Skip to main content
SpringerLink
Log in

Mechanochemical reactions of cellulose and styrene

  • Original Paper
  • Published:
Cellulose Aims and scope Submit manuscript

Abstract

Vibratory ball milling of cotton in the presence and absence of styrene was studied by electron paramagnetic resonance spectroscopy, gel permeation chromatography and ultraviolet resonance Raman (UVRR) spectroscopy. Mechanoradical formation in ball milling of cellulose was detected, but the radical content was significantly lower and the molar mass slightly higher in the presence of styrene. UVRR also showed a small but consistent increase in aromatic signal, even after 5 h acetone extraction. A small portion of styrene was attached to cellulose, which was observed as an increase in the aromatic band intensity. Stabilization or a slight increase in molar mass of the samples that were milled in the presence of styrene was also observed. Overall, under the studied conditions, ball milling is not sufficient to significantly polymerize styrene onto cellulose. For future trials of mechanochemical copolymerization, it is recommended that a vacuum or an inert atmosphere be used.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  • Agarwal UP (1999) An overview of Raman spectroscopy as applied to lignocellulosic materials. In: Argyropoulos DS (ed) Advances in lignocellulosic characterization. Tappi Press, Atlanta, pp 201–225

    Google Scholar 

  • Ago M, Endo T, Hirotsu T (2004) Crystalline transformation of native cellulose from cellulose I to cellulose II polymorph by a ball-milling method with a specific amount of water. Cellulose 11:163–167

    Article  CAS  Google Scholar 

  • Ago M, Endo T, Okajima K (2007) Effect of solvent on morphological and structural change of cellulose under ball-milling. Polym J 39(5):435–441

    Article  CAS  Google Scholar 

  • Amiri O, Salavati-Niasari M, Sabet M, Ghanbari D (2013) Synthesis and characterization of CuInS2 microsphere under controlled reaction conditions and its application in low-cost solar cells. Mater Sci Semicond Process 16:1485–1494

    Article  CAS  Google Scholar 

  • Baytekin B, Baytekin HT, Grzybowski BA (2012) What really drives chemical reactions on contact charged surfaces? J Am Chem Soc 134:7223–7226

    Article  CAS  Google Scholar 

  • Beyer MK, Clausen-Schaumann H (2005) Mechanochemistry: the mechanical activation of covalent bonds. Chem Rev 105(8):2921–2948

    Article  CAS  Google Scholar 

  • Boldyreva E (2013) Mechanochemistry of inorganic and organic systems: what is similar, what is different? Chem Soc Rev 42:7719–7738

    Article  CAS  Google Scholar 

  • Bovey FA, Kolthoff IM (1948) Inhibition and retardation of vinyl polymerization. Chem Rev 42(3):491–525

    Article  CAS  Google Scholar 

  • Burchard W (2003) Solubility and solution structure of cellulose derivatives. Cellulose 10:213–225

    Article  CAS  Google Scholar 

  • Burke JM, Kincaid JR, Spiro TG (1978) Resonance Raman spectra and vibrational modes of iron(III) tetraphenylporphine µ-oxo dimer. Evidence for phenyl interaction and lack of dimer splitting. J Am Chem Soc 100(19):6077–6083

    Article  CAS  Google Scholar 

  • Chadha S, Ghiamati E, Manoharan R, Nelson WH (1992) UV-excited Raman and resonance Raman spectra of synthetic polymers. Appl Spectr 46(7):1176–1181

    Article  CAS  Google Scholar 

  • Cravotto G, Cintas P (2012) Harnessing mechanochemical effects with ultrasound-induced reactions. Chem Sci 3:295–307

    Article  CAS  Google Scholar 

  • Cunha AG, Gandini A (2010) Turning polysaccharides into hydrophobic materials: a critical review. Part 1. Cellulose. Cellulose 17:875–889

    Article  CAS  Google Scholar 

  • Dufresne A (2010) Processing of polymer nanocomposites reinforced with polysaccharide nanocrystals. Molecules 15:4111–4128

