CN111234041A - Acidolysis-crosslinking-sulfonation composite modified starch slurry and preparation method thereof - Google Patents
Acidolysis-crosslinking-sulfonation composite modified starch slurry and preparation method thereof Download PDFInfo
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Abstract
The invention discloses acidolysis-crosslinking-sulfonation compound modified starch slurry and a preparation method thereof. The method eliminates the defects of poor viscosity thermal stability, insufficient adhesive property, brittle and hard starch film and the like of starch by carrying out acidolysis-crosslinking-sulfonation composite modification treatment on the starch, so that the prepared acidolysis-crosslinking-sulfonation composite modified starch slurry has the properties of high viscosity thermal stability, strong adhesive property to fibers and good mechanical property of the starch film.
Description
Technical Field
The invention relates to the technical field of modified starch slurry, in particular to acidolysis-crosslinking-sulfonation composite modified starch slurry and a preparation method thereof.
Background
In the yarn for textile fabrics, except for strong twisted yarns, folded yarns and textured yarns with higher network degree, most of staple fibers and filaments need to be sized before weaving. The reason is that in the warp sizing process, the slurry coating the surface of the warp can increase the bonding fastness between the slurry film and the yarn body through the bonding effect, and improve the wear resistance of the warp; the serous membrane formed by the serous fluid can effectively resist the friction mechanical action of each part on the warp yarns, thereby playing the role of protecting the warp yarns; in the process of forming the serous membrane, the serous fluid has the function of attaching to the filoplume, and the filoplume on the surface of the warp is reduced. The slurry permeating into the warp forms an adsorption layer through wetting, spreading and adsorption, so that a colloid body is formed between fibers, mutual bonding between the fibers is realized, mutual slippage between the fibers is prevented, the strength of the warp is increased, and the purposes of reducing the weaving breakage rate, improving the production efficiency and improving the product quality are achieved.
Currently, the slurries used on the market are mainly starches, polyvinyl alcohol (PVA) and polyacrylic acids. In the field of textile warp sizing, the starch size is used as the main size of warp sizing, the dosage is large, the consumption of the starch size accounts for more than 70% of the total consumption of the size, and the starch size has the advantages of wide source, low price, easy biodegradation and the like.
However, the starch size has the defects of poor viscosity and thermal stability, poor adhesion performance, brittle and hard formed size film and the like, so that the warp sizing application effect is not satisfactory, and the starch cannot be used alone on high count yarns and is usually mixed with PVA for use. However, since PVA has extremely poor biodegradability and is not favorable for environmental protection, it has been classified as "dirty slurry" and prohibited in some countries in the European and American countries. In recent years, PVA (polyvinyl alcohol) is not used or is rarely used, so that the development of environment-friendly high-performance size to replace PVA is a development trend in the future.
Disclosure of Invention
In view of the above, the invention aims to provide an acidolysis-crosslinking-sulfonation composite modified starch slurry and a preparation method thereof, wherein a starch modification mode is developed and designed, so that the preparation technology of the modified starch slurry not only comprises environment-friendly crosslinking modification, but also has good viscosity thermal stability, adhesion performance and slurry membrane mechanical property.
The invention provides an acidolysis-crosslinking-sulfonation composite modified starch slurry, wherein the crosslinking of the composite modified starch slurry occurs between hydroxyl groups of anhydroglucose residues in starch molecules, and a sulfonated sulfonate functional group is introduced to a double bond in an itaconic acid functional group, and the composite modified starch slurry comprises the following molecular formula:
a method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry comprises the following steps:
acid hydrolysis: preparing starch into starch milk, heating to 30-50 ℃, adding a hydrochloric acid solution, stirring for reaction for 1-6 hours, neutralizing with a sodium carbonate solution until the pH is 6.5-7, performing suction filtration, washing with distilled water, and drying in an oven to obtain acidolysis starch;
and (3) crosslinking: preparing acidolysis starch, itaconic acid and distilled water into starch milk, stirring for reaction for 25-60 min, carrying out vacuum filtration, carrying out stepped heating drying on a filter cake, dispersing the dried product into an ethanol solution, neutralizing with a sodium hydroxide solution, carrying out suction filtration, washing, and drying to obtain acidolysis-crosslinked starch;
sulfonation: mixing the acidolysis-crosslinking starch and the sulfonation liquid into emulsion, stirring and reacting for 3-6 hours at the temperature of 30-45 ℃, neutralizing the pH value to 6.5-7 by using a sodium carbonate solution, carrying out suction filtration, washing, drying, crushing and sieving to obtain acidolysis-crosslinking-sulfonation composite modified starch slurry.
