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Surface-Modified Cellulose Nanofibers-graft-poly(lactic acid)s Made by Ring-Opening Polymerization of l-Lactide

  • Chaniga Chuensangjun
  • Kyohei Kanomata
  • Takuya Kitaoka
  • Yusuf Chisti
  • Sarote SirisansaneeyakulEmail author
Original paper

Abstract

Highly crystalline cellulose nanofibers with a high density of carboxylate groups only on the surfaces were prepared from both softwood and non-wood cellulose pulp. The preparation method used 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO)-mediated oxidation of native cellulose fibrils in an aqueous TEMPO/NaBr/NaClO system and subsequent postoxidation with NaClO2 in acetate buffer (pH 4.8). The TEMPO-oxidized cellulose nanofibers (TOCNs) possessed a carboxylate content of 1.7 mmol g−1 and a crystallinity of 67–69% with a crystallite size of ∼3 nm. The TOCNs were used to produce highly crystalline TOCN-graft-poly(lactic acid) (PLA) nanocomposites via ring-opening polymerization of l-lactide in a polar aprotic solvent. Effects of the reaction temperature and the molar ratio of l-lactide to carboxylate surface groups, on the efficiency of surface grafting were investigated to potentially improve the crystallinity and thermal properties of the nanocomposites. The crystallinity of TOCN-g-PLA products was 59–66% greater than the crystallinity of neat PLA.

Keywords

Cellulose nanofibers Nanocomposites Cellulose-poly(lactic acid) composites TEMPO-mediated oxidation Ring-opening polymerization 

Abbreviations

BBP

Bagasse bleached pulp

CDA

Cellulose diacetate

CDA-g-PLAs

Cellulose diacetate-graft-poly(lactic acid)s

CNC

Cellulose nanocrystals

Cr

Crystallinity (%)

CS

Crystallite size (nm)

DMSO

Dimethyl sulfoxide

DSC

Differential scanning calorimetry

DTGA

Derivative thermogravimetric analysis

Iam

Minimum height (i.e. the plateau) between peaks at 200 and 110 planes

I200

Intensity of diffraction peak at 200 plane of crystalline contribution

K

Dimensionless crystal shape factor

LA

l-lactide

N

Molarity (M) of NaOH solution

NMR

Nuclear magnetic resonance

PTFE

Polytetrafluoroethylene

PLA

Polylactic acid

QP1

Production rate of carbonyl groups (C=O) through ester formation (h−1)

QP2

Production rate of carbonyl groups (C=O) through PLA formation (h−1)

Qs

Consumption rate of carboxylate groups (COO) of TOCN–COOLi (h−1)

R

Molar ratio of l-lactide to carboxylate content of TOCNs

ROP

Ring-opening polymerization

SBKP

Softwood bleached kraft pulp

SD

Standard deviation

SEM

Scanning electron microscopy

Tdeg

Degradation temperature

TEMPO

2,2,6,6-Tetramethylpiperidine-1-oxyl

Tg

Glass transition temperature

Tm

Melting temperature

TGA

Thermogravimetric analysis

TOCNs

TEMPO-oxidized cellulose nanofibrils

TOCNs–COONa

TOCNs sodium salts

TOCNs–COOLi

TOCNs lithium salts

TOCN-g-PLA

TEMPO-oxidized cellulose nanofibers-graft-poly(lactic acid)s

V

Volume (mL) of alkali consumed

W

Mass (g) of dried TOCNs–COONa sample

YP1/S

Yield of ester carbonyl groups on carboxylate groups

YP2/S

Yield of PLA carbonyl groups on carboxylate groups

Greek letters

β

Diffraction peak width in radians

θ

Bragg angle corresponding to the 200 plane

λ

Wavelength (nm) of the incident X-ray

Notes

Acknowledgements

This research was supported by a Research and Researchers for Industries (RRI) PhD Scholarship awarded by the Thailand Research Fund under the Office of the Prime Minister, Royal Thai Government (code: PHD57I0037), and PTT Global Chemical Public Company Limited, Thailand. We are grateful to Assistant Professor Dr Shingo Yokota for advice on FTIR measurements.

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of Biotechnology, Faculty of Agro-IndustryKasetsart UniversityBangkokThailand
  2. 2.King Mongkut’s University of Technology North BangkokBangkokThailand
  3. 3.Department of Agro-Environmental Sciences, Faculty of AgricultureKyushu UniversityFukuokaJapan
  4. 4.School of EngineeringMassey UniversityPalmerston NorthNew Zealand
  5. 5.Center for Advanced Studies in Tropical Natural Resources (CASTNAR)National Research University-Kasetsart University (NRU-KU)BangkokThailand

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