Effect of Reaction Time on Phosphation Process


CHAPTER 3. RESULTS AND DISCUSSION


3.1. Phosphating starch with sodium hydrogen phosphate


In this study (Eq. 17-26) starch was phosphated with sodium hydrogen phosphate, in which the influencing factors such as reaction time, temperature, pH, phosphate/starch ratio on the properties of starch phosphate were studied.

3.1.1. Effect of reaction time

To study the effect of reaction time, the phosphating process was carried out at 160 C with a molar ratio of salt/glucose of 1:1 for periods of 1h, 2h, 3h, 4h (hours). The results are shown in Table 3.1.

Table 3.1. Effect of reaction time on phosphatization process


Time (h)

P content (%)

Potential (DS)

Solubility (%)

1

1.34

0.073

27.1

2

1.53

0.084

36.5

3

1.80

0.10

52.0

4

1.92

0.107

46.3

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The results in Table 3.1 show that the amount of phosphate bound to starch increases with the extension of the reaction time, the solubility of starch phosphate also increases due to the increase in polarity. Extending the reaction time beyond h also increases the degree of phosphating but reduces the solubility of the product due to side reactions such as intramolecular and intermolecular etherification and network formation. Furthermore, after 3 hours the phosphating product tends to turn yellow-brown as a result of prolonged heat treatment and under dry heating conditions at room temperature.


high. Therefore, the reaction time h is considered the appropriate time for the synthesis of starch phosphate.

In this study, the use of vacuum drying increased the water retention capacity, increased the phosphatization capacity, and could reduce unwanted side reactions (such as oxidation reactions) and limit the moisture content in the reaction medium to avoid physical effects.

3.1.2. Effect of temperature

To study the effect of reaction temperature, the phosphatization process was carried out for 3 hours with a molar ratio of phosphate/glucose of 1:1 at temperatures of 150, 160, 170, 180 C, respectively. The results are shown in Table 3.2.

Table 3. Effect of temperature on the phosphatization process


Reaction temperature ( o C)

Content

phosphorus (%)

Degree of power

(DS)

Solubility (%)

150

1,314

0.072

43.6

160

1.53

0.084

52.0

170

1,619

0.089

47.5

180

1,896

0.106

42.9


The results in Table 3.2 show that the phosphorus content increases with increasing reaction temperature. The effect of reaction temperature is similar to that of time. Higher reaction temperatures can facilitate the breaking of intramolecular hydrogen bonds between starch chains, allowing the reactant molecules to approach the active hydroxy groups. However, increasing the temperature beyond a certain limit also promotes side reactions as described above, reducing the solubility of the product. In addition, phosphatized starch above 170 C tends to turn yellow-brown. The results show that the


The solubility of phosphatized starch at 160 C is higher than that of phosphatized starch at 150 C, 170 C, 180 C. Therefore, the suitable temperature for synthesizing phosphatized starch is 160 C.

3.1.3. Effect of pH

To study the effect of pH, the phosphatization process was carried out for 3 h with a phosphate/glucose ratio of 1:1 at 160 C, with pH ranging from 4 to 9. The results are shown in Table 3.3.

Table 3.3. Effect of pH on phosphatization process


pH

Phosphorus content (%)

Potential (DS)

4

0.861

0.044

5

1,487

0.082

6

1.53

0.084

7

1,239

0.067

8

1,137

0.062

9

0.974

0.053


The results in Table 3.3 show that the phosphatization process occurs best at pH 5 - 6 but is reduced in acidic (pH 4) and alkaline (pH = 8 - 9) environments. Starch binds best with phosphate at pH 6. In low pH environments, starch can be hydrolyzed, broken down, reducing molecular weight, while high pH affects the strength of the ester bonds formed between phosphate groups and starch molecules. High pH also causes starch degradation, making the product brittle.

3.1.4. Effect of molar ratio of phosphate/glucose

To study the effect of molar ratio of phosphate/glucose on the phosphatization process, the reaction was carried out for 3 hours with molar ratios of phosphate/glucose from 0.5-3.5, temperature of 160 C and pH 6. The results are shown in Table 3.4.


