FOODS AND BIOTECHNOLOGY VOL. 6, NO. 2, pp. 118121 (1997) Preparation of Hydroxypropylated Corn Starch at High Degrees of Substitution in Aqueous Alcohol, and Pasting Properties of the Starch Yu Jin Choi, Seung-Taik Lim* and Sung-Soon Im! Center for Advanced Food Science and Technology, Graduate School of Natural Resources, Korea University, Seoul 136-701, Korea "Department of Textile Engineering, Hanyang University, Seoul 133-791, Korea Abstract - Hydroxypropylated com starches at high degrees of sub- stitution were prepared in an aqueous ethanol (70%). Effects of various reaction conditions such as alkali content, propylene ox- ide content, temperature, and reaction time on the reaction Yield and the degree of molar substitution (MS) were compared. Pasting viscosity and light transmittance of the starch were also investigated. At 65°C, with 1.08% NaOH (based on starch dry weight) and 30% propylene oxide (based on starch dry weight) in starch sluny in 70% ethanol (1:3), reaction yield reached a- bout 50% (MS 0.4) by a 24-hour reaction, High amylose (70%) com starch gave @ slightly higher molar substitution and reac- tion yield than normal starch (259% amylose) under the same reaction conditions. Pasting temperature on a viscogram de- creased as the MS increased, whereas peak viscosity and light tuansmittance increased. Hydroxypropylated high amylose com starch was gelatinized below 95°C, but the paste viscosity was ‘much less than that of the normal corn starch of an equivalent degree of substitution Key words: hydroxypropylated com starch, pasting. properties, high amylose com starch Introduction When starch was hydroxypropylated, the hydrogen bonds between starch chains were inhibited and gela- tinization temperature was reduced. The amylose molec- ules lost some degree of the molecular association a- bility which resulted in an increased clarity of the starch paste and stability at low temperature, This ret- arded retrogradation of starch achieved by hydroxypro- pylation is well practiced in food and paper industries, where starch is used as an ingredient (1-4). Recently hy- droxypropylated starch is also used as a biodegradable plastic material (5). When starch was chemically modified at room tem- perature, aqueous dispersion of insoluble starch gran- ules was the common reaction medium for the re iness of recovery of the reacted starch with a relatively high yield of reaction. For a high degree of reaction yield, however, concentrated alkali or high reaction tem- perature is often required but not permitted in aqueous 18 dispersion because the starch granules are swollen or even gelatinized, Therefore, saturated salt solution or aqueous alcohol is used to prevent starch swelling or gelatinization at high alkali and clevated temperatures (1, 6). In this study, com starch was hydroxypropylated in aqueous alcohol medium to achieve relatively high de- gree of substitution under various reaction conditions. Normal com and high amylose com starches which diff- ered in amylose content were compared in the reactivity and pasting properties. Mate and Methods Materials Normal comm and high amylose com starches which contained approximately 25 and 70% amylose, respecti- vely, were donated by Samyang Genex (Seoul, Korea) and Crestar USA (Hammond, IN, USA), respectively. Propylene oxide was purchased from Sigma Chemical Company (St. Louis, MO, USA). Hydroxypropylation Starch (50 g, dry weight) was dispersed in 70% aque- ous ethanol solution (150 ml), and NaOH solution (4 or 6%) was slowly added to the dispersion. The alkalinity of the dispersion was varied by adding different amounts of the NaOH solution (3-25 ml) and the change in the reaction yield was compared. After the dispersion was mixed with propylene oxide (5-15 ml) and flushed with nitrogen, it was stirred at different temperatures. (45- 70°C) for 24 hours in a sealed container. The reaction was finished by adding 1N HCI until the pH of the mix- ture reached 5-6 measured with pH paper. The mixture was centrifuged at 1800%g for 10 min to remove the supematant. The precipitated starch was washed twice with 200 ml of 70% ethanol and then dried at 40°C overnight. Determination of degree of substitution ‘The percentage of hydroxypropyl groups in starch was measured according to the spectrometric procedure (7-9), and converted to degree of molar substitutionHydroxypropylated Corn Starch at High Degrees of Substitution (MS) by using the following equation. Reaction yield corresponding the MS was also calculated. Degree of Molar Substitution=(162 x hydroxypropyl%) (5800-58 x hydroxypropyl”) Reaction yield=(MS x starch weight (g) 100)(moles of added propylene oxide x 162) Paste viscosi Paste viscosity of the starch was measured by using Rapid Visco-Analyzer (New