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Cellulose

, Volume 22, Issue 2, pp 1063–1074 | Cite as

Surface characteristics of cellulose nanoparticles grafted by surface-initiated ring-opening polymerization of ε-caprolactone

  • Linn Carlsson
  • Tobias Ingverud
  • Hanna Blomberg
  • Anna Carlmark
  • Per Tomas LarssonEmail author
  • Eva MalmströmEmail author
Original Paper

Abstract

In this study, surface-initiated ring-opening polymerization has been employed for the grafting of ε-caprolactone from cellulose nanoparticles, made by partial hydrolysis of cellulose cotton linters. A sacrificial initiator was employed during the grafting reactions, to form free polymer in parallel to the grafting reaction. The degree of polymerization of the polymer grafts, and of the free polymer, was varied by varying the reaction time. The aim of this study was to estimate the cellulose nanoparticle degree of surface substitution at different reaction times. This was accomplished by combining measurement results from spectroscopy and chromatography. The prepared cellulose nanoparticles were shown to have 3.1 (±0.3) % of the total anhydroglucose unit content present at the cellulose nanoparticle surfaces. This effectively limits the amount of cellulose that can be targeted by the SI-ROP reactions. For a certain SI-ROP reaction time, it was assumed that the resulting degree of polymerization (DP) of the grafts and the DP of the free polymer were equal. Based on this assumption it was shown that the cellulose nanoparticle surface degree of substitution remained approximately constant (3–7 %) and seemingly independent of SI-ROP reaction time. We believe this work to be an important step towards a deeper understanding of the processes and properties controlling SI-ROP reactions occurring at cellulose surfaces.

Keywords

Solid-state cross-polarization magic angle spinning carbon-13 nuclear magnetic resonance (CP/MAS 13C-NMR) Surface grafting Ring-opening polymerization Degree of substitution Cotton linters Cellulose 

Abbreviations

FRP

Free radical polymerization

RDRP

Reversible-deactivation radical polymerization

ÐM

Molar-mass dispersity

ATRP

Atom transfer radical polymerization

RAFT

Reversible addition-fragmentation chain-transfer

NMP

Nitroxide-mediated polymerization

ROP

Ring-opening polymerization

SI-ROP

Surface-initiated ring-opening polymerization

AGU

Anhydroglucose unit

CNF

Cellulose nanofibrils

CNC

Cellulose nanocrystals

Sn(Oct)2

Tin 2-ethylhexanoate

PCL

Poly(ε-caprolactone)

ε-CL

ε-Caprolactone

CCL

Cellulose cotton linters

HCCL

Hydrolyzed cellulose cotton linters

CP/MAS

Cross-polarization/magic angle spinning

DSBM

Bulk monomer degree of substitution

PCL-g-HCCL

PCL-grafted HCCL

DP

Degree of polymerization

SEC

Size exclusion chromatography

DSSP

Degree of polymer/cellulose nanoparticle surface substitution

NaClO4

Sodium perchlorate

BnOH

Benzyl alcohol

THF

Tetrahydrofuran

MeOH

Methanol

Notes

Acknowledgments

Wallenberg Wood Science Center (WWSC), the Swedish Research Council (VR) and  the Swedish Research Council Formas are acknowledged for financial support. Dr. Xuewei Zhang, LCPP C2P2, CPE, Lyon, France is greatly acknowledged for support with SEC analyses.

Supplementary material

10570_2014_510_MOESM1_ESM.pdf (400 kb)
Supplementary material 1 (PDF 400 kb)

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Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Linn Carlsson
    • 1
    • 2
  • Tobias Ingverud
    • 2
  • Hanna Blomberg
    • 2
  • Anna Carlmark
    • 2
  • Per Tomas Larsson
    • 1
    • 2
    • 3
    Email author
  • Eva Malmström
    • 2
    Email author
  1. 1.Wallenberg Wood Science Centre, School of Chemical Science and EngineeringKTH Royal Institute of TechnologyStockholmSweden
  2. 2.School of Chemical Science and Engineering, Fibre and Polymer TechnologyKTH Royal Institute of TechnologyStockholmSweden
  3. 3.Innventia ABStockholmSweden

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