CN109897137B - Super water-absorbing starch and preparation method thereof - Google Patents
Super water-absorbing starch and preparation method thereof Download PDFInfo
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- CN109897137B CN109897137B CN201910237321.6A CN201910237321A CN109897137B CN 109897137 B CN109897137 B CN 109897137B CN 201910237321 A CN201910237321 A CN 201910237321A CN 109897137 B CN109897137 B CN 109897137B
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Abstract
The invention provides super water-absorbent starch and a preparation method thereof, belonging to the technical field of high polymer materials. Adding water into a starch raw material for humidifying, and mixing with a polymer monomer to obtain a mixture; sequentially carrying out ray irradiation and extrusion treatment on the mixture to obtain an extruded material; and carrying out microwave irradiation on the extruded material to obtain the super water-absorbing starch. The invention utilizes the ray irradiation to fully open the chain block of the starch amorphous area, provides more grafting sites for the polymer monomer, improves the reaction speed of the polymer monomer and the starch, leads the reaction to be more thorough, thereby improving the grafting efficiency of the starch and further improving the water absorption of the starch; the preparation method provided by the invention has the advantages of simple process, less investment equipment, lower cost, no volatilization of toxic and harmful gases, contribution to environmental protection and health of operators and accordance with the requirement of green production. The example result shows that the water absorption rate of the super absorbent starch prepared by the invention is 800-3000%.
Description
Technical Field
The invention relates to the technical field of high polymer materials, and particularly relates to super water-absorbent starch and a preparation method thereof.
Background
Modified starch is a kind of new-type high molecular material, it uses hydrophilic and semi-rigid starch macromolecule as skeleton, utilizes physical and chemical method to initiate and produce free radical, and makes it produce copolymerization reaction with polymer monomer, and utilizes the introduction of different functional groups and regulation of proportion of hydrophilic and oleophylic chain segment structure, so that it not only possesses polysaccharide compound, intermolecular action and reactivity, but also possesses the stability of mechanical and biological action of synthetic high molecule and development capability of linear method structure. The super absorbent starch is modified starch with unique water absorption performance, can absorb water which is dozens of times or even thousands of times of the self weight, and can be widely used in the aspects of textile, papermaking, oilfield chemicals, degradable mulching films, polymeric flocculants, water absorption materials, plastics and the like, such as sizing agents, stabilizers, degradable film base materials, flocculants, desiccants, degradable plastics and the like.
The preparation method of the super absorbent starch mainly comprises a physical method and a chemical method. The physical methods such as ultrahigh pressure treatment, hydrothermal treatment and the like, and the chemical methods generally use an initiator to initiate the generation of starch free radicals, and then cross-link with monomers. The existing physical method and chemical method have the problems of insufficient reaction, slow reaction and the like, and the water absorption rate of the obtained super water-absorbent starch needs to be further improved.
Disclosure of Invention
In view of the above, the present invention aims to provide a super absorbent starch and a preparation method thereof. The preparation method provided by the invention has the advantages that the reaction is rapid and thorough, and the water absorption rate of the obtained super absorbent starch is extremely high.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of super water-absorbing starch comprises the following steps:
(1) adding water into a starch raw material for humidifying, and mixing with a polymer monomer to obtain a mixture;
(2) sequentially carrying out ray irradiation and extrusion treatment on the mixture to obtain an extruded material; the ray irradiation is electron beam irradiation or cobalt-60 irradiation;
(3) and carrying out microwave irradiation on the extruded material to obtain the super water-absorbing starch.
Preferably, the starch material is native starch or a starch derivative.
Preferably, the native starch comprises one or more of corn starch, wheat starch, sorghum starch, rice starch, potato starch, tapioca starch, kudzu root starch and sweet potato starch;
the starch derivative comprises one or more of dextrin, pregelatinized starch and oxidized starch.
Preferably, the mass of the water in the step (1) is 20-40% of the mass of the starch raw material.
Preferably, the polymer monomer in step (1) is acrylamide.
Preferably, the mass of the polymer monomer in the step (1) is 30-50% of the mass of the starch raw material.
Preferably, the radiation dose is 5-80 kGy.
Preferably, the microwave irradiation time is 3-8 min, the power is 500-1200W, and the frequency is 1.5-3.5 GHz.
The invention provides the super absorbent starch prepared by the preparation method in the scheme, and the water absorption rate of the super absorbent starch is 800-3000%.
