CN103923261A - Preparation method of composite high-performance water-absorbing resin - Google Patents
Preparation method of composite high-performance water-absorbing resin Download PDFInfo
- Publication number
- CN103923261A CN103923261A CN201410129141.3A CN201410129141A CN103923261A CN 103923261 A CN103923261 A CN 103923261A CN 201410129141 A CN201410129141 A CN 201410129141A CN 103923261 A CN103923261 A CN 103923261A
- Authority
- CN
- China
- Prior art keywords
- starch
- preparation
- add
- solution
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Abstract
The invention provides a preparation method of composite high-performance water-absorbing resin. The preparation method comprises the following steps of: adding starch into sulfuric acid solution, stirring, and carrying out centrifugal filtering to obtain starch nano crystal whisker precipitate; adding acrylic acid and acrylamide into the starch nano crystal whisker precipitate in sequence, then dripping N, N'-methylene bisacrylamide solution and ammonium persulfate solution simultaneously, and reacting under protection of nitrogen gas to obtain the composite high-performance water-absorbing resin. The preparation method provided by the invention has the advantages that starch nano crystal whisker and acrylic acid/acrylamide are adopted for reacting under the condition that a cross-linking agent and an initiating agent to prepare the high-performance water-absorbing resin material; due to an advanced three-dimensional cross-linking space structure of the starch crystal whisker inside and a large amount of hydrophilic groups on the surface, the composite high-performance water-absorbing resin material has better water absorbing performance, good water-absorbing effect, low cost and environment-friendly and safe effects compared with the common water-absorbing resin material.
Description
Technical field
The invention belongs to a kind of nano modification macromolecule resin technical field, be specifically related to a kind of composite high-performance absorbent resin preparation method
Background technology
Macromolecule water uptake resin is to have the low crosslinking degree of many hydrophilic radicals or the high molecular polymer of partial crystallization, it can absorb the water of own wt hundred times, the water of thousands of times even, and have very strong water retention capacity, therefore it has the huge market requirement at agriculture water-keeping material, wastewater treatment, medical field and physiological hygiene material.Current high performance absorbent resin is mainly made by inorganic material-modified macromolecule resin, as chitosan/polyacrylic acid composite absorbent material, graphene oxide and vinylformic acid composite absorbent material and silicon-dioxide, nano titania composite high-molecular water-absorbing resin, wherein chitosan/polyacrylic acid composite absorbent material, graphene oxide and vinylformic acid composite absorbent material water-absorbent are lower, and cost is higher; Although silicon-dioxide, nano titania composite high-molecular water-absorbing resin have better water-absorbent, but this type of material exists metallics residual, during for medical field, physiological hygiene material, can there is potential potential safety hazard, and also have the shortcomings such as metallic pollution in the time that other field uses.
Summary of the invention
The invention provides a kind of composite high-performance absorbent resin preparation method, provide that a kind of soaking effect is good, cost is low and the absorbent resin of tool Environmental Safety.
Technical scheme of the present invention is as follows:
A preparation method for composite high-performance absorbent resin, comprises the following steps:
(1) starch is added and in sulphuric acid soln, stir 3-5 hour, then centrifuging obtains starch nano whisker throw out;
(2) add vinylformic acid to stir to (1) middle starch nano whisker throw out, then add alkaline solution to neutralize it;
(3) after solution in (3) is cooling, adds acrylamide and stir;
(4) drip N, N '-methylene-bisacrylamide solution and ammonium persulfate solution react 3-5 hour at nitrogen protection, 50-80 DEG C simultaneously;
(5) reactant in (4) is obtained to composite high-performance absorbent resin after being dried.
Further, in described step (1), the ratio of starch and sulphuric acid soln is that every 1 liter of sulphuric acid soln adds 4-9 gram of starch, and the mass percent of described sulphuric acid soln is 30-60%.
In described step (1), the number of times of centrifuging is 3-8 time.
In described step (2), acrylic acid add-on is that every 20 milliliters of starch nano whisker throw outs add 3-6 gram;
In described step (2), alkaline solution is that mass percent is the sodium hydroxide solution of 30-80%.
In described step (3), the add-on of acrylamide is that every 20 milliliters of nano whisker throw outs add 1-3 gram.
N in described step (4), the mass percent of N '-methylene-bisacrylamide solution is 30-70%, its add-on is that every 20 milliliters of nano whisker throw outs drip 1-2 milliliter; The mass percent of described ammonium persulfate solution is 20-80%, and its add-on is that every 20 milliliters of nano whisker throw outs drip 2-5 milliliter.
So beneficial effect of the present invention:
1, the present invention adopts starch nano whisker to react and prepare high-performance water-absorbing resin material in the situation that linking agent exists with initiator with acrylic acid/acrylamide monomer, and its soaking effect is good, cost is low and tool Environmental Safety.