    Article  CAS  Google Scholar 

  • Gilman JJ (1996) Mechanochemistry. Science 274:65

    Article  CAS  Google Scholar 

  • Granström M, Kettunen M, Jin H et al (2011) Highly water repellent aerogels based on cellulose stearoyl esters. Polym Chem 2:1789–1796

    Article  Google Scholar 

  • Griller D, Ingold KU (1980) Electron paramagnetic resonance and the art of physical–organic chemistry. Acc Chem Res 13(7):193–200

    Article  CAS  Google Scholar 

  • He X, Zhang X, Zhang W, Tian D, Lu C (2014) Mechanochemically activated waste-derived cellulose as a novel functional additive to enhance melt processability and mechanical properties of poly(vinyl alcohol). J Vinyl Addit Technol 20:177–184

    Article  CAS  Google Scholar 

  • Hon D (1979) Formation and behavior of mechanoradicals in pulp cellulose. J Appl Polym Sci 23(5):1487–1499

    Article  CAS  Google Scholar 

  • Hu Y, Catchmark JM, Vogler EA (2013) Factors impacting the formation of sphere-like bacterial cellulose particles and their biocompatibility for human osteoplast growth. Biomacromolecules 14(10):3444–3452

    Article  CAS  Google Scholar 

  • Karatekin E, O’Shaughnessy B, Turro NJ (1998) Time-resolved EPR: a novel method for studying living chains. Macromolecules 31:7992–7995

    Article  CAS  Google Scholar 

  • Karinkanta P, Illikainen M, Niinimäki J (2013) Effect of grinding conditions in oscillatory ball milling on the morphology of particles and cellulose crystallinity of Norway spruce (Picea abies). Holzforschung 67(3):277–283

    Article  CAS  Google Scholar 

  • Kaupp G (2009) Mechanochemistry: the varied applications of mechanical bond-breaking. CrystEngComm 11:388–403

    Article  CAS  Google Scholar 

  • Kleine T, Buendia J, Bolm C (2013) Mechanochemical degradation of lignin and wood by solvent-free grinding in a reactive medium. Green Chem 15:160–166

    Article  CAS  Google Scholar 

  • Kondo S-I, Sasai Y, Hosaka S et al (2004) Kinetic analysis of the mechanolysis of polymethylmethacrylate in the course of vibratory ball milling at various mechanical energy. J Polym Sci 42:4161–4167

    Article  CAS  Google Scholar 

  • Kushawa SK, Maurya KK, Vijayan N, Bhagavannarayana G (2011) Crystalline perfection, EPR, prism coupler and UV–VIS–NIR studies on Cz-grown Fe-doped LiNbO3: a photorefractive nonlinear optical crystal. CrystEngComm 13:4866–4872

    Article  Google Scholar 

  • Kuzuya M, Yamauchi Y, Kondo S-I (1999) Mechanolysis of glucose-based polysaccharides as studied by electron spin resonance. J Phys Chem B 103:8051–8059

    Article  CAS  Google Scholar 

  • Malmström E, Carlmark A (2012) Controlled grafting of cellulose fibres—an outlook beyond paper and cardboard. Polym Chem 3:1702–1713

    Article  Google Scholar 

  • Ohura T, Tsutaki Y, Sakaguchi M (2014) Novel synthesis of cellulose-based diblock copolymer of poly(hydroxyethyl methacrylate) by mechanochemical reaction. World J Sci. doi:10.1155/2014/127506

    Google Scholar 

  • Paes SS, Sun S, MacNaughtan W et al (2010) The glass transition and crystallization of ball milled cellulose. Cellulose 17:693–709

    Article  CAS  Google Scholar 

  • Pönni R (2014) Changes in accessibility of cellulose for kraft pulps measured by deuterium exchange. Dissertation, Aalto University

  • Roy D, Semsarilar M, Guthrie JT, Perrier S (2009) Cellulose modification by polymer grafting: a review. Chem Soc Rev 38:2046–2064

    Article  CAS  Google Scholar 

  • Saariaho A-M (2004) Resonance Raman spectroscopy in the analysis of residual lignin and other unsaturated structures in chemical pulps. Dissertation, Helsinki University of Technology

