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Cellulose

, Volume 16, Issue 6, pp 1075–1087 | Cite as

Controlled thermo-catalytic modification of regenerated cellulosic fibres using magnesium chloride Lewis acid

  • Dimtra Domvoglou
  • Roger IbbettEmail author
  • Franz Wortmann
  • Jim Taylor
Article

Abstract

The Lewis-acid catalytic reactions of magnesium chloride with regenerated cellulosic fibres under baking conditions can be interpreted using existing semi-crystalline morphological models. Reaction at 180 °C is associated with chain scission, which takes place randomly within the accessible regions of the fibre structure. This causes a rapid reduction in the cellulose degree of polymerization, which stabilizes at a limiting value, analogous to that observed with wet-state mineral acid catalysed hydrolysis. A slower scission-reaction is also observed, believed to be due to the liberation of single glucan units from crystallite ends, again analogous to wet-state mineral acid hydrolysis. Dry-state catalysis is promoted by thermal molecular motion, allowing migration of catalyst ions and also conformational flexing of the cellulose polymer, which also induces a small amount of recrystallisation at crystallite lateral surfaces. Differences in the dry-state reaction have been observed for lyocell, viscose and modal regenerated fibres, which can be related to differences in crystallinity and resulting accessibility of the magnesium chloride catalyst. For lyocell the accessibility towards magnesium chloride is lower than found with mineral acids, which may be significant in the development of treatments to promote mechanical fibrillation, without sacrificing fibre tensile properties.

