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Preparation of glycolether lignin from Sugi (Cryptomeria japonica D. Don) woodmeal by acid-catalyzed solvolysis in 2-phenoxyethanol has been performed. The glycolether lignin had the hydroxyl content of 0.677 mmol/g and average molecular weight of 2.5×103. The glycolether lignin showed good solubility to various common organic solvents, such as methanol, ethanol, acetone, 2-butanone and chloroform. Crosslinked glycolether lignin, obtained by esterification with adipoyl chloride in acetone, showed thermal stability up to 230 °C. Key-words: Glycolether lignin, Acid-catalyzed solvolysis, Polyesters Note J. Jpn. Soc. Colour Mater., 92〔8〕,220–224(2019) 220 © 2019 Journal of the Japan Society of Colour Material -8solvents, and moderate affinity to cellulosic polysaccharides and lignins. On the other hand, hydroxy groups of these solvents are not dissociative enough to cause solvolysis of lignins solely by the solvents themselves. Therefore, catalytic amounts of inorganic acids, such as sulfuric acid, or organic sulfonic acids are required for the preparation. In the present paper, we have investigated the solubilized state of lignin condensates in 2-PhEtOH or EGMBE (referred to as glycolether lignins in the following sections) prepared by using catalytic amount of dodecylbenzene sulfonic acid. Furthermore, we have prepared aromatic polyesters from the lignin condensates by esterification with various dicarboxylic acid chlorides. We also report the thermal properties of the glycolether lignin polyesters. 2.Materials and methods 2.1 Preparation of Glycolether Lignin Condensate In a 300-mL double-necked flask equipped with thermometer and condenser placed on magnetic stirrer, 10 g of 65 mesh-passed wood meal of Sugi (Cryptomeria japonica D. Don), 10 g of 2-PhEtOH, 85 g of EGMBE, and 0.663 g (2 mmol) of dodecylbenzenesulfonic acid were mixed at 160 °C for 2 h. After cooled to the ambient temperature, the solvolysis product was collected by suction filtration by using No.2 filter paper. Solid reside on the Buffner funnel was washed with diethyleneglycol monoethyl ether (DEGMEE) and 2-butanone (100 ml each). The filtrate of reaction mixture, mixed with the wash liquid, was condensed at 120 °C for 3 h to obtain 47 g of the glycolether lignin condensate. 2.2 Characterization of Glycolether Lignin Glycolether lignin was firstly assessed for the solubility in various common organic solvents. Based on the results of solubility test, characterization of glycolether lignin in the solvated state was performed by the following methods: FTIR analysis, liquid film method on KBr with the resolution of 4 cm-1 by using Horiba FT-720 spectrometer (Horiba Corporation, Kyoto, Japan); molecular weight distribution by gel permeation chromatography by using HLC-8020 chromatograph (Tosoh Corporation, Tokyo, Japan) equipped with refractive index detector and GMHHR-M column (7.8 mm i.d.×300 mm) calibrated by polystyrene standards, to which chloroform was eluted with the flow rate of 0.8 ml/min; 1H NMR analysis (Avance DPX400, Bruker Biospin, Billerica, MA, USA, solvent: CDCl3). 2.3 Fractionation of glycolether lignin condensate Glycolether lignin condensate (47 g) was mixed with 200 ml of 1-butanol / hexane = 1/1 (v/v) and kept at 4 °C overnight. Supernatant and precipitate were separated by centrifugation (9,800×g, 4 °C, for 5 min). Supernatant was vacuum-condensed by rotary evaporator. Precipitate was washed with 1-butanol and vacuum-dried. Yield of the supernatant and precipitate was 43.5 g and 2.6 g, respectively. 2.4 Esterification of Glycolether lignin with diacid chlorides To 0.2 g of Glycolether lignin condensate dissolved in 0.3 ml of acetone, dicarboxylic acid chlorides with the corresponding molarity to hydroxy groups in glycolether lignin condensate (0.15 g of adipoyl chloride, 0.28 g of sebacoyl chloride, or 0.15 g of terephthaloyl chloride) and the corresponding amount of triethylamine were added and mixed at 4 °C. Esterification product, precipitate in acetone, was washed by acetone, methanol, and distilled water. Afterwards, the esterification product was centrifuged (9,800×g, 4 °C, for 5 min). After the supernatant was decanted, precipitated esterification product was vacuum dried at 50 °C for 1 day. Yield of the product was 0.124 g (62.2%). Characterization of the esterification product was performed by FT-IR (Horiba FT-720), observation of phase transition behaviour by hotstage-equipped optical microscopy (Nikon ECLIPSE 50i POL polarized optical microscope, Nikon Corporation, Tokyo, Japan), equipped with Linkam 10013L hotstage (Linkam Scientific Instruments, Tadworth, UK), heating rate of 10 K/min, and thermal degradability by differential scanning calorimetry (DSC, DSC-8230, Rigaku Corporation, Tokyo, Japan). 3.Results and discussion 3.1 Properties of Glycolether Lignin Condensate The obtained glycolether lignin condensate had an appearance of dark-brownish tar-like liquid. Glycolether lignin condensate was fully soluble in methanol, ethanol, acetone, 2-butanone and chloroform, partially soluble in ethyl acetate, but insoluble in hexane toluene, 1-butanol, and 2-propanol. Hydroxyl content of glycolether lignin condensate, estimated by titration of released acetic acid after acetylation, was 38 mg/g (0.677 mmol OH/g). 3.2 Molecular weight Distribution of Glycolether Lignin Condensate and Its Fractions Fig. 1 shows elution profiles of glycolether lignin condensate and its fractions. Each elution profiles are mainly composed of two regions. While the region 1 contains broad elution peak, the region 2 contains sharp peaks with positive or negative polarities. The broad peak in the region 1 originates from the polymeric components in the condensate. The negative peaks in the region 2 (the components with relatively smaller refractive indices than chloroform) are attributed to solvent species in the reaction medium. Therefore, the regions 1 and 2 are mainly composed of glycolether lignin and residual solvents, respectively. While condensate and soluble fraction are mainly composed of the 221 Preparation of Glycolether Lignin from Sugi (Cryptomeria japonica D. Don) Woodmeal by Acid-Catalyzed Solvolysis and Preparation of Heat-Resistant Polyester from the Glycolether Lignin

shikizai kyōkaishi/shikizai kyokaishi

Preparation of Glycolether Lignin from &lt;i&gt;Sugi&lt;/i&gt; (&lt;i&gt;Cryptomeria japonica&lt;/i&gt; D. Don) Woodmeal by Acid-Catalyzed Solvolysis and Preparation of Heat-Resistant Polyester from the Glycolether Lignin