Maderas-Cienc Tecnol 19(1):2017 Ahead of Print: Accepted Authors Version 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

DOI:10.4067/S0718-221X2017005000002

DIMENSIONAL STABILIZATION OF WOOD BY CHEMICAL MODIFICATION USING ISOPROPENYL ACETATE B. N. Giridhar1, K.K. Pandey1, *, B. E.Prasad1, S.S. Bisht1, H.M. Vagdevi2 1

Institute of Wood Science and Technology, 18th Cross Malleswaram, Bengaluru -560003, India 2 Department of Chemistry, Sahyadri Science College, Kuvempu University, Shimoga 577451, India *Corresponding author ([email protected]; [email protected]) Received: May 30, 2016 Accepted: October 02, 2016 Posted online: October 03, 2016

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ABSTRACT

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Chemical modification of wood with isopropenyl acetate (IPA) using iodine (I2) as catalyst

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has been carried out. Rubber wood (Hevea brasiliensis) specimens were reacted with IPA

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using iodine (I2) catalyst at 95°C up to 10 h under solvent free conditions. The effect of

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catalyst concentration and reaction time was studied. The extent of acetylation was measured

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by determining weight percent gain and the modified wood was characterized by FTIR-ATR

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and

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acylating reagent for wood. Modified wood exhibited high dimensional stability.

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Keywords: Chemical modification, dimensional stability, iodine, isopropenyl acetate, rubberwood.

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INTRODUCTION

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Wood is hygroscopic, dimensionally unstable especially in high humidity environment and

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prone to biological decay due to fungus and other microorganisms (Rowell 1983; 2013). All

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the major cell wall constituents of wood (lignin, cellulose and hemi-celluloses) contain an

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abundance of free hydroxyl groups. These free hydroxyl groups absorb and release water

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upon changes in the climatic conditions resulting in dimensional movements of wood. The

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dimensional stability and biological resistance of wood can be improved considerably by

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C NMR spectroscopy. It was found that IPA in the presence of iodine is an excellent

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chemical modification by converting hydrophilic –OH groups of cell wall components into

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larger more hydrophobic groups by forming covalent bonds (Rowell 1983, 2013, Matsuda

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1996, Hill 2006). Modification with thermosetting resins improves compression strength and

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performance against marine borers (Lopes et. al. 2014, 2015). Treatment with tall oils also

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reduced water absorption (Can and Sivrikaya 2016). Modified wood has outstanding

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dimensional stability, improved durability towards insects and micro-organisms.

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Chemical modification of grounded wood has been carried out by transesterification

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with vinyl esters (Jebrane et al. 2009). Giridhar and Pandey (2016) reported chemical

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modification of wood by transesterification using IPA in presence of AlCl3 as catalyst and

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examined dimensional stability and UV resistance of modified wood. In this work, chemical

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modification of wood with isopropenyl acetate (IPA) in presence of I2 catalyst was carried out.

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The reaction of wood with IPA forms acetone as byproduct (Figure 1) which can be easily

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removed from modified wood. O Wood OH

Catalyst H3C

O

CH 3

CH2

O

CH2 Wood O

CH3

HO

CH3

O H3C

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CH3

Figure 1: Scheme of reaction between wood and isopropenyl acetate (IPA).

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MATERIALS AND METHODS

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The specimens of rubberwood (Hevea brasiliensis) measuring 20 x 20 x 10 mm3 were prepared

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from defect free wood. Specimens were extracted with a mixture of ethanol:acetone:toluene

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(1:1:4) for 6 h in a Soxhlet apparatus and then oven dried at 100-105°C and their weights were

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determined.

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Isopropenyl acetate (IPA) (99% AR Grade) was purchased from M/s Sigma Aldrich,

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Bengaluru, India. Iodine (I2) (AR Grade) was purchased from M/s SD Fine Chemicals,

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Bengaluru, India. Oven-dried specimens of rubberwood were reacted with IPA in a reaction

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vessel containing preheated IPA and a desired amount of I2. The concentration of I2 varied

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from 0.02 mol L-1 to 0.035 mol L-1. The reaction was carried out at 95 °C for different

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durations up to 10 h. Modified specimens were then soaked in cold acetone to stop the

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reaction and subsequently extracted with acetone:toluene (1:1) to remove un-reacted reagents

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and oven dried to determine weight percent gain (WPG). WPG of specimens was calculated

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using equation;

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WPG = [(Wm-Wo) / Wo] × 100

(1)

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where Wo and Wm are oven dried weight of unmodified and chemically modified wood

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samples, respectively.

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The volumetric swelling coefficient (S) and anti-swelling efficiency (ASE) were determined based on the water-soaking method (Rowell and Ellis 1978).

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S (%) = 100(V2-V1)/V1

(2)

where V2 is the volume of saturated sample and V1 is volume of oven dried sample. ASE (%) = 100(Su-Sm)/Su

(3)

where Su and Sm are volumetric swelling coefficients of unmodified and modified samples, respectively.

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The ATR-FTIR spectra were measured directly on the wood surfaces (Bruker

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Germany, Tensor-27 model FTIR Spectrometer; spectral resolution 4 cm-1; 64 scans). Solid

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state NMR spectra were obtained by a JEOL ESX 400 MHz, CP/MAS 13C NMR spectrometer

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at the NMR Research Center, Indian Institute of Science, Bengaluru.

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RESULTS AND DISCUSSIONS

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Reaction between IPA and wood in absence of any catalyst (I-0) is insignificant. Figure 2

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shows the effect of iodine concentration on weight percent gain (WPG) of modified wood.