Optionally, in the acidolysis, the concentration of the starch milk is 20-40%, the concentration of the hydrochloric acid is 0.5-2.0 mol/L, and the mass fraction of the sodium carbonate solution is 2-8%.
Optionally, in the crosslinking, the concentration of the starch milk is 15-40%, the mass fraction of the sodium hydroxide solution is 0.5-2%, and the dosage of the itaconic acid is 2.16-8.64% of the mass of the starch.
Optionally, in the sulfonation, the concentration of the emulsion is 25-40%, and the mass fraction of the sodium carbonate solution is 2-8%.
Optionally, the step-type heating and drying includes the following steps: pre-drying the filter cake at 30-60 ℃ for 1.5-3.5 h, raising the temperature to 65-85 ℃, drying for 2-5h, and finally drying at 120-140 ℃ for 2-4 h.
Optionally, the sulfonation liquid is a mixed liquid of sodium bisulfite and anhydrous sodium sulfate.
Optionally, the amount of the sodium bisulfite is 10.8-43.2% of the mass of the starch.
Optionally, the amount of the anhydrous sodium sulfate is 6-15% of the mass of the starch.
Optionally, the starch is one of potato starch, corn starch, sweet potato starch, wheat starch and tapioca starch.
From the above, according to the acidolysis-crosslinking-sulfonation composite modified starch slurry and the preparation method thereof provided by the invention, the starch is subjected to acidolysis slurry adhesion treatment to improve the fluidity of the starch, then the acidolysis starch is subjected to crosslinking modification treatment by using itaconic acid as a crosslinking agent to prepare acidolysis-crosslinking starch slurry, and then the acidolysis-crosslinking starch slurry is subjected to sulfonation modification treatment by using sodium bisulfite to introduce sulfonate functional groups onto starch molecular chains, so that the acidolysis-crosslinking-sulfonation composite modified starch slurry is prepared. The method eliminates the defects of poor viscosity thermal stability, insufficient adhesive property, brittle and hard starch film and the like of starch by carrying out acidolysis-crosslinking-sulfonation composite modification treatment on the starch, so that the prepared acidolysis-crosslinking-sulfonation composite modified starch slurry has the properties of high viscosity thermal stability, strong adhesive property to fibers and good mechanical property of the starch film.
The use of the environment-friendly itaconic acid cross-linking agent avoids the harm of the used formaldehyde cross-linking agent to the environment and the human health, and meets the requirement of green and environment-friendly development of the current slurry industry. The prepared acidolysis-crosslinking-sulfonation composite modified starch size is suitable for sizing textile warp yarns, is not only suitable for a common sizing machine, but also suitable for a high-speed sizing machine. In addition, the molecular chain of the prepared composite modified starch size contains hydrophobic ester groups and hydrophilic sulfonate functional groups, so that the composite modified starch size has a wider warp variety application range, and is suitable for hydrophilic and hydrophobic warp varieties and blended warp varieties of the hydrophilic and hydrophobic warp varieties.
Drawings
FIG. 1 is a scanning electron microscope image of starch (a) and acidolysis-crosslinking-sulfonation composite modified starch slurry (b) according to an example of the present invention;
FIG. 2 is a scanning electron microscope image of a film cross section of starch (a) and acidolysis-crosslinking-sulfonation composite modified starch slurry (b) in example of the present invention;
FIG. 3 is a surface tension trend chart of acidolysis-crosslinking-sulfonation composite modified starch slurry;
FIG. 4 is a graph showing the tendency of acid hydrolysis-crosslinking-sulfonation composite modified starch size membrane to resist flexural fatigue.
Detailed Description
In the following description of the embodiments, the detailed description of the present invention, such as the manufacturing processes and the operation and use methods, will be further described in detail to help those skilled in the art to more fully, accurately and deeply understand the inventive concept and technical solutions of the present invention.