The invention provides a preparation method of super water-absorbent starch, which comprises the following steps: adding water into a starch raw material for humidifying, and mixing with a polymer monomer to obtain a mixture; sequentially carrying out ray irradiation and extrusion treatment on the mixture to obtain an extruded material; the ray irradiation is electron beam irradiation or cobalt-60 irradiation; and carrying out microwave irradiation on the extruded material to obtain the super water-absorbing starch. According to the invention, chain blocks in the amorphous region of the starch are fully opened by utilizing ray irradiation, so that more free radicals are generated by the starch, more grafting sites are provided for polymerization of a polymer monomer, the reaction speed of the polymer monomer and the starch is increased, the reaction is more thorough, the grafting efficiency of the starch is increased, and the water absorption of the starch is further increased; the preparation method provided by the invention has the advantages of simple process, less investment equipment, lower cost and high production efficiency, and no volatilization of toxic and harmful gases, is beneficial to environmental protection and health of operators, and meets the requirement of green production.
The invention provides the super-absorbent starch prepared by the scheme, and the example result shows that the water absorption rate of the super-absorbent starch prepared by the invention is 800-3000%.
Detailed Description
The invention provides a preparation method of super water-absorbent starch, which comprises the following steps:
(1) adding water into a starch raw material for humidifying, and mixing with a polymer monomer to obtain a mixture;
(2) sequentially carrying out ray irradiation and extrusion treatment on the mixture to obtain an extruded material; the ray irradiation is electron beam irradiation or cobalt-60 irradiation;
(3) and carrying out microwave irradiation on the extruded material to obtain the super water-absorbing starch.
The starch raw material is added with water for humidifying and then is mixed with the polymer monomer to obtain a mixture. In the present invention, the starch feedstock is preferably native starch or a starch derivative; the native starch preferably comprises one or more of corn starch, wheat starch, sorghum starch, rice starch, potato starch, tapioca starch, kudzu root starch and sweet potato starch; the starch derivative preferably comprises one or more of dextrin, pregelatinized starch and oxidized starch; the viscosity of the starch raw material is preferably 40-50 mp · s, and the water content is preferably 12-15 wt%.
In the present invention, the mass of the water is preferably 20 to 40%, more preferably 25 to 35%, and further preferably 30% of the mass of the starch raw material. The starch raw material and the water are uniformly mixed without special requirements on the humidity adjustment.
In the present invention, the polymer monomer is preferably acrylamide; the mass of the polymer monomer is preferably 30% to 50%, more preferably 50%, of the mass of the starch raw material. In the present invention, the wet starch after conditioning and the polymer monomer are preferably mixed uniformly by using a mixer.
After the mixture is obtained, the invention sequentially carries out ray irradiation and extrusion treatment on the mixture to obtain the extruded material. In the present invention, the radiation irradiation is electron beam irradiation or cobalt-60 irradiation; the radiation dose is preferably 5-80 kGy, more preferably 10-70 kGy, and further preferably 20-60 kGy. The invention utilizes ray irradiation to fully open the chain block of the starch amorphous region, provides more grafting sites for the polymerization of the polymer monomer, improves the reaction speed of the polymer monomer and the starch, leads the reaction to be more thorough and further improves the grafting efficiency of the starch.
The invention has no special requirements on the extrusion treatment, and only needs to use a screw extruder for extrusion. In the present invention, the temperature of the extrusion treatment is preferably 95 ℃ and the rotation speed is preferably 1400 rpm. The invention further and fully carries out the grafting reaction of the polymer monomer and the starch under the shearing action of mechanical force by screw extrusion.
After the extruded material is obtained, the invention carries out microwave irradiation on the extruded material to obtain the super water-absorbing starch. In the invention, the time of microwave irradiation is preferably 3-8 min, more preferably 4-6 min, and further preferably 5 min; the power is preferably 500-1200W, more preferably 600-1000W, and further preferably 800W; the frequency is preferably 1.5 to 3.5GHz, more preferably 2 to 3GHz, and further preferably 2.45 GHz. The extrusion material is heated and dehydrated through microwave radiation, so that the obtained product has a more stable structure.
After the microwave irradiation is finished, the extruded material after the microwave irradiation is preferably sequentially cooled and crushed to obtain the super absorbent starch. The cooling method has no special requirement, and the cooling can be carried out by air cooling or room temperature; the invention has no special requirement on the granularity of the pulverization, and can obtain uniform and fine powder.
The super absorbent starch prepared by the preparation method provided by the invention has the water absorption rate of 800-3000%, and has a good application prospect in the aspects of spinning, papermaking, oil field chemicals, degradable mulching films, polymeric flocculants, water absorbent materials, plastics and the like.
