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

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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.

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Abbreviations

FRP:

Free radical polymerization

RDRP:

Reversible-deactivation radical polymerization

Ð M :

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

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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.

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Authors and Affiliations

  1. Wallenberg Wood Science Centre, School of Chemical Science and Engineering, KTH Royal Institute of Technology, 100 44, Stockholm, Sweden

    Linn Carlsson & Per Tomas Larsson

  2. School of Chemical Science and Engineering, Fibre and Polymer Technology, KTH Royal Institute of Technology, 100 44, Stockholm, Sweden

    Linn Carlsson, Tobias Ingverud, Hanna Blomberg, Anna Carlmark, Per Tomas Larsson & Eva Malmström

  3. Innventia AB, Box 5604, 114 86, Stockholm, Sweden

    Per Tomas Larsson

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  1. Linn Carlsson
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  2. Tobias Ingverud
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  3. Hanna Blomberg
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  4. Anna Carlmark
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  5. Per Tomas Larsson
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  6. Eva Malmström
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Correspondence to Per Tomas Larsson or Eva Malmström.

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Carlsson, L., Ingverud, T., Blomberg, H. et al. Surface characteristics of cellulose nanoparticles grafted by surface-initiated ring-opening polymerization of ε-caprolactone. Cellulose 22, 1063–1074 (2015). https://doi.org/10.1007/s10570-014-0510-1

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