2, the raw starch that the present invention adopts is a kind of wide material sources, green reproducible natural polysaccharide compound, cheap, environmental protection; Use the cheap of absorbent resin that cheap starch prepared as modification composite base-material, have more the feature of environmental protection, security.
3, the starch nano whisker that starch obtains after vitriolization has high specific surface area and gap structure, and itself surface exists a large amount of hydrophilic radicals, attracts entering of water.
4, the composite high-performance absorbent resin that the present invention makes, due to the flourishing three-dimensional cross-linked space structure of its inner starch nano whisker, makes the more common absorbing resin material of material, has better water absorbing properties.
Embodiment
embodiment 1
(1) 6g starch being added to 1L mass percent is in 40% sulphuric acid soln, at room temperature stirring reaction 4 hours; Centrifuging 6 times, obtains starch nano whisker throw out;
(2) get 20 milliliters of the starch nano whisker throw outs of above-mentioned preparation, add 4g vinylformic acid to stir, in the sodium hydroxide solution that is then 60% with mass percent with mixed solution in vinylformic acid;
(3) after above-mentioned solution is cooling, add 2 grams of acrylamides, stir;
(4) drip the N that 1.5mL mass percent is 50%, N '-methylene-bisacrylamide and 3mL mass percent are 50% ammonium persulfate solution, under nitrogen protection, temperature 70 C, react 4 hours;
(5) reactant in (4) is dried, obtains composite high-performance absorbent resin.
embodiment 2
(1) 7g starch being added to 1L mass percent is in 50% sulphuric acid soln, at room temperature stirring reaction 3 hours; Centrifuging 4 times, obtains starch nano whisker throw out;
(2) get 20 milliliters of the starch nano whisker throw outs of above-mentioned preparation, add 5g vinylformic acid, then vinylformic acid in the sodium hydroxide solution that is 50% by mass percent and in mixed solution;
(3) after above-mentioned solution is cooling, add 1.5 grams of acrylamides, stir;
(4) drip the N that 1.2mL mass percent is 60%, N '-methylene-bisacrylamide and 4mL mass percent be 60% ammonium persulfate solution under nitrogen protection, temperature 60 C, react 3 hours;
(5) above-mentioned reactant is dried, obtains composite high-performance absorbent resin.
embodiment 3
(1) 9g starch being added to 1L mass percent is in 30% sulphuric acid soln, at room temperature stirring reaction 5 hours, and centrifuging 8 times, obtains starch nano whisker throw out;
(2) get 20 milliliters of the starch nano whisker throw outs of above-mentioned preparation, add 6g vinylformic acid, in the sodium hydroxide solution that is 80% by mass percent and vinylformic acid;
(3) after above-mentioned solution is cooling, add 3 grams of acrylamides, stir;
(4) drip the N that 2mL mass percent is 30%, N '-methylene-bisacrylamide and 2mL mass percent are 80% ammonium persulfate solution; At 80 DEG C of nitrogen protections, temperature, react 5 hours,
(5) above-mentioned reactant is dried, obtains composite high-performance absorbent resin.
embodiment 4
(1) 4g starch being added to 1L mass percent is in 60% sulphuric acid soln, at room temperature stirring reaction 4 hours, and centrifuging 3 times, obtains starch nano whisker throw out;
(2) get 20 milliliters of the starch nano whisker throw outs of above-mentioned preparation, add 3g vinylformic acid, the vinylformic acid in the sodium hydroxide solution that is 30% by mass percent and in mixed solution;
(3) after above-mentioned solution is cooling, add 1 gram of acrylamide, stir;
(4) drip the N that 1mL mass percent is 70%, N '-methylene-bisacrylamide and 5mL mass percent be 70% ammonium persulfate solution under nitrogen protection, temperature 50 C, react 5 hours;
(5) above-mentioned reactant is dried, obtains composite high-performance absorbent resin.
embodiment 5
(1) 7g starch being added to 1L mass percent is in 45% sulphuric acid soln, at room temperature stirring reaction 3.5 hours, and centrifuging 5 times, obtains starch nano whisker throw out;
(2) get 20 milliliters of the starch nano whisker throw outs of above-mentioned preparation, add 4.5g vinylformic acid, the vinylformic acid in the sodium hydroxide solution that is 30% by mass percent and in mixed solution;
(3) after above-mentioned solution is cooling, add 2.7 grams of acrylamides, stir;
(4) drip the N that 1.8mL mass percent is 60%, N '-methylene-bisacrylamide and 3mL mass percent be 20% ammonium persulfate solution under nitrogen protection, temperature 70 C, react 3 hours;
(5) above-mentioned reactant is dried, obtains composite high-performance absorbent resin.