Port Scientific, Australia) (10). Starch dispersion (10% in water) was heated from 25°C to 95°C at a heating rate of 3.5°C/min, and then held at 95°C for 5 min Light transmittance of paste Starch dispersion (50 mg in 4.95 ml water) was heat ed in a sealed test tube with occasional stirring in a boil- ing water-bath for 30 min. The starch solution was cool- ed for 1 hour at room temperature, stirred shortly and then the light transmittance of the solution was measur- ed at 650 nm (11) Results and Discussion Effect of alkalinity When the starch dispersion in an alcohol solution (1 3) was reacted with 30% propylene oxide (v/w based on starch) at 45°C for 24 hrs, the increased amount of 4% NaOH solution from 3 to 25 ml resulted in a MS in- crease from 0.04 to 0.31 (Fig. 1). Especially with 21 ml ‘of the alkaline solution, the MS and reaction yield values were respectively 0.30 and 36%, which were sig- nificantly greater than the values measured with the ad- ition of 19 ml. With more than 21 ml of the NaOH solution, however, no significant increase in either MS ‘or reaction yield was achieved. When 6% NaOH solu- “0 ———— [ es gensce jes as} som 6NaOH | Eas we z i £m se x qn Za a = 4% f 410 os : ool ° nr ee) ‘Amount of NaOH Solution (i) Fig. 1. Effect of alkalinity on the reaction yield during the hydroxypropylation of corn starch (50 g) in 70% ethanol (150 mi) with propylene oxide (1S ml) for 24 hes at 45°C. 119 tion was used, up to 23 ml, the MS gradually increased from 0.08 to 0.36, but at 25 ml the MS was reduced to 0.34. The maximum reaction yield in the hydroxypro- pylation with 30% propylene oxide at 45°C for 24 hrs was 43% when 23 ml of 6% NaOH solution was added. When approximately 15 mi of both alkaline solutions was added, the reaction yield became slightly reduced (Fig. 1). This result was reproduced, Various attributes, might be considered for the reactivity change in this range. Catalytic activity and solubility of NaOH in the alcohol solution are some of the rate-determining vari- ables in the reaction. More experiments are needed for clear understandings, Effect of reaction temperature With 5-11 ml of the 6% NaOH solution, reaction tem- perature was varied from 45 to 70°C to examine the temperature effects. The temperature increase from 50 to 55°C decreased the reaction yield by 2-7%, and above 55°C the reaction yield increased at a relatively propor- tional rate (Fig. 2) with the temperature increase. With high amount of NaOH (9 or I1 ml), the reaction yield at 75°C was not significantly different from that at 70°C. At a high temperature with high alkalinity, the starch granules tend to swell and possibly increase the viscos- ity of the dispersion. The viscosity increase usually reduces the reactivity. According to Tuschoff, hy- droxypropylation in aqueous starch dispersion became significantly slow when the temperature was decreased below 55°C (1). The cause for the reduced reactivity at 50°C was not clearly understood. The volatile propylene ‘oxide might be less dissolved in the reaction medium at 50°C compared to at 45°C, and this difference in the Soluble concentration caused the reactivity. As shown in Fig. 1, 21 ml addition of 6% NaOH at 45°C resulted in 9 om aL wo) ta tm Dion “ Ba se & | 8 Eo. nf gn ag Z & jag ssh | ® fo 6 85 608870 Reaction Temperature (°C) Fig. 2. Effect of reaction temperature on the reaction yield during the hydroxypropylation with various contents of 6% NaOH solution. Cora starch (50 g) in 70% ethanol (150 ml) ‘was reacted with propylene oxide (1S ml) for 24 hrs.120 4 43% reaction yield. At 65°C, however, only a 9 ml ad- dition of 6% NaOH exhibited 2 50% reaction yield (Fig. 2), implying the importance of reaction temperature for the reactivity of hydroxypropylation Effect of propylene oxide concentration From the previous results, the starch dispersion con- taining 20 ml of 6% NaOH solution was reacted with various amounts of propylene oxide (10, 20 and 30% based on the starch weight) at 60°C. Both normal and high amylose com starches were compared in the reacti- vity and the reaction time was varied from 6 to 24 hours. Propylene oxide content increase resulted in the relat vely proportional increase of the degree of substitution (Fig. 3). The reaction yield, however, exhibited a slight decrease with the propylene oxide content (Table 1). By extending the reaction period from 6 to 24 hours, the reaction yield could be raised approximately twice. Al- Nomalcorte 4) 050 gn amyioes com (0.0 8) us| a Moar Substation gE g ost 040 | — Reaction Tne he) 3. Effect of propylene oxide content (10%, @ 0; 20%, 3 30%, AA, based on the dry weight of starch) and reaction time on’ the degree of molar substitution during the hydroxypropylation of corn starch with 20 ml of 6% NaOH