The embodiments of the present invention will be described in detail with reference to the following examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Taking 8g of corn starch (viscosity 46mp & s, water content 13.4 wt%), adding 2g of water for humidifying, then adding 4g of acrylamide monomer for mixing with the humidified starch, and uniformly stirring by a stirrer to obtain a mixture;
(2) performing electron beam irradiation on the mixture, wherein the irradiation dose is 5kGy, and extruding the irradiated starch by a screw extruder to obtain an extruded material;
(3) and (3) carrying out microwave irradiation on the extruded material for 5min, wherein the microwave power is 800W, and the frequency is 2.45GHz, and then cooling and crushing to obtain the super absorbent starch.
The water absorption test shows that the water absorption of the super absorbent starch is 900%.
Example 2
Other conditions were the same as in example 1 except that the corn starch was replaced with dextrin (viscosity 43 mp. multidot.s, moisture content 14 wt%) to obtain super absorbent starch.
The water absorption test shows that the water absorption of the super absorbent starch is 2300%.
Example 3
The other conditions are the same as the example 1, only the irradiation method in the step (2) is changed into cobalt-60 irradiation, the irradiation dose is 5kGy, the microwave irradiation time in the step (3) is changed into 3min, the microwave power is changed into 500W, and the frequency is changed into 1.5 GHz.
The water absorption of the obtained super absorbent starch was 2800% by a water absorption test.
Example 4
The other conditions are the same as the example 1, and the super absorbent starch is obtained by only changing the irradiation method in the step (2) into cobalt-60 irradiation with the irradiation dose of 15 kGy.
The water absorption test shows that the water absorption of the super absorbent starch is 3000%.
Example 5
Other conditions were the same as in example 1 except that the amount of acrylamide used in step (1) was changed to 5 g. The water absorption test shows that the water absorption of the super absorbent starch is 2500%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (4)
1. A preparation method of super absorbent starch is characterized by comprising the following steps:
(1) adding water into a starch raw material for humidifying, and mixing with a polymer monomer to obtain a mixture; the mass of the polymer monomer is 30-50% of that of the starch raw material; the polymer monomer is acrylamide;
(2) sequentially carrying out ray irradiation and extrusion treatment on the mixture to obtain an extruded material; the ray irradiation is electron beam irradiation or cobalt-60 irradiation; the radiation dose is 5-80 kGy;
(3) performing microwave irradiation on the extruded material to obtain super water-absorbing starch; the microwave irradiation time is 3-8 min, the power is 500-800W, and the frequency is 1.5-2.45 GHz.
2. The method of claim 1, wherein the starch material is native starch or a starch derivative.
3. The method of claim 2, wherein the raw starch comprises one or more of corn starch, wheat starch, sorghum starch, rice starch, potato starch, tapioca starch, kudzu starch and sweet potato starch;
the starch derivative comprises one or more of dextrin, pregelatinized starch and oxidized starch.
4. The preparation method according to claim 1, wherein the mass of the water in the step (1) is 20-40% of the mass of the starch raw material.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19619680A1 (en) * | 1996-05-15 | 1997-11-20 | Buna Sow Leuna Olefinverb Gmbh | Starch based superabsorbent |
| CN103819615A (en) * | 2014-02-28 | 2014-05-28 | 湖北省农业科学院农产品加工与核农技术研究所 | Method of preparing starch-base highly-water-absorbent material by radiation |
| CN107151291A (en) * | 2017-07-11 | 2017-09-12 | 武汉纺织大学 | A kind of technique of utilization dry production graft starch |
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2019
- 2019-03-27 CN CN201910237321.6A patent/CN109897137B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19619680A1 (en) * | 1996-05-15 | 1997-11-20 | Buna Sow Leuna Olefinverb Gmbh | Starch based superabsorbent |
| CN103819615A (en) * | 2014-02-28 | 2014-05-28 | 湖北省农业科学院农产品加工与核农技术研究所 | Method of preparing starch-base highly-water-absorbent material by radiation |
| CN107151291A (en) * | 2017-07-11 | 2017-09-12 | 武汉纺织大学 | A kind of technique of utilization dry production graft starch |
Non-Patent Citations (2)
| Title |
|---|
| 淀粉接枝丙烯酸乙酯及其增容性;于九皋等;《CHINESE JOURNAL OF APPLIED CHEMISTRY》;19970630;第12-15页 * |
| 淀粉絮凝剂的研究概况;王小雄等;《工业水处理》;20090131;第6-9页 * |
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