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  • 1
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 13 (1975), S. 1441-1456 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The chemical nature of starch xanthate (SX)-polyethylenimine (PEI) reaction products has been studied because of their effectiveness as wet-end additives for improving strength properties of paper. Model compounds, in conjunction with ultraviolet, infrared, and chemical analyses, served to elucidate SX-PEI reaction mechanisms. Aqueous solutions of SX (degrees of substitution 0.1-0.5) were titrated with PEI at pH 5-7 (25-30°C) to form SX-PEI flocculent precipitates that were determined to be polyelectrolyte complexes. However, when solutions of SX-PEI were kept at pH 10-12, products were formed that included dithiocarbamic acid salts in major quantities, PEI thioureas, and minor quantities of O-starch PEI thinocarbamate. Acid precipitation of these SX-PEI polymeric reaction products from their alkaline solutions, which contained residual xanthate and PEI, also yielded polyelectrolyte complexes. Model systems suggest that PEI thiuram disulfide and starch xanthide, possible products of air oxidation, could be present in minor amounts and would react rapidly with PEI to yield thioureas and thioncarbamates, respectively. Apparently, mixtures of xanthate and amine gave (1) dithiocarbamic acid salts from both xanthate groups and CS2 (decomposition from xanthate), (2) thioureas from both dithiocarbamic acid salts and thiuram disulfide, and (3) thioncarbamates, principally from xanthate as opposed to xanthide.
    Additional Material: 7 Ill.
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 22 (1978), S. 897-904 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Starch polyampholytes (xanthated starch amines) that contained either diethylaminoethyl or 2-hydroxypropyltrimethylammonium ether and xanthate substituents were prepared, characterized, and evaluated as wet- and dry-strength agents in paper handsheets. In aqueous solutions, these xanthated starch amines (XSA), which had degrees of substitutions (D.S.) of 0.023-0.33 amine and 0.005-0.165 xanthate, underwent intra- and interionic bonding at their isoelectric points to form soft flocculent precipitates. Properties of XSA resembled those of “complex coacervates.” Paper that was prepared from an unbleached kraft furnish treated with XSA (amine/xanthate molar ratios, from 1.5 to 4.0) had significantly stronger wet and dry strengths than paper treated with cationic starch amines typically used in commercial papermaking.
    Additional Material: 5 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 45 (1992), S. 1093-1100 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Acrylonitrile (AN) was graft polymerized onto unmodified cornstarch by a continuous reactive extrusion process and, for comparison, by a typical batch reaction process. The effect of AN/starch weight ratios, level of ceric ammonium nitrate (CAN) initiator, starch in water concentration, reaction temperature, reaction time, and extruder screw speed in the reactive extrusion process was studied. Add-on, reaction efficiency, grafting frequency, weight average molecular weight (MW) and MW distribution of polyacrylonitrile (PAN), and water absorbency of the saponified copolymers were determined. Processing times in the twin-screw extruder (ZSK) were 2-3 min, and total reaction time was about 7 min before reaction of the extruded material was terminated, compared to a reaction time of 2 h used in the typical batch procedure. The continuous reactive extrusion process was found to be a rapid and efficient means of preparing St-g-PAN with high add-on (% PAN of the grafted product). For example, 42% add-on was achieved within the 7-min reaction period using an AN/starch weight ratio of 1.0 (3.5% CAN, starch weight basis), as compared to 38-49% for the 2-h batch process (0.75-1.5 AN/starch ratio). Percentages of homopolymer of the copolymers were low for both extrusion and batch processes. Grafting frequencies were substantially higher while MWs were significantly lower for grafts from the extrusion process. Water absorbency of the saponified St-g-PAN products was somewhat greater for the products prepared by the batch process.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 44 (1992), S. 1477-1483 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Rigid polyurethane foams were prepared containing 20% (based on weight of polyol) unmodfied or modified cornstarches. The cornstarches had been modified by breeding or conversion methods and included waxy, acid-modified waxy, malto-dextrin, and canary dextrin. Due to its more favorable role as an extender, canary dextrin was added to additional foam formulations at 10-40%. Foams containing dextrins responded to compressive stress as control foams with yield points before 10% deformation. Foams filled with the unmodified or waxy cornstarches did not give clearly defined yield points and were measured at 10% deformation. After 14 days under 70°C and ambient conditions, volume increases for the filled foams were 4.0-7.1% vs. 4.6% for the control. The foams filled with canary dextrin increased in volume 4.3%. With the addition of 40% canary dextrin, the volume increases for the foams were 4.4% under thermal conditions and 4.5% under humid conditions (38°C and 98% relative humidity). Under humid conditions for 14 days, the foams containing canary dextrin increased in weight as dextrin content increased (1.5, 3.2, 3.4, and 7.6% with 10, 20, 30, and 40% dextrin, respectively). with 40% canary dextrin in the foams, thermal conductivity was 0.0235 vs. 0.0242 W/mK (0.163 vs. 0.168 Btu in/ft2h°F) for the control.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 42 (1991), S. 45-53 