In the weaving process, the warp yarns are subjected to the friction action among the warp yarns and between the warp yarns and mechanical parts such as heddle eyes, shuttle boards, weft insertion devices and the like, and are subjected to repeated stretching, bending and impacting actions of thousands of times of movement of each mechanism. The unsized warp has a large amount of hairiness on the surface, and the warp is intertwined with each other under the various actions during weaving, so that the opening is unclear and the weaving cannot be smooth; in addition, the cohesive force among the yarn-forming fibers is low, so that the sliver is fluffy, the strength is low, and the fibers are pulled out of the sliver under the various actions during weaving, so that the structure of the sliver is damaged, the ends of the warp are broken, the efficiency of the weaving machine is influenced, the weaving cannot be smoothly carried out, and the weavability of the warp is influenced. With the rapid development of economy, petroleum resources are increasingly in shortage, the price of petroleum rises, and a series of environmental pollution problems are brought about by using petroleum products as raw materials to synthesize polymer materials (such as polyvinyl alcohol), so that the research, development and utilization of low-price, natural, renewable and degradable polymer materials are increasingly paid attention by people. In addition, with the development of national economy and the improvement of the living standard of people, the requirements of people on the quality of clothes are higher and higher, the use proportion of high-count high-performance yarns is higher and higher, and the requirements on the quality and performance of textile size are higher.
The fluctuation range of the sizing rate of the warp is an important quality index which must be controlled during the production of sizing, and the fluctuation range has great influence on the use effect of sizing agent or the weaving end breakage rate. In order to minimize the fluctuation range of the warp sizing rate, it is necessary to ensure that the hot size viscosity of the size is relatively stable. In order to overcome the above defects, the current technology mainly uses a cross-linking agent to moderately cross-link starch. The Chinese patent with the patent application number of 03113350.9 discloses a preparation method of modified starch slurry with high adhesive force and good stability, which comprises the steps of firstly carrying out cross-linking modification treatment on starch by adopting formaldehyde as a cross-linking agent, and then carrying out etherification modification treatment on the starch to overcome side effects generated by cross-linking modification, effectively recovering the adhesive property of the starch slurry, and further improving the stability of the slurry. However, the crosslinking agent used for crosslinking in the patent is formaldehyde. Formaldehyde is a substance which can cause cancer, and the formaldehyde has high hazard when being used in large quantities. The use of safe cross-linking agents is therefore an important option for solving this problem.
In order to solve the defects of poor viscosity and thermal stability, poor adhesion performance, brittle and hard formed starch film and the like of a warp sizing material starch slurry in the prior art, the invention provides acidolysis-crosslinking-sulfonation composite modified starch slurry, wherein the crosslinking of the composite modified starch slurry occurs among hydroxyl groups of anhydroglucose residues in starch molecules, and a sulfonated sulfonate functional group is introduced to a double bond in an itaconic acid functional group, and the composite modified starch slurry comprises the following molecular formula:
the starch is subjected to acidolysis slurry adhesion treatment to improve the fluidity of the starch, then the acidolysis starch is subjected to cross-linking modification treatment by using itaconic acid as a cross-linking agent to prepare acidolysis-cross-linked starch slurry, and then the acidolysis-cross-linked starch slurry is subjected to sulfonation modification treatment by using sodium bisulfite, and sulfonate functional groups are introduced to starch molecular chains, so that the acidolysis-cross-linking-sulfonation composite modified starch slurry is prepared. The method eliminates the defects of poor viscosity thermal stability, insufficient adhesive property, brittle and hard starch film and the like of starch by carrying out acidolysis-crosslinking-sulfonation composite modification treatment on the starch, so that the prepared acidolysis-crosslinking-sulfonation composite modified starch slurry has the properties of high viscosity thermal stability, strong adhesive property to fibers and good mechanical property of the starch film.
