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  • Polymer and Materials Science  (21)
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  • 1
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 9 (1965), S. 3869-3885 
    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: Rates of decrease in crystallinity, as measured by x-ray crystallinity index, have been followed throughout periodate oxidations of cotton cellulose and formaldehyde-treated cotton celluloses. Depending upon the conditions under which the agent was introduced, a low level of formaldehyde crosslinks exerted small or large retardation on the rate of decrease of crystallinity index. The extents of decrystallization per unit of oxidation of cotton and crosslinked cotton celluloses are substantially smaller in the initial phase of oxidation than in the later stage, indicative of preferential oxidative attack in the early stage on chain segments of predominantly noncrystalline regions. Relative to unmodified cotton, crosslinked cotton celluloses are characterized by more extensive decrystallization per unit of oxidation in the early phase of oxidative attack (to approx. 40%). From these data, supplemented by electron micrographs and solubilities in cupriethylenediamine hydroxide, uniformity of distribution of crosslinks is shown to increase in this series of formaldehyde-modified cotton celluloses (at the same level of agent) in the order: form D cotton (nonaqueous treatment) 〈 form W cotton (aqueous treatment) 〈 form V cotton (vapor treatment). Effectiveness of crosslinking (i. e., composite of number of linkages, ratio of intermolecular to intramolecular bonds, low degree of polymerization in crosslink) is indicated to increase from form W to form D to form V cotton.
    Additional Material: 7 Ill.
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  • 2
    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 distribution of formaldehyde crosslinks in cotton cellulose has been followed by electron micrographic analyses of fiber cross-sections and by kinetic analyses of rates of reactions of formaldehyde with cotton. Rapid and slow phases of the crosslinking reactions are indicated to extents which vary with the specific processes of reaction. A wide range in heterogeneity of distribution of crosslinks is found among the compositions investigated, the most heterogeneous distribution appearing in a high concentration of crosslinks in peripheral regions of the fiber. It is evident that additional substantial differences among the formaldehyde-crosslinked cottons are due to different extents of reaction of agent per accessible hydroxyl group.
    Additional Material: 6 Ill.
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 10 (1966), S. 1751-1761 
    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: Sol-gel fractions have been measured for cotton celluloses crosslinked with formaldehyde under widely different conditions of reaction and have been employed for estimation of the efficiency of crosslinking in the various processes. Most efficient utilization of formaldehyde for insolubilization of molecular chains is indicated for an aqueous process (form W′) and least efficient utilization is indicated for a nonaqueous process (form D′), the difference in efficiency being approximately a factor of 40. Interpretation of sol-gel data has been made relative to a model assuming random reaction of crosslinking agent throughout the cotton cellulose and by relationships developed by Charlesby and Pinner and by Shultz. This leads to estimates of relative numbers (moles) of effective chain elements per gram, ve (i.e., twice the number of effective crosslinks), which decrease in the following sequence for cottons at the 0.20% level of formaldehyde (i.e., 6.7 × 10-5 mole/g.): aqueous process, higher formaldehyde concentration (W′, ve = 4.8 × 10-5), vapor process (V, ve = 1.75 × 10-5), bake-cure process (C, ve = 1.37 × 10-5), aqueous process, lower formaldehyde concentration (W, ve = 0.95 × 10-5), nonaqueous process (D, ve = 0.03 × 10-5).
    Additional Material: 3 Ill.
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 10 (1966), S. 1777-1786 
    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: A method for assessing extent of swelling of the gel fraction of formaldehyde-modified cottons, employing cupriethylenediamine hydroxide as the swelling agent, is described. Substantial differences in apparent specific volumes of swollen gel fractions are observed for cottons crosslinked by different processes to the same level of agent. The apparent crosslink density measured by the swelling of gel fraction increases with formaldehyde content of the cotton; at 0.20% formaldehyde the order of increasing crosslink density in the various processes of reaction is as follows: nonaqueous system (forms D and D′) 〈 aqueous system (forms W and W′) 〈swelling system (form F) 〈 vapor system (form V) 〈 bake-cure system (form C).
    Additional Material: 4 Ill.
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  • 5
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 18 (1980), S. 2577-2583 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Availabilities of O(3)H relative to O(2)H (that is, [O(3)H]a/[O(2)H]a) on accessible surfaces of microstructural units of cotton fibers were measured by chemical microstructural analysis (CMA). CMA involves a mild chemical reaction with N,N-diethylaziridinium chloride, determination of substituent distribution for this product and a corresponding product from decrystallized cellulose, and simple computations. Measurements for fibers in commercial cotton fabric, for field-dried fibers, and for never-dried fibers are reported. The [O(3)H]a/[O(2)H]a, an inverse measure of intact O(3)H ·· O(5′) bonds, decreased in the stated order; thus, intact O(3)H ·· O(5′) hydrogen bonding increased in this same order. Results indicate a high degree of order in intramolecular bonding in the never-dried fiber and an increasing disruption of this bonding as the never-dried fiber is dried and processed.
    Additional Material: 1 Tab.