  • Saariaho A-M, Argyropoulos DS, Jääskeläinen A-S, Vuorinen T (2005) Development of the partial least squares models for the interpretation of the UV resonance Raman spectra of lignin model compounds. Vib Spectrosc 37(1):111–121

    Article  CAS  Google Scholar 

  • Sakaguchi M, Ohura T, Iwata T et al (2010) Diblock copolymer of bacterial cellulose and poly(methyl methacrylate) initiated by chain-end-type radicals produced by mechanical scission of glycosidic linkages of bacterial cellulose. Biomacromolecules 11:3059–3066

    Article  CAS  Google Scholar 

  • Sakaguchi M, Ohura T, Iwata T, Enomoto-Rogers Y (2012) Nanocellulose particles covered with block copolymer of cellulose and methyl methacrylate produced by solid mechanochemical polymerization. Polym Degr Stab 97(3):257–263

    Article  CAS  Google Scholar 

  • Schult T, Hjerde T, Optun OI, Kleppe PJ, Moe S (2002) Characterization of cellulose by SEC-MALLS. Cellulose 9:149–158

    Article  CAS  Google Scholar 

  • Schwanninger M, Rodrigues JC, Pereira H, Hinterstoisser B (2004) Effects of short-time vibratory ball milling on the shape of FT-IR spectra of wood and cellulose. Vib Spectrosc 36(1):23–40

    Article  CAS  Google Scholar 

  • Solala I, Volperts A, Andersone A et al (2012) Mechanoradical formation and its effects on birch kraft pulp during the preparation of nanofibrillated cellulose with Masuko refining. Holzforschung 66:477–483

    Article  CAS  Google Scholar 

  • Stefanovic B, Rosenau T, Potthast A (2013) Effect of sonochemical treatments on the integrity and oxidation state of cellulose. Carbohydr Polym 92:921–927

    Article  CAS  Google Scholar 

  • Stefanovic B, Pirker KF, Rosenau T, Potthast A (2014) Effects of tribochemical treatments on the integrity of cellulose. Carbohydr Polym 111:688–699

    Article  CAS  Google Scholar 

  • Stubičar N, Šmit I, Stubičar M, Tonejc A, Jánosi A, Schurz J, Zipper P (1998) An X-ray diffraction study of the crystalline to amorphous phase change in cellulose during high-energy ball milling. Holzforschung 52:455–458

    Article  Google Scholar 

  • Tian D, Zhang X, Lu C, Yuan G, Zhang W, Zhou Z (2014) Solvent-free synthesis of carboxylate-functionalized cellulose from waste cotton fabrics to the removal of cationic dyes from aqueous solutions. Cellulose 21:473–484

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the Multidisciplinary Institute of Digitalisation and Energy (MIDE) for the financial support that enabled this collaboration. We also thank Dr. Bojan Stefanovic and Dr. Gerald Ebner for additional millings, and Ms. Mirja Reinikainen for her help in the UVRR measurements.

Author information

Authors and Affiliations

  1. Department of Forest Products Technology, Aalto University, Espoo, Finland

    Iina Solala & Tapani Vuorinen

  2. Christian-Doppler-Laboratory, Department of Chemistry, BOKU – University of Natural Resources and Life Sciences, Vienna, Konrad-Lorenz-Straße 24, 3430, Tulln an der Donau, Austria

    Ute Henniges, Thomas Rosenau & Antje Potthast

  3. Department of Chemistry, Division of Biochemistry, BOKU – University of Natural Resources and Life Sciences, Vienna, Muthgasse 18, 1190, Vienna, Austria

    Katharina F. Pirker

Authors
  1. Iina Solala
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Ute Henniges
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Katharina F. Pirker
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Thomas Rosenau
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Antje Potthast
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Tapani Vuorinen
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Iina Solala.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary material 1 (DOCX 14 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Solala, I., Henniges, U., Pirker, K.F. et al. Mechanochemical reactions of cellulose and styrene. Cellulose 22, 3217–3224 (2015). https://doi.org/10.1007/s10570-015-0724-x

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10570-015-0724-x

Keywords

Search

Navigation