solution (2.4% NaOH based on starch, w/w) at 60°C. aco RV) Tenperanse) Fig. 4. Pasting viscograms of the hydroxypro 1) was heated to 95 120 Yl. Choi et al though the MS values of the hydroxypropylated starches, could reach up to 0.5 by using a high concentration of the reagents, approximately half of the reagent became lost during the reaction under experimental conditions. For a practical process in industries, this loss might be too high, High amylose com starch has larger amorphous re- gions than normal com starch. The reactions in the gran- ular state of starch occurs mainly in the amorphous re- gions of starch granule where the reagents are highly ac~ cessible. In the hydroxypropylation in aleohol, the reac tion yield with high amylose com starch appeared slight- ly higher than that with normal com starch (Table 1). Paste viscosity Pasting temperature where the viscosity of starch paste started increasing on the viscogram was decreased whereas the peak viscosity was increased as the degree of substitution increased (Fig. 4). The peak temperature Table 1. Effect of propylene oxide content and reaction temperature on the reaction yield for the hydroxypropylation of normal and high amylose corn starches Reaction time and Reaction yield (%) ropylene | —_—_eeseton Yield ()_ oxide eoatent (%)'___Nowmal com High amylose corm 6 hours 10% 245 229 2096 269 v4 50st 282 208 12 hours 108 as 44s 20% 373 a8 30% 392 463 18 hours 108 528 soo 208% at 00 50% 381 S74 24 hours 10% 556 592 20% 60 573 30% 480 607 With 20 ml of 6% NaOH (24% NaOH based on starch) at onc. Tea anyon Tempera ated normal corn and high amylose corn starches. Starch dispersion (10% w/ Eat a heating rate of 3.5°C/min, and then held at 95°C for 5 min.Hydroxypropylated Corn Starch at High Degrees of Substitution [ Normal come m a) ro LH ampose cra(oo 4) Light Transmitance (4) Reaction Time (hr) Fig. 5. Paste light transmittance (1% in water) of the hy- droxypropylated normal and high amylose corn starches treated with various contents of propylene oxide (10%, © ©} 20%, m0; 30%, AA, based on the dry weight of starch) and reaction time. was also decreased with MS increase. At MS 0.38, the starch started forming paste at 41°C and the viscosity reached a maximum (approximately 300 RVU) at a tem- perature below 50°C. But the shear thinning became ‘more substantial than the native starch. Unmodified high amylose starch was not gelatinized at 95°C showing no viscosity increase. By hydroxypro- pylation above MS 0.12, the starch formed paste with viscosity increase. Pasting temperature gradually deci ased with the MS value, but the peak viscosity of the paste did not change significantly. Therefore high amylose com starch could be gelatinized in water under ordinary boiling conditions by an adequate level of hydroxypro- pylation. The hydroxypropyl substitutes. promoted the dissociation of the adjacent starch chains when the starch granules were gelatinized Light transmittance of the paste The light transmittance of the hydroxypropylated star- ches increased as the treated amount of the propylene oxide and the reaction period increased (Fig. 5). The starch chains became more hydrophilic and the col- Ioidal dispersion of the chain was expected to be more stable and homogeneous. Comparing the two types of com starch which diff- ered in the amylose content, high amylose corn starch showed more significant increases in the light transmit- tance values than normal com starch as the reaction lev- el was increased. By treatment with 10% propylene ox- ide, normal starch pastes appeared more transpareat than high amylose com starch pastes. But when 30% propylene oxide was reacted, high amylose com starch paste showed higher transmittance results than normal 12 starch. High amylose com starch was able to be gela- inized by the hydroxypropylation at temperatures. be- low 100°C resulting in the substantial difference in the paste clarity Conclusions Hydroxypropylation of normal and high amylose ‘com starches at high degrees of substitution (>0.1) could be carried out by reacting starch at elevated temperatures in 70% ethanol solution with the reaction yields up to 50-60%. Hydroxypropylated starches became readily soluble in warm water (40-S0°C) forming highly vis- ‘cous and clear pastes, Especially high amylose com starch became gelatinized at a temperature below 100°C with the modification, Acknowledgements ‘The authors thank the MOST for the research fund (Han's project), and Samyang Genex and Crestar USA for providing the starches, The journal paper number of CAFST 97014 of Korea University, Seoul, References 1. Tuschhoff, J.R: Hydroxypropylated starches. p. 89, In: ‘Starches: ‘Properties and Uses. Wurzburg. 0.B. (ed). 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