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  • 1
    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 reaction of methyl iodide with cellulose β-mercaptoethylaminocarboxylate (RDTC) made from cotton was investigated. The product was found to contain dimethyl sulfonium groups in addition to S-methyl groups, with accompanying hydrolytic cleavage of some of urethane linkages. The iodide counterions could be easily exchanged with hydroxide and chloride ions. The dyeabilty of RDTC and its sulfonium derivatives toward Direct Sky Blue A was studied. The equilibrium uptake of the dye by RDTC decreased with increasing sulfur content, while the uptake by the sulfonium derivatives was higher than that of control cotton and increased with increasing sulfonium content. The counterions did not affect the dyeability. The dye adsorbed onto the sulfonium derivatives was very fast against solvent extraction, and could be extracted only with Cadoxen containing 0.5% sodium hydroxide. The equilibrium uptake of the dye was much more than the amount calculated on basis of the 1 : 1 ionic bonding between the sulfonic acid group in the dye molecule and the sulfonium group in the modified cotton. The spatial effect in the dye-sulfonium bonding is discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 13 (1969), S. 1845-1858 
    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: Mercaptan and disulfide contents of modified cotton fabrics could be determined by application of Leach's polarographic method for wool, with minor modification.It was found that mercaptocellulose prepared by the reaction of tosyl cellulose and potassium thiolacetate followed by alkaline hydrolysis contained considerable amounts of disulfided in addition to mercaptain. Iodometric titration of mercaptocellulose gave a higher value of mercaptan than that obtained by the polarographic method. The mercaptan and disulfide contents and methylene blue uptake of the iodine-treated samples indicate that some of the mercaptan groups further undergo oxidation to acidic groups as a result of the iodine treatment.The spatial effect in the oxidation of mercapto groups in modified cotton is briefly discussed.
    Additional Material: 7 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 14 (1970), S. 865-878 
    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: Bis-β-isocyanatoethyl disulfide (BIED) was synthesized from diethyl dithiodipropionate and its reaction with cotton in dimethylformamide was investigated. The sulfur content of the treated cotton decreased by reduction with tri-n-butylphosphine. The polarographic and infrared analyses revealed that BIED reacted with cotton both monofunctionally and bifunctionally to form branches and crosslinks, respectively. The ratio of the crosslinks to the total amount of BIED combined increased in general as the reaction progressed. X-Ray study indicated that the reaction took place mainly in the original amorphous region.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 16 (1972), S. 1495-1503 
    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: Reactions of tosylated cotton with potassium thiolacetate followed by alkaline hydrolysis yielded products containing both mercaptan and disulfide. The proportion of disulfide in the products depended much on the solvent used for the thiolacetylation. Reactions of tosylcellulose with thiolacetate in various solvents were investigated by polarographic and infrared analyses. Part of the acetylthio groups produced in acetone or in dimethylformamide was found to undergo rearrangement to form mercaptocellulose acetate. On the other hand, acetylthio groups formed in methanol were found to undergo complete methanolysis to form mercaptocellulose, and most of the mercapto groups thus produced were oxidized before hydrolysis treatment to yield the corresponding disulfide. This could account for the high disulfide proportion in the sample obtained through the reaction of tosylcellulose in methanol. Reaction of tosylcellulose with sodium thiosulfate yielded cellulose disulfide without mercaptan formation.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 11 (1973), S. 1961-1971 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Cellulose β-mercaptoethylaminocarboxylate made from unmercerized cotton was partially oxidized in various solvents of different swelling power followed by treatment with excess methyl iodide to yield partially disulfide-crosslinked cotton samples of about the same degrees of crosslinking containing sulfonium groups of about the same contents. The effect of the solvent in crosslinking on the equilibrium and kinetics of dyeing with three dyes (Orange II, Direct Scarlet B, and Direct Sky Blue A) of different molecular size was investigated. The 1:1 ionic bonding was observed at equilibrium between sulfonic acid groups in dye molecules and sulfonium groups in modified cottons in cases of Orange II and Direct Scarlet B. The equilibrium uptake of the largest dye, Direct Sky Blue A, was much influenced by the solvent used in crosslinking; the higher the degree of swelling in crosslinking, the larger the equilibrium uptake. The diffusion rate of Direct Scarlet B was much affected by the solvent used; the higher the degree of swelling, the higher the diffusion rate. The pore structure of the crosslinked cotton was discussed. The crosslinked cotton seemed to have a “memory” of the state at the time of crosslinking and to have a tendency to come back close to that state when placed in a dye bath.
    Additional Material: 4 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Die Makromolekulare Chemie 99 (1966), S. 232-242 
    ISSN: 0025-116X
    Keywords: Chemistry ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Physics
    Description / Table of Contents: Die Copolymerisation von Tetrahydrofuran (THF) mit Diketen (DK) bei 0°C mit einem Triäthylaluminium/Wasser-System als Initiator, führt zu schwach gelben, festen Produkten. Der Nachweis fär eine Copolymerisation wurde durch IR-Analyse der benzolunlöslichen Fraktion erbracht; hierbei wurden Banden gefanden, die kristallinem Poly-THF zuzuordnen sind. Außerdem liefert die alkalische Hydrolyse dieser Fraktion homopolymere Tetrahydrofurane mit Molekulargewichten zwischen 1500 und 3100; sie besitzen OH- und COOH-Endgruppen. Diese experimentellen Befunde bestätigen die Annahme, daß es sich hier um Block-Copolymere und nicht um statische Copolymere handelt.
    Notes: Copylymerization of tetrahydrofuran (THF) with diketene (DK) was carried out at O°C. using the triethylaluminum/water-system as catalyst. The produced polymer was a yellow solid. The formation of a copolymer was shown by the existence of THF units in the benzene-insoluble fraction of the polymeric product. The IR-spectrum of the benzeneinsoluble fraction had a band which can be ascribed to the crystalline poly-THF. Furthermore poly-THF having molecular weights of 1,500 to 3,100 was isolated from the hydrolyzed mixture of the benzene-insoluble fraction high yield; it has OH- and COOH-end groups. These facts have been taken to assume that the copolymerization of THF with DK leads to the formation of block copolymers instead of random copolymers.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    ISSN: 0449-296X
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation behavior of mercaptocellulose prepared from tosylated cotton and of cellulose β-mercaptoethylaminocarboxylate (RDTC), which was prepared by reduction of a cotton derivative made by the reaction with bis-β-isocyanatoethyl disulfide, was studied, and the factors controlling the oxidation behaviors of solid polymeric mercaptans were discussed. RDTC was converted quantitatively to the corresponding disulfide by oxidation under mild conditions. Repeated oxidation-reduction cycles were applied to RDTC to demonstrate complete reversibility of disulfide crosslinking. On the other hand, only a portion of the mercaptan in mercaptocellulose could form disulfide by oxidation. It is considered that the mobility of the mercapto groups necessary for the oxidation coupling is restricted because they are attached directly to rigid cellulose chains. The oxidation of RDTC with air in alkaline medium was studied kinetically. It was found that the oxidation of the mercaptan in paired placement in the cellulose matrix proceeded more than ten times faster than that of the randomly placed mercaptan.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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