Simultaneously provides a preparation method of the acidolysis-crosslinking-sulfonation composite modified starch slurry, which comprises the following steps:
acid hydrolysis: preparing starch into starch milk, heating to 30-50 ℃, adding a hydrochloric acid solution, stirring for reaction for 1-6 hours, neutralizing with a sodium carbonate solution until the pH is 6.5-7, performing suction filtration, washing with distilled water, and drying in an oven to obtain acidolysis starch;
and (3) crosslinking: preparing acidolysis starch, itaconic acid and distilled water into starch milk, stirring for reaction for 25-60 min, carrying out vacuum filtration, carrying out stepped heating drying on a filter cake, dispersing the dried product into an ethanol solution, neutralizing with a sodium hydroxide solution, carrying out suction filtration, washing, and drying to obtain acidolysis-crosslinked starch;
sulfonation: mixing the acidolysis-crosslinking starch and the sulfonation liquid into emulsion, stirring and reacting for 3-6 hours at the temperature of 30-45 ℃, neutralizing the pH value to 6.5-7 by using a sodium carbonate solution, carrying out suction filtration, washing, drying, crushing and sieving to obtain acidolysis-crosslinking-sulfonation composite modified starch slurry.
The use of the environment-friendly itaconic acid cross-linking agent avoids the harm of the used formaldehyde cross-linking agent to the environment and the human health, and meets the requirement of green and environment-friendly development of the current slurry industry. The prepared acidolysis-crosslinking-sulfonation composite modified starch size is suitable for sizing textile warp yarns, is not only suitable for a common sizing machine, but also suitable for a high-speed sizing machine. In addition, the molecular chain of the prepared composite modified starch size contains hydrophobic ester groups and hydrophilic sulfonate functional groups, so that the composite modified starch size has a wider warp variety application range, and is suitable for hydrophilic and hydrophobic warp varieties and blended warp varieties of the hydrophilic and hydrophobic warp varieties.
In order to improve the property of the composite modified starch slurry, during acidolysis, the concentration of starch milk is 20-40%, the concentration of hydrochloric acid is 0.5-2.0 mol/L, and the mass fraction of a sodium carbonate solution is 2-8%; in the crosslinking, the concentration of the starch milk is 15-40%, the mass fraction of the sodium hydroxide solution is 0.5-2%, and the consumption of the itaconic acid is 2.16-8.64% of the mass of the starch; in sulfonation, the concentration of the emulsion is 25-40%, and the mass fraction of the sodium carbonate solution is 2-8%;
the step-type temperature rise drying comprises the following steps: pre-drying the filter cake at 30-60 ℃ for 1.5-3.5 h, raising the temperature to 65-85 ℃, drying for 2-5h, and finally drying at 120-140 ℃ for 2-4 h.
The sulfonation liquid is a mixed liquid of sodium bisulfite and anhydrous sodium sulfate; the using amount of the sodium bisulfite is 10.8-43.2% of the mass of the starch; the using amount of the anhydrous sodium sulfate is 6-15% of the mass of the starch; the starch is one of potato starch, corn starch, sweet potato starch, wheat starch and tapioca starch.
Specifically, for example, the preparation method of the acidolysis-crosslinking-sulfonation composite modified starch slurry provided in embodiment 1 of the present invention includes the following steps:
acid hydrolysis: 800g of corn starch was weighed out in dry weight, and prepared into a starch emulsion with a mass fraction of 40% with distilled water, and transferred to a 2000mL four-necked flask equipped with a thermometer and a stirring device. After the temperature is raised to 50 ℃, 27mL of 2mol/L hydrochloric acid solution is added dropwise, and the reaction is carried out for 4.5h under constant stirring. Neutralizing with 6% by mass of sodium carbonate solution until the pH value is 6.5-7, performing suction filtration, washing with distilled water for 4 times, and drying in an oven at 50 ℃ to obtain the acid hydrolyzed starch. The reaction equation is as follows:
and (3) crosslinking: adding 7g of itaconic acid and distilled water into 324g of acid hydrolyzed starch to prepare starch milk with the mass fraction of 40%. Stirring for 30min, performing suction filtration once on a vacuum pump, pre-drying the filter cake in a 50 ℃ oven for 2h, raising the temperature of the oven to 75 ℃, drying for 4h, and finally raising the temperature of the oven to 130 ℃ and drying for 2.5 h. And then dispersing the dried substance into an ethanol/water solution (volume ratio of 1:1), neutralizing with a sodium hydroxide solution with the mass fraction of 2% until the pH value is 6.5-7, performing suction filtration, fully washing with the ethanol/water solution (volume ratio of 1:1) for 4 times, and drying in an oven at 40 ℃ to obtain the acidolysis-crosslinked starch. The reaction equation is as follows:
sulfonation: an acid hydrolysis-crosslinked starch (162 g in dry weight) was dispersed in distilled water containing 17.5g of sodium hydrogen sulfite and 16.2g of anhydrous sodium sulfate to prepare a mixed emulsion having a mass fraction of 35%. Stirring and reacting for 5 hours at 40 ℃, neutralizing the pH value to 6.5-7 by using a 6% sodium carbonate solution, carrying out suction filtration, fully washing the ethanol/water solution (volume ratio is 1:1) for 4 times, drying in an oven at 40 ℃, crushing, and sieving by using a 100-mesh sieve to obtain the acidolysis-crosslinking-sulfonation composite modified starch slurry. The reaction equation is as follows:
the prepared acidolysis-crosslinking-sulfonation composite modified starch slurry has the crosslinking degree of 82.3(AGU/CL) and the sulfonation degree of 0.012.