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  • 6
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 445-454 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relative availabilities of hydroxyl groups at C(2), C(3), and C(6) on the D-glucopyranosyl units of a particular, highly ordered hydrocellulose II have been studied by means of the reaction of N,N-diethylaziridinium chloride, which introduces 2-(diethyl-amino)ethyl substituents. The hydrocellulose II was formed by hydrolysis of fibrous cotton cellulose II during 40 min reflux in 2.5M hydrochloric acid and is designated EHC-II (exemplar hydrocellulose II) because it represents the most highly ordered (crystalline) particles in a series of hydrocelluloses. The deviation in the distribution of substituents among the 2-O-, 3-O-, and 6-O- positions of the D-glucopyranosyl units in EHC-II from that in a disordered cellulose, in which the three types of hydroxyl groups are equally available, is the basis for estimated availabilities of the three types of hydroxyl groups on the surfaces of elementary fibrils in EHC-II. The experimental values of relative availabilities of O(2)H:O(3)H:O(6)H for EHC-II were 1.0:0.26:0.72 compared to estimated values of 1.0:0.0:.075 for surfaces of elementary fibrils of an idealized, perfectly ordered cellulose II, a model that is based on intensities of x-ray diffraction peaks.
    Additional Material: 2 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York : Wiley-Blackwell
    Journal of Polymer Science: Polymer Chemistry Edition 12 (1974), S. 2099-2103 
    ISSN: 0360-6376
    Keywords: Physics ; Polymer and Materials Science
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 26 (1981), S. 3885-3894 
    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: An estimation of structures of reagent residues in cotton fabrics treated with N-methylolmethacrylamide (NMMA) and N-methylolacrylamide (NMA) and comparison of textile performance of the NMMA-cotton and NMA-cotton provide the basis for insight into the structure-performance relationship in these fabrics. The α-methyl substituent, which constitutes the difference between NMMA and NMA, accounts for an altered composition of reagent residues in the treated cotton. The more attractive balance of strength-abrasion resistance with resilience for the NMMA-cotton seems to be a result of a lower degree of covalent crosslinking, which appears compensated by a higher elastic modulus in the NMMA network polymer.
    Additional Material: 4 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 31 (1986), S. 2769-2777 
    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 pore structures of three liquid-ammonia-treated cottons were compared via a reverse gel permeation chromatographic technique. Cotton battings were treated with liquid ammonia which was removed by volatilization at ambient temperature or at elevated temperature and by water exchange. Three series of water-soluble solutes were used to study the elution characteristics of whole fiber columns prepared from these battings. The solutes were oligomeric sugars, ethylene glycols, and glymes (ethylene glycol dimethyl ethers) having molecular dimensions in the range of conventional finishing agents for cotton. All three liquid ammonia treatments increased the internal pore volumes accessible to small molecules. The greatest increase was noted when the ammonia was removed by water exchange and the least when volatilization at elevated temperature was employed. Ambient temperature volatilization had an intermediate effect. Decreases in the volumes of large pores were effected by ammonia treatments followed by volatilization at ambient or elevated temperature. Water exchange of the ammonia resulted in an increase in the volume of large pores as well as of the small pores.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY [u.a.] : Wiley-Blackwell
    Journal of Applied Polymer Science 37 (1989), S. 2371-2382 
    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: Hydrolyses of selected soluble polysaccharides (e.g., polyoses) and disordered and crystalline celluloses, each bearing 2-diethylaminoethyl (DEAE) substituents at low degree of substitution (DS 〈 0.05) were explored in 100% and 2N trifluoroacetic acid (TFA). Analyses were evaluated relative to hydrolysis with 72% sulfuric acid. DEAE-polyoses hydrolyzed readily in 100% and 2 N TFA during extended reaction periods with complete liberation of DEAE-glucoses. Hydrolyses of cellulose and DEAE-celluloses in 100% TFA were critically dependent upon cautious incremental dilution of the TFA during stepwise reaction to avoid precipitation of incompletely hydrolyzed products. DEAE-celluloses were partially solubilized and hydrolyzed in heterogeneous reaction in 2N TFA at 121°C. Complete liberation of DEAE-glucoses in the solubilized components was achieved after supplementary hydrolysis at 121°C. In all hydrolyses, including those with 72% sulfuric acid, extended hydrolyses were essential for complete liberation of the 2-O- and 6-O-DEAE-glucoses. Under optimum conditions, results of hydrolyses in 100% TFA were comparable to those in 72% sulfuric acid. Ease of release of DEAE-glucopyranoses in hydrolyses of DEAE-cellulose in 2N TFA was in the same order (3-O- 〉 6-O-〉 2-O-) as in homogeneous hydrolyses in sulfuric acid and in 100% TFA. Differences in release of isomeric DEAE-glucoses were greater in the heterogenous system. Degradation of glucose and DEAE-glucopyranoses occurred in extended periods of reaction in all acidic media. Rates of degradation of glucose and DEAE-glucopyranoses in dilute acid at 100°C were similar for glucose and 6-O-DEAE-glucose. The rates were about half as fast for 3-O-DEAE-glucose and an order of magnitude lower for 2-O-DEAE-glucose.
    Additional Material: 5 Ill.
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