Keywords

Regenerated Fibres Lewis Acid Thermal Degradation 

References

  1. Brandrup J, Immergut EH, McDowell W (1975) In the polymer handbook. Wiley-Interscience, NJGoogle Scholar
  2. Bredereck F, Hermanutz F (2005) Man-made cellulosics. Review of progress in coloration and related topics. Soc Dye Colour 35:59–75Google Scholar
  3. Broido A, Javier-son AC, Ouano AC, Barrall EM (1973) Molecular weight decrease in the early pyrolysis of crystalline and amorphous cellulose. J Appl Polym Sci 17:3627–3635CrossRefGoogle Scholar
  4. Calvini P (2005) The influence of levelling-off degree of polymerisation on the kinetics of cellulose degradation. Cellulose 12:444–447CrossRefGoogle Scholar
  5. Carrillo F, Colom X, Sunol JJ, Saurina J (2004) Structural FTIR analysis and thermal characterisation of lyocell and viscose type fibres. Eur Polym J 40:2229–2234CrossRefGoogle Scholar
  6. Hancock BC, Zografi G (1994) The relationship between the glass transition temperature and the water content of amorphous pharmaceutical solids. Pharm Res 11(4):471–477PubMedCrossRefGoogle Scholar
  7. Hermans PH, Weidinger A (1949) Chnages in crystallinity upon heterogeneous acid hydrolysis of cellulose fibres. J Polym Sci IV:317–322CrossRefGoogle Scholar
  8. Ibbett RN (2009a) A solid-state carbon-13 NMR investigation of the morphological reorganisation in regenerated cellulosic fibres induced by controlled acid hydrolysis. Submitted to CelluloseGoogle Scholar
  9. Ibbett RN, Domvoglou D, Fasching M (2007) Characterisation of the supramolecular structure of chemically and physically modified regenerated cellulosic fibres by means of high-resolution Carbon-13 solid-state NMR. Polymer 48:1287–1296CrossRefGoogle Scholar
  10. Ibbett RN, Domvoglou D, Phillips DAS (2008) The hydrolysis and recrystallisation of lyocell and comparative cellulosic fibres in solutions of mineral acid. Cellulose 15(2):241–254CrossRefGoogle Scholar
  11. Ibbett RN, Su Y, Renfrew AH, Phillips DAW, Taylor JM (2009) Evaluation of the mechanical properties of lyocell textile materials cross-linked with 2,4-diacrylamidobenzenesulphonic acid under swollen and non-swollen conditions. Accepted by J Appl Polym Sci, March 2009Google Scholar
  12. Ibrahim NA, Refai R, Hebeish A (1986) Basics of easy-care cotton finishing-part X1: improved performance with modified magnesium chloride catalysts. Am Dyest Report 75(7):25–33Google Scholar
  13. Jayme G, Roffael E (1969) Über dir anderungen der aöntgenkristallinität bei der heterogenen hydrolyse der cellulose. Das Pap 23(1):1–7Google Scholar
  14. Kan IS, Yang CO, Wei W, Lickfiled GC (1998) Mechanical strength of durable press finished cotton fabrics part 1: effects of acid degradation and crosslinking of cellulose by polycarboxylic acids. Text Res J 68(11):865–870CrossRefGoogle Scholar
  15. Kandola BK, Horrocks AR, Price D, Coleman GV (1996) Flame-retardant treatments of cellulose and their influence on the mechanism of cellulose pyrolysis. Polym Rev 36(4):721–794Google Scholar
  16. Kim S, Park JK (1995) Characterisation of thermal reactions by peak temperature and height of DTG curves. Thermochim Acta 264:137–156CrossRefGoogle Scholar
  17. Mak CM, Yuen CWM, Ku SKA, Kan CW (2006) Changes in surface morphology of Tencel fabric during the fibrillation process. J Text Ins 97(3):241–246CrossRefGoogle Scholar
  18. Morgado J, Cavaco-Paulo A, Rousselle MA (2000) Enzymatic treatment of lyocell—clarification of depilling mechanisms Jose Morgado. Text Res J 70(8):696–699CrossRefGoogle Scholar
  19. Nelson ML, Tripp VW (1953) Determination of the levelling-off degree of polymerisation of cotton and rayon. J Polym Sci 10(6):577–586CrossRefGoogle Scholar
  20. Nevell TP (1985) Acid and alkali reactions of cellulose. In: Nevell TP, Zeronian SH (eds) Cellulose chemistry and its applications. Ellis Horwood, UKGoogle Scholar
  21. Öztürk HB, Okubayashi S, Bechtold T (2006) Splitting tendency of cellulosic fibers—part 1. The effect of shear force on mechanical stability of swollen lyocell fibers. Cellulose 13(6):393–402CrossRefGoogle Scholar
  22. Pierce AG, Frick JG (1968) Highly active catalysts for wrinkle resistance and wash-wear finishing of cotton fabric. Am Dyest Report, Oct 21, pp 47–51Google Scholar
  23. Pierce AG, Reinhardt RM, Kullman MH. (1976) Catalytic effects in the reaction of methylolamide cross-linking agents with cellulose. Text Res J, June, pp 420–428CrossRefGoogle Scholar
  24. Salmén NL, Back EL (1977) The influence of water on the glass transition temperature of cellulose. Tappi J 60(12):137–140Google Scholar
  25. Scheirs J, Camino G, Tumiatti W (2001) Overview of water evolution during the thermal degradation of cellulose. Eur Polym J 37:933–942CrossRefGoogle Scholar
  26. Sharples A (1954) The hydrolysis of cellulose part 1. The fine structure of Egyptian cotton. J Polym Sci 13:393–401CrossRefGoogle Scholar
  27. Sharples A (1957) The hydrolysis of cellulose and its relation to structure. Trans Faraday Soc 53:1003–1014CrossRefGoogle Scholar
  28. Sheirs J, Camino G, Avidano M, Tumiatti W (1998) Origin of furanic compounds in thermal degradation of cellulosic insulating paper. J Appl Polym Sci 69:2541–2547CrossRefGoogle Scholar
  29. Solomon OF, Ciut IZ (1962) Determination de la Viscosite Intrinseque de Solutions de Polymeres par une Simple determination de la viscosite. J Appl Polym Sci 4(24):68–86Google Scholar
  30. Taylor JM, Colllins GW. (2007) Patent: dyeing of lyocell fabrics. WO02103104Google Scholar
  31. Trotman ER (1970) Dyeing and chemical technology of textile fibres, 4th edn. Charles Griffin, LondonGoogle Scholar
  32. Wood BF, Conner AH, Hill CG (1989) The heterogeneous character of the dilute acid hydrolysis of crystalline cellulose. J Appl Polym Sci 37:1373–1394CrossRefGoogle Scholar
  33. Wooten JB, Seeman JL, Hajaligol MR (2004) Observation and characterization of cellulose pyrolysis intermediates by 13C CPMAS NMR. A new mechanistic model. Energy Fuels 16(1):1–15CrossRefGoogle Scholar
  34. Yan CQ, Wei W, Lickfiled GC (2000) Mechanical strength of durable press finished cotton fabric, part III: change in cellulose molecular weight. Text Res J 70(10):910–915CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2009

Authors and Affiliations

  • Dimtra Domvoglou
    • 1
  • Roger Ibbett
    • 1
    • 2
    Email author
  • Franz Wortmann
    • 1
  • Jim Taylor
    • 3
  1. 1.The Christian Doppler Laboratory for Fibre and Textile Chemistry of CelluloseUniversity of ManchesterManchesterUK
  2. 2.Division of Food Sciences, School of BiosciencesUniversity of NottinghamLoughboroughUK
  3. 3.Lenzing AGLenzingAustria

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