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Previously, starch-derived glycol and glycerol glucosides were prepared by batch-reaction processes and had excellent potential as chemical intermediates for a wide range of products. However, more efficient processes for preparation of these derivatives are needed. In this present work, a modern corotating, intermeshing, twin-screw extruder with a barrel length/screw diameter (L/D) ratio of 43: 1 was used to study the reaction of starch with ethylene glycol and glycerol in the presence of sulfuric acid catalyst at elevated temperatures. A fully continuous process was used. Variables that were investigated included temperature (140-180°C), glycol or glycerol/starch AGU mol ratio (1.5-4.0), starch feed rate (5-30 lb/h), screw speed (100-475 rpm), residence time, specific energy, and several types of commercial cornstarch and corn flour products. Rates and extents of reaction that occurred in the barrel were determined by analyzing samples that were quenched just prior to extrusion. The major glucosides were quentitated by high-performance liquid chromatography. Results of this study show that starch can be continuously, rapidly, and efficiently converted to glucosides in 90% yield at high production rates. Such processing is expected to be technically feasible for the reaction of a wide range of polyhydroxy alcohols with various starch substrates.
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  • 6
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Cationic starch, an important additive for papermaking and other uses, was prepared from native cornstarch and 3-chloro-2-hydroxypropyltrimethylammonium chloride in aqueous sodium hydroxide using a twin-screw extruder as the reactor. The effects of physical and chemical reaction variables on reaction efficiency (RE) and degree of substitution (DS) of up to 0.05 were studied. RE was based on nitrogen content contributed by cationization of the starch after the products were exhaustively washed to remove unreacted monomer. Under certain reaction conditions, exceptionally high RE (90%+) was achieved, exceeding maximum values previously reported using laboratory-batch reaction procedures. The combined effects of high reaction temperature (90°C), intense mixing, high-starch solids (65%), and appropriate levels of catalyst contributed to the unusually high RE values achieved by the reactive extrusion process. © 1994 John Wiley & Sons, Inc.†
    Additional Material: 4 Ill.
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  • 7
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: The efficacy of oxidatively crosslinked starch xanthate for improving wet- and dry-strength properties of paper prompted the present study of an alternative, interpolymeric crosslinking procedure. Sodium starch xanthate of degrees of substitution 0.05-0.25 was reacted with a commercial paper additive (a polyamide-polyamine-epichlorohydrin wet-strength resin) which was found to contain 3-hydroxyazetidinium chloride, epoxy-propyl, and chlorohydrin groups (3:1:1) to give an interpolymer crosslinked by both ionic and covalent bonds. Model systems, in conjunction with nuclear magnetic resonance, infrared, and ultraviolet spectral data, served to elucidate reaction mechanisms and structures of the interpolymer and the commercial resin. Reaction conditions that favored formation of either ionic (polysalt) or covalent (xanthate ester) crosslinks were investigated. In preliminary evaluations, incorporation of the interpolymer into paper handsheets resulted in excellent wet- and dry-strength improvements.
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  • 8
    ISSN: 0021-8995
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics , Physics
    Notes: Polyurethane foams containing equal amounts of commercial unmodified cornstarch and a polyisocyanate-terminated polyether exhibit properties suitable for horticultural applications. The use of cornstarch in the foam formulation increased the volume by one-fourth as compared to the foam without cornstarch. This volume increase represents an economic advantage of 20% savings based on material cost. When cornstarch or corn flour is added to the foam formulation, the foams are more resistant to compressive force. Upon wetting and draining, the foams prepared with no auxiliary blowing agent and containing corn products exhibit higher volumes than do the unfilled foams. Radish seeds planted inside 25 mm cubes of foams began to sprout after 1 day. Early developmental growth for the plants was similar in the control and cornstarch-filled foams. Spectroscopic analyses of the starch-containing foams revealed that 60-70% of the cornstarch was metabolized within 4-5 weeks by a microbial consortium. Control polyurethane foams were not affected by the microorganisms tested. © 1994 John Wiley & Sons, Inc.This article is a U.S. Government work and, as such, is in the public domain in the United States of America.
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