene in DMSO, SO₂–DMSO, and DEA–DMSO was evident, while the retardation of homopolymerization in the SO₂–DEA–DMSO medium was measurable. Sulfur atoms were detected in the polymers obtained in both of SO₂–DMSO and SO₂–DEA–DMSO solutions. All of the molecular weights of polymers obtained in the present experiment were very low (3.9 × 10³?1.75 × 10⁴).     

Electrical conductivity of urea–formaldehyde–cellulose composites loaded with copper

This work is concerned with the preparation and characterization of composite materials prepared by compression molding of mixtures of copper powder and a commercial grade thermosetting resin of urea–formaldehyde filled with α‐cellulose in powder form. The electrical conductivity of the composites is <10⁻¹² S/cm, unless the metal content reaches the percolation threshold of 24.0 vol %, beyond which the conductivity increases markedly by as much as 11 orders of magnitude, indicating an insulator–conductor phase transition. The homogeneity of these composites was checked by the morphologies of the constituents (filler and matrix) and the composites characterized by optical microscopy. The density of the composites was measured and compared with values calculated assuming different void levels within the samples to discuss the porosity effect. Finally, the obtained results on electrical conductivity have been well interpreted with the statistical percolation theory. The deduced critical parameters, such as the threshold of percolation, V_f*, the critical exponent, t, and the packing density coefficient, F, were in good accord with earlier studies. In addition, the hardness of samples remained almost constant with the increase of metal concentration. POLYM. COMPOS., 2011. © 2010 Society of Plastics Engineers     

Dissolution mechanism of cellulose in SO2–amine–dimethylsulfoxide

The dissolution mechanism of cellulose in SO₂–amine–dimethylsulfoxide systems was studied by using ¹H- and ¹³C-NMR spectroscopy. SO₂ and amine (diethylamine or triethylamine) were found to form a complex in DMSO, and the SO₂–amine complex, in turn, reacts with an alcoholic hydroxyl group of methanol to produce a new complex. In the case of cellulose, it was proved that all hydroxyl groups in cellulose react with the SO₂–amine complexes and form the same complexes in the solution state as those formed in methanol.     

Graft copolymers prepared by anionic techniques–a review

The synthesis of graft copolymers by anionic polymerization techniques is reviewed. Two basic procedures are described. In one a polymer having a reactive end-group is prepared and allowed to react with another polymer having suitable functional groups. In the second procedure, anions are generated on a preformed polymer backbone and used to initiate the polymerization of subsequently added monomers.     

Infrared–deuteration study of regenerated cellulose fibers

This paper describes a study by infrared, deuteration, and other techniques of the fine structure of three regenerated cellulose fibers (Fortisan, a super tire yarn, and a fiber of high wet modulus). The infrared and deuteration measurement provide information on the amount and perfection of the hydrogen-bond ordered material in these celluloses. The three fibers are markedly different in structure: the Fortisan contains about 40% ordered cellulose of a high average degree of perfection, whereas the super tire yarn contains a smaller amount (about 20%) of ordered cellulose of a lower average degree of perfection: the yarn of high wet modulus contains about as much ordered material as the Fortisan, but of an average degree of perfection more similar to that of the super tire yarn. Infrared-dichroism measurements on the fibers are described. The infrared and dichroism studies are discussed in relation to the results of x-ray, moisture regain, acid hydrolysis, and birefringence measurements on the fibers. The infrared-deuteration behavior of acid hydrolysis residues prepared from the three fibers is described; these residues are more highly ordered than the patent fibers, but yield no information of any value in characterizing the structures of the parent fibers.     

Flow visualization of cellulose acetate–acetone solutions

The flow behavior of four cellulose acetate–acetone solutions varying from 20.00% to 28.18% solids concentration was observed using flow visualization techniques at 24°C with an industrial-type dry spinning system. Fibrous particulate matter entertained in the solutions and crossed polars revealed the streamlines and the birefringence due to flow in glass spinnerets. The streamlines of the four solutions were radially convergent at all obtainable throughputs. The crossed polars revealed a cone of birefringence with the order of the interference colors decreasing upstream of the capillary inlet. The intensity and extent of birefringence varied somewhat with concentration and throughput. Except for kneeing, the emerging extrudates were undeformed. The kneeing was not a result of flow instability a t the capillary inlet but was due to another, undetermined instability. A separate study of the kneeing revealed both a concentration dependence and hysteresis. The birefringence of the emerging extrudates was a function of both concentration and throughput, and it yielded some information about the structure of the solutions.     

Electron-microscopic investigation of cerium–cotton cellulose reactions

Cotton fibers were treated with an aqueous solution of ceric ammonium nitrate and examined with the electron microscope. The greatest deposition of cerium occurred in the primary wall due largely to the reaction with noncellulosic constituents in this area of the fiber. The use of ceric ions for an electron-microscopic stain was found ineffective for producing the desired contrast in the cotton fiber.     

Preparation of PMMA–PS–PMMA via combination of anionic and photoinduced charge‐transfer polymerization

PMMA–PS–PMMA triblock copolymers were prepared by the combination of an anionic mechanism with charge‐transfer polymerization. Polystyrene with aromatic tertiary amino groups at both ends (PS_ba) was synthesized first by the reaction of a living polystyrene macrodianion with excess p‐(dimethylamino)benzaldehyde; then, the PS_ba was constituted into a binary system with benzophenone (BP) to initiate the polymerization of methyl methacrylate (MMA) under UV irradiation. The intermediate and resulting block copolymers were characterized by GPC, IR, and ¹H‐NMR. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2072–2076, 1999     

Soy protein–lignosulphonate plastics strengthened with cellulose

A series of biodegradable plastics from soy protein and lignosulphonate (SL) were strengthened with cellulose powder (CP) by melt blending and compression molding. The effects on the morphology and properties of the blends of introducing CP were investigated by wide‐angle X‐ray diffraction, differential scanning calorimetry, dynamic mechanical thermal analysis, scanning electron microscopy, and tests of tensile and water absorption. It is worth noting that introducing CP obviously improved the mechanical properties and water resistivity of composite plastics. With an increase in CP content, the tensile strength and Young's modulus of the blend materials increased. The experimental results indicate that a certain degree of miscibility between SL and CP and a strong interaction among various molecules of the components, resulting in strengthened materials. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1685–1689, 2003     

Electrospinning of ethyl–cyanoethyl cellulose/tetrahydrofuran solutions

In this study, electrospinning was used to fabricate ethyl–cyanoethyl cellulose [(E‐CE)C] fiber from a solution of (E‐CE)C/tetrahydrofuran. The diameter of the thinnest fiber fabricated during the electrospinning was about 200 nm. It was found that the diameters of the fibers and their distribution depend on the processing parameters and properties of the solution, such as viscosity, temperature, and concentration, for example. The morphology of the fiber was also observed by SEM. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 242–246, 2004