Table 3.4. Effect of molar ratio of phosphate/glucose on phosphatization process


Molar ratio

phosphate/glucose

Phosphorus content (%)


Potential (DS)


Solubility (%)

0.5

1.31

0.072

31.4

1.0

1.53

0.084

36.5

1.5

1.68

0.093

41.7

2.0

1.84

0.102

48.3

2.5

2.16

0.122

51.6

3.0

2.37

0.134

46.1

3.5

2,408

0.137

38.9


The results in Table 3.4 show that the degree of substitution increases with increasing molar ratio of phosphate/glucose. This is because the hydroxyl groups of starch are less mobile and their reactivity depends on the reactant with which they are reacted. Therefore, the higher the concentration of the reactant, the more reactant molecules are available in the vicinity of the hydroxyl groups of starch, thus increasing the possibility of phosphatization. The solubility of the product also increases with increasing molar ratio of phosphate/glucose. However, when this ratio is too high, it also increases the network formation process, reducing the solubility. The results also showed that highly substituted starch phosphate monoester was synthesized by using high phosphate salt concentration, high reaction temperature, long reaction time and pH 5 - 6. In general, it can be concluded that the best reaction conditions were: reaction time of 3h, reaction temperature of 160 C, molar ratio of phosphate/glucose of 2.5/1 and pH 6.

3.1.5. Effect of substitution on properties of starch phosphate monoester

* Ash content


Ashing at high temperatures can sublimate small molecules such as


NaCl. In this experiment, the ashing process was carried out at 525 C, at which temperature NaCl does not sublimate. The results are shown in Fig. 1.


Figure 3.1. Effect of molar ratio of phosphate/glucose on ash content.


The results showed that the ash content increased with increasing phosphate group content. This is because the ash content is closely related to the phosphate groups on starch in the esterification reaction.

* Solubility


The room temperature solubility of starch phosphate synthesized with different phosphate/glucose molar ratios is shown in Fig. 2.

The room temperature solubility of native starch is almost zero due to the strong bonding force between starch molecules, while phosphatized starch with increased substituents gives a relatively high room temperature solubility value. The increased solubility may be due to the repulsion between negatively charged phosphate groups in starch molecules, which reduces the intramolecular bonding force.




Figure 3. Effect of molar ratio of phosphate/glucose on starch solubility.


Too high a substituent decreases solubility possibly due to the formation of cross-links in the starch chain. This is especially the case with amylose or amylopectin present in starch which increases the cross-linking process.

* Swelling


The change in starch swelling ability at different potentials is shown in the figure. .



Figure 3.3. Effect of substituent on the swelling ability of starch


The results showed that native starch does not have the ability to swell at room temperature due to the bonding force between starch molecules. Meanwhile, phosphate starch swells in water at any potential. These results are consistent with the studies of some authors who stated that phosphate starch granules begin to swell at a potential of about 0.07. Furthermore, phosphated starch with the lowest potential gives the highest swelling degree and the swelling degree decreases with increasing potential. This is the result of the mutual repulsion between phosphate groups on starch molecules and between starch granules. Too high a potential can weaken the effect of H-bonds between molecules, reducing the swelling ability.

Swelling ability is affected by the chemical bonds between starch granules and non-hydrocarbon compounds such as lipids and phosphates. High amylose content increases intramolecular bonds leading to a decrease in swelling ability. In addition, the swelling ability of starch is also affected by phosphate ions in the ester group (leading to repulsive forces between charges). There is a close relationship between swelling ability and solubility. Some authors believe that the swelling and dissolution of starch granules during gelatinization is due to the loss of double-helical structure rather than the loss of crystallinity. The binding forces in starch granules affect its swelling ability, so highly aggregated starch granules with tightly bound structures have relatively low solubility and swelling ability. The introduction of phosphate groups into starch can reduce the strong bonds of the lamellar structure thereby increasing both solubility and swelling ability.

* Viscosity


The viscosity of starch phosphate paste at different potential values ​​was determined using a Brookfield rotational viscometer. The results are shown in Fig. 4.

The lowest phosphated starch paste gives the highest viscosity. Starch viscosity is influenced by various factors including molecular weight, amylopectin:amylose ratio and degree of branching. Studies have shown that at low concentrations of about 10g starch/400ml water, the viscosity of the paste is


Native starch has almost zero viscosity while low potential phosphated starch gives high viscosity.



Figure 3.4. Effect of molar ratio of phosphate/glucose on starch viscosity.


Furthermore, the viscosity of phosphated starch is inversely proportional to temperature, which is completely opposite to that of native starch. This means that the stability of starch paste is enhanced by the phosphate group. Therefore, phosphated starch opens up the possibility of use in food products used at low temperatures.

The viscosity of starch phosphate paste decreases with increasing substituent because increasing substituent weakens the structure between the granules. In addition, adding phosphate groups to starch also reduces the number of hydrogen bonds on the starch molecule. However, when the molar ratio of phosphate/glucose is too high, it increases the reticular reaction, thus increasing the viscosity.

* Freeze-thaw resistance


The freeze-thaw stability of starch phosphate at different molar ratios of phosphate/glucose is given in Table 3.5.

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