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

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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.

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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

I am :

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

I 200 :

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

Q P1 :

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

Q P2 :

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

Q s :

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

T deg :

Degradation temperature

TEMPO:

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

T g :

Glass transition temperature

T m :

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

Y P1/S :

Yield of ester carbonyl groups on carboxylate groups

Y P2/S :

Yield of PLA carbonyl groups on carboxylate groups

β :

Diffraction peak width in radians

θ :

Bragg angle corresponding to the 200 plane

λ :

Wavelength (nm) of the incident X-ray

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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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Authors and Affiliations

  1. Department of Biotechnology, Faculty of Agro-Industry, Kasetsart University, 50 Ngam Wong Wan Road, Ladyaow, Chatuchak, Bangkok, 10900, Thailand

    Chaniga Chuensangjun & Sarote Sirisansaneeyakul

  2. King Mongkut’s University of Technology North Bangkok, 1518 Pracharat 1 Road, Wongsawang, Bangsue, Bangkok, 10800, Thailand

    Chaniga Chuensangjun

  3. Department of Agro-Environmental Sciences, Faculty of Agriculture, Kyushu University, 6-10-1 Hakozaki, Higashi-ku, Fukuoka, 812-8581, Japan

    Kyohei Kanomata & Takuya Kitaoka

  4. School of Engineering, Massey University, Private Bag 11 222, Palmerston North, New Zealand

    Yusuf Chisti

  5. Center for Advanced Studies in Tropical Natural Resources (CASTNAR), National Research University-Kasetsart University (NRU-KU), 50 Ngam Wong Wan Road, Ladyaow, Chatuchak, Bangkok, 10900, Thailand

    Sarote Sirisansaneeyakul

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  1. Chaniga Chuensangjun
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  2. Kyohei Kanomata
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Correspondence to Sarote Sirisansaneeyakul.

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Chuensangjun, C., Kanomata, K., Kitaoka, T. et al. Surface-Modified Cellulose Nanofibers-graft-poly(lactic acid)s Made by Ring-Opening Polymerization of l-Lactide. J Polym Environ 27, 847–861 (2019). https://doi.org/10.1007/s10924-019-01398-y

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