Specifically, for example, the preparation method of the acidolysis-crosslinking-sulfonation composite modified starch slurry provided in embodiment 2 of the present invention is the same as that of embodiment 1, except that the mass of the added itaconic acid is 14g, and the mass of the sodium bisulfite is 35 g. The prepared acidolysis-crosslinking-sulfonation composite modified starch slurry has the crosslinking degree of 49.4(AGU/CL) and the sulfonation degree of 0.019.
Specifically, for example, the preparation method of the acidolysis-crosslinking-sulfonation composite modified starch slurry provided in embodiment 3 of the present invention is the same as that in embodiment 1, except that the mass of the added itaconic acid is 21g, and the mass of the sodium bisulfite is 52.5 g. The prepared acidolysis-crosslinking-sulfonation composite modified starch slurry has the crosslinking degree of 26.0(AGU/CL) and the sulfonation degree of 0.037.
Specifically, for example, the preparation method of the acidolysis-crosslinking-sulfonation composite modified starch slurry provided in embodiment 4 of the present invention is the same as that in embodiment 1, except that the mass of the added itaconic acid and sodium bisulfite is different, the mass of the itaconic acid is 28g, and the mass of the sodium bisulfite is 70 g. The crosslinking degree of the prepared acidolysis-crosslinking-sulfonation composite modified starch slurry is 19.8(AGU/CL), and the sulfonation degree is 0.048.
The slurry viscosity thermal stability, adhesion to cotton fibers and mechanical properties of the slurry of the example samples and starch (control) are shown in tables 1 and 2.
TABLE 1 slurry viscosity thermal stability, adhesion to cotton and polyester fibers for starch slurry
As can be seen from the above table, compared with the comparative sample, the acidolysis-crosslinking-sulfonation composite modified starch slurry prepared by the embodiment of the invention has obviously improved viscosity thermal stability and adhesion to cotton and polyester fibers.
TABLE 2 starch slurry mechanical Properties
| Starch | Degree of crosslinking (AGU/CL) | Degree of sulfonation, DSs | Breaking Strength (MPa) | Elongation at Break (%) |
| Control sample | 0 | 0 | 37.4 | 2.83 |
| Example 1 | 82.3 | 0.012 | 36.6 | 3.58 |
| Example 2 | 49.4 | 0.019 | 34.7 | 3.82 |
| Example 3 | 26.0 | 0.037 | 32.8 | 3.96 |
| Example 4 | 19.8 | 0.048 | 29.9 | 4.28 |
As can be seen from the above table, compared with the comparative sample, the acid hydrolysis-crosslinking-sulfonation composite modified starch size film prepared by the embodiment of the invention has the advantages that the elongation at break is obviously increased, and the breaking strength is reduced, which shows that the acid hydrolysis-crosslinking-sulfonation composite modification can improve the mechanical property of the starch size film, and plays a role in reducing the brittleness and improving the toughness of the starch size film.