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Figure 2: Plot of WPG versus reaction time for IPA modified rubber wood at 95oC. Catalyst (iodine) concentrations are: I-0 = 0 mol L-1; I-1 = 0.02 mol L-1; and I-2 = 0.035 mol L-1

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The average WPG increased with increasing reaction time. Samples up to weight gains of 17 %

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were obtained using to 0.035 mol L-1 (I-2) of iodine. This WPG value compares well with

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acetylation of wood using acetic anhydride and corresponds to the level of modification

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necessary for exhibiting good dimensional stability and durability (Rowell 1983, 2006, 2013).

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Figure 3: FTIR Spectra of unmodified (a) and modified (b) rubber wood.

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FTIR spectra of unmodified and modified rubberwood are shown in Figure 3. The

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FTIR spectra of unmodified wood shows strong O-H stretching absorption at 3347 cm-1 and

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several other well defined peaks due to various functional groups present in cellulose,

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hemicelluloses and lignin (Harrington et al. 1964, Faix 1992, Pandey 1999). A significant

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decrease in the O–H stretching band at 3347 cm-1 with a corresponding increase in the C=O

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stretching absorbance at 1740 cm-1 and C–O stretching at 1216 cm-1 indicates esterification of

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wood.

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Figure 4: NMR Spectra of unmodified (a) and modified (b) rubber wood.

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The modified wood was further characterized by

C CPMAS NMR (Figure 4). The

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occurrence of two strong signals at 22.7 and 176.1 ppm in modified wood confirms

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esterification of wood by IPA. The signal at 22.7 is characteristic of a methyl (-CH3) carbon of

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the acetyl group and a signal at 176.1 ppm arises due to carbonyl (-C=O) carbon of acetyl

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group of acetylated wood (Sun et al. 2004)

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Figure 5: Anti-swelling efficiency (ASE) versus WPG for IPA modified wood using iodine catalyst.

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volumetric swelling coefficient (S) and anti-shrink/anti-swell efficiency (ASE), using the

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repeated water-soaking method (Rowell and Ellis 1978). After modification, the volumetric

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swelling coefficient of modified wood was reduced significantly. The values of ASE after first

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water soaking cycle against weight gain are plotted in Figure 5. Modified wood exhibited a

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high ASE value which increases with increase in WPG values. Anti-Swelling Efficiency up to

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~ 60.0% was obtained corresponding to WPG values of ~17%. This indicates high

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dimensional stability of IPA modified wood.

The dimensional stability of modified wood was determined by estimating the

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Above results indicate that iodine is a good catalyst for chemical modification of

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wood using IPA. The modified wood has high dimensional stability. Modification with IPA

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may have advantages since there is no acid byproduct.

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CONCLUSIONS

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A process of acetylation of solid wood with IPA in presence of iodine has been reported. A high

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level of modification (~ 17% WPG) was achieved. The average WPG increased with increasing

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reaction time and catalyst concentration. Modified wood exhibited high dimensional stability.

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ACKNOWLEDGEMENT

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This research was supported by CSIR New Delhi (Grant No. 38(1357)/13/EMR (II)).

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REFERENCES

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Can, A.; Sivrikaya, H. 2016. Dimensional stabilization of wood treated with Tall oil

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dissolved in different solvents. Maderas. Ciencia y Tecnología 18(2):317-324. Faix, O. 1992. Fourier transform infrared spectroscopy. In: Methods in Lignin Chemistry. Eds. Lin, S.Y., Dence, C.W. Springer-Verlag, New York. pp. 83-109. Giridhar, B. N.; Pandey, K. K. 2016. UV resistance and dimensional stability of wood modified with isopropenyl acetate. J Photochem Photobiol B: Biology 155:20-27. Harrington, K. J.; Higgins, H. G.; Michell, A. J. 1964. Infrared spectra of Eucalypus regnans F. Muell. and Pinus radiata D. Don. Holzforschung 18:108-113. Hill CAS. 2006. Wood Modification: Chemical, Thermal and Other Processes. John Wiley and Sons, Ltd., Chichester Jebrane, M.; Sèbe, G.; Cullis, I.; Evans, P. D. 2009. Photostabilization of wood using aromatic vinyl esters. Polym Degrad Stabil 94:151-157. Lopes, D.B.; Mai, C.; Militz, H. 2014. Marine borers resistance of chemically modified Portuguese wood. Maderas. Ciencia y Tecnología 16(1):109-124. Lopes, D.B.; Mai, C.; Militz, H. 2015. Mechanical properties of chemically modified Portuguese pinewood. Maderas. Ciencia y Tecnología 17(1):179-194. Matsuda, H. 1996. Chemical modification of solid wood. In: Chemical Modification of

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Lignocellulosic Materials. Ed. Hon, D.N.S. Marcel Dekker, New York. pp. 159-183.

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Pandey, K. K. 1999. A study of chemical structure of softwood and hardwood and wood

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polymers by FTIR spectroscopy. J Appl Polym Sci 71:1969-1975. Rowell, R. M. 1983. Chemical modification of wood. Forest Products Abstracts 6:363-382.

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Rowell, R.M. 2006. Chemical modification of wood: A short review. Wood Mat Sci Eng

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1:29-33.

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Rowell, R. M. 2013. Chemical modification of wood. In: Handbook of Wood Chemistry and

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Wood Composites. Ed. Rowell, RM. Taylor and Francis, CRC press, Florida. pp. 537-

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598.

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Rowell, R. M.; Ellis, W. D. 1978. Determination of dimensional stabilization of wood using the water-soaked method. Wood Fiber Sci 10:104-111.

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Sun, X. F.; Sun, R. C.; Sun, J. X. 2004. Acetylation of sugarcane bagasse using NBS as a

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catalyst under mild reaction conditions for the production of oil sorption-active

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materials. Biores Techn 95:343-350.

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