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  • 1
    Electronic Resource
    Electronic Resource
    Springer
    Cellulose 6 (1999), S. 153-165 
    ISSN: 1572-882X
    Keywords: cellulose functionalisation ; carboxymethyl cellulose ; cellulose solvents ; homogeneous procedure ; reactive microstructure
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Carboxymethylation of cellulose in the new and highly efficient aqueous solvent Ni(tren)(OH)2, [tren=tris(2‐aminoethyl)amine] and in melts of LiClO4· 3H2O or N‐methyl‐morpholine‐N‐oxide (NMMNO), which is now widely applied for cellulose fibre production, was investigated. In case of Ni(tren)(OH)2, a totally homogeneous carboxymethylation of cellulose with sodium monochloroacetate, in the presence of an aqueous NaOH solution is possible for the first time. Structure analysis by means of HPLC and 1 H‐NMR after chain degradation showed results comparable with findings for CMC obtained by the heterogeneous slurry process, that is, a statistic distribution of substituents along the polymer chain and functionalisation of the hydroxyl groups in the order C‐6 ≥ C‐2 〉 C‐3. The etherification of cellulose in a melt of LiClO4· 3H2O, a new type of cellulose solvent, was shown to be possible and gave products of a statistic functionalisation pattern as well. In contrast, carboxymethylation starting from solutions of cellulose in NMMNO initiated with solid NaOH particles yields polymers with a nonstatistic distribution of functional groups along the chain, as observed for cellulose ethers prepared in reactive microstrctures starting from solutions of cellulose intermediates in dimethyl sulfoxide as well as of unmodified cellulose dissolved in N,N‐dimethyl acetamide/LiCl.
    Type of Medium: Electronic Resource
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  • 2
    ISSN: 1572-882X
    Keywords: soluble cellulose trifluoroacetates ; thermal and hydrolytic behaviour ; extent of depolymerization ; distribution of substituent ; application of chlorinated hydrocarbons
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Abstract Cellulose trifluoroacetate (CTFA) with DS values of 1.5 and 2.1 and DP values ranging from 170 to 800 have been prepared free from impurities of the reaction mixture (weakly bound trifluoroacetic acid) and of the procedure of isolation (diethyl ether). The CTFAs are soluble in DMSO, DMF, pyridine, and THF and thermostable up to 250 °C. A convenient synthetic method for CTFAs with DS 1.5 involves the acylation of cellulose with mixtures of trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAA, 33% v/v) at room temperature for 4 h and subsequent treatment of the crude polymer at 150 °C and 80 Pa for 40 min. The preparation of CTFAs with DS-values up to 2.1 requires the addition of chloroform and 16 h reaction time.13 C-NMR studies as well as HPLC analyses after methylation and chain degradation show a preferred trifluoroacetylation of the primary hydroxy groups of the cellulose. The extent of depolymerization during the trifluoroacetylation was investigated for various cellulose materials. The cleavage of the trifluoroacetyl groups is possible by treating the derivative with a protic medium like water. Total hydrolysis of CTFA dissolved in DMF with water (room temperature) takes 6 min.
    Type of Medium: Electronic Resource
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