From the stretched cross-sections of the starch film and the acidolysis-crosslinking-sulfonation composite modified starch film in fig. 2, it was verified that the acidolysis-crosslinking-sulfonation composite modification reduced the brittleness of the starch film. FIG. 3 shows that the surface tension of the acidolysis-crosslinking-sulfonation complex modified starch slurry is significantly reduced compared to starch. The reduction in surface tension improves wetting and spreading of the starch slurry on the fiber surface, thereby increasing adhesion to the fiber. Fig. 4 shows that the flexural fatigue resistance of the acidolysis-crosslinking-sulfonation composite modified starch film is obviously better than that of the starch film, and the starch film subjected to acidolysis-crosslinking-sulfonation composite modification has better flexibility, so that warp yarns can be better protected in the weaving process.
Those of ordinary skill in the art will understand that: the discussion of any embodiment above is meant to be exemplary only, and is not intended to intimate that the scope of the disclosure, including the claims, is limited to these examples; within the idea of the invention, also features in the above embodiments or in different embodiments may be combined, steps may be implemented in any order, and there are many other variations of the different aspects of the invention as described above, which are not provided in detail for the sake of brevity.
The embodiments of the invention are intended to embrace all such alternatives, modifications and variances that fall within the broad scope of the appended claims. Therefore, any omissions, modifications, substitutions, improvements and the like that may be made without departing from the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (10)
1. An acidolysis-crosslinking-sulfonation composite modified starch slurry, wherein the crosslinking of the composite modified starch slurry occurs between hydroxyl groups of anhydroglucose residues in starch molecules, and a sulfonated sulfonate functional group is introduced onto a double bond in an itaconic acid functional group, and the composite modified starch slurry comprises the following formula:
2. the preparation method of the acidolysis-crosslinking-sulfonation composite modified starch slurry is characterized by comprising the following steps of:
acid hydrolysis: preparing starch into starch milk, heating to 30-50 ℃, adding a hydrochloric acid solution, stirring for reaction for 1-6 hours, neutralizing with a sodium carbonate solution until the pH is 6.5-7, performing suction filtration, washing with distilled water, and drying in an oven to obtain acidolysis starch;
and (3) crosslinking: preparing acidolysis starch, itaconic acid and distilled water into starch milk, stirring for reaction for 25-60 min, carrying out vacuum filtration, carrying out stepped heating drying on a filter cake, dispersing the dried product into an ethanol solution, neutralizing with a sodium hydroxide solution, carrying out suction filtration, washing, and drying to obtain acidolysis-crosslinked starch;
sulfonation: mixing the acidolysis-crosslinking starch and the sulfonation liquid into emulsion, stirring and reacting for 3-6 hours at the temperature of 30-45 ℃, neutralizing the pH value to 6.5-7 by using a sodium carbonate solution, carrying out suction filtration, washing, drying, crushing and sieving to obtain acidolysis-crosslinking-sulfonation composite modified starch slurry.
3. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 2, wherein in the acidolysis, the concentration of starch milk is 20 to 40%, the concentration of hydrochloric acid is 0.5 to 2.0mol/L, and the mass fraction of sodium carbonate solution is 2 to 8%.
4. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 2, wherein in the crosslinking, the concentration of starch milk is 15-40%, the mass fraction of sodium hydroxide solution is 0.5-2%, and the dosage of itaconic acid is 2.16-8.64% of the mass of starch.
5. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 2, wherein in the sulfonation, the emulsion concentration is 25-40%, and the mass fraction of the sodium carbonate solution is 2-8%.
6. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 2, wherein the step-wise temperature rise drying comprises the following steps: pre-drying the filter cake at 30-60 ℃ for 1.5-3.5 h, raising the temperature to 65-85 ℃, drying for 2-5h, and finally drying at 120-140 ℃ for 2-4 h.
7. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 2, wherein the sulfonation liquid is a mixed liquid of sodium bisulfite and anhydrous sodium sulfate.
8. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 7, wherein the amount of sodium bisulfite is 10.8-43.2% of the mass of starch.
9. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 7, wherein the amount of the anhydrous sodium sulfate is 6-15% of the mass of the starch.
10. The method for preparing acidolysis-crosslinking-sulfonation composite modified starch slurry according to claim 2, wherein the starch is one of potato starch, corn starch, sweet potato starch, wheat starch and tapioca starch.
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