Composite high-performance absorbent resin prepared by above-described embodiment 1-3 and existing water-absorbing material: chitosan/polyacrylic acid composite absorbent material, graphene oxide and vinylformic acid composite absorbent material, SiO2 modified polyacrylic acid composite absorbent material, TiO2 modified polyacrylic acid composite absorbent material, measure its water absorbing properties separately according to standard A STM D570-1998 (2010) e1, the water regain of each material is as shown in the table:
| Material | Water regain |
| Embodiment 1 | 652% |
| Embodiment 2 | 671% |
| Embodiment 3 | 703% |
| Chitosan/polyacrylic acid composite absorbent material | 351% |
| Graphene oxide and vinylformic acid composite absorbent material | 382% |
| SiO2 modified polyacrylic acid composite absorbent material | 456% |
| TiO2 modified polyacrylic acid composite absorbent material | 587% |
Can find out from above table, the high water absorption of starch nano whisker composite high-performance absorbent resin that the present invention makes reaches 703%, the water regain of more current traditional water-absorbing material is 351%, has increased by 352%, so the absorbent resin of explanation the present invention shooting has more excellent water absorbing properties.
Claims (7)
1. a preparation method for composite high-performance absorbent resin, is characterized in that: comprise the following steps:
(1) starch is added and in sulphuric acid soln, stir 3-5 hour, then centrifuging obtains starch nano whisker throw out;
(2) add vinylformic acid to stir to (1) middle starch nano whisker throw out, then add alkaline solution to neutralize it;
(3) after solution in (3) is cooling, adds acrylamide and stir;
(4) drip N, N '-methylene-bisacrylamide solution and ammonium persulfate solution react 3-5 hour at nitrogen protection, 50-80 DEG C simultaneously;
(5) reactant in (4) is obtained to composite high-performance absorbent resin after being dried.
2. preparation method according to claim 1, is characterized in that: in described step (1), the ratio of starch and sulphuric acid soln is that every 1 liter of sulphuric acid soln adds 4-9 gram of starch, and the mass percent of described sulphuric acid soln is 30-60%.
3. preparation method according to claim 1, is characterized in that: in described step (1), the number of times of centrifuging is 3-8 time.
4. preparation method according to claim 1, is characterized in that: in described step (2), acrylic acid add-on is that every 20 milliliters of starch nano whisker throw outs add 3-6 gram.
5. preparation method according to claim 1, is characterized in that: in described step (2), alkaline solution is that mass percent is the sodium hydroxide solution of 30-80%.
6. preparation method according to claim 1, is characterized in that: in described step (3), the add-on of acrylamide is that every 20 milliliters of nano whisker throw outs add 1-3 gram.
7. preparation method according to claim 1, is characterized in that: N in described step (4), and the mass percent of N '-methylene-bisacrylamide solution is 30-70%, its add-on is that every 20 milliliters of nano whisker throw outs drip 1-2 milliliter; The mass percent of described ammonium persulfate solution is 20-80%, and its add-on is that every 20 milliliters of nano whisker throw outs drip 2-5 milliliter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410129141.3A CN103923261B (en) | 2014-04-02 | 2014-04-02 | A kind of preparation method of composite high-performance water-absorbing resins |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410129141.3A CN103923261B (en) | 2014-04-02 | 2014-04-02 | A kind of preparation method of composite high-performance water-absorbing resins |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103923261A true CN103923261A (en) | 2014-07-16 |
| CN103923261B CN103923261B (en) | 2019-03-05 |
Family
ID=51141671
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410129141.3A Active CN103923261B (en) | 2014-04-02 | 2014-04-02 | A kind of preparation method of composite high-performance water-absorbing resins |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103923261B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942740A (en) * | 2019-03-25 | 2019-06-28 | 四川轻化工大学 | A kind of preparation method of the Sodium Polyacrylate composite material of wastewaters with modified calcium sulfate whiskers doping |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157295A (en) * | 1996-12-26 | 1997-08-20 | 国内贸易部谷物油脂化学研究所 | Method for preparation of starch graft copolymer acrylic acid (acrylate) super water-absorbing agent |
| CN1339513A (en) * | 2000-08-22 | 2002-03-13 | 上海众伟生化有限公司 | High water absorption resin and its producing method |
| CN102153703A (en) * | 2011-03-23 | 2011-08-17 | 浙江理工大学 | Preparation method of cellulose-based high-water-absorption high-water-retention resin |
| CN102344532A (en) * | 2011-07-21 | 2012-02-08 | 东华大学 | Method for synthesizing super absorbent resin by using invasive plant |
| CN103159895A (en) * | 2011-12-16 | 2013-06-19 | 四川师范大学 | Preparation method of biodegradable and farm-oriented water-absorbing adhesive resin |
| CN103554371A (en) * | 2013-11-19 | 2014-02-05 | 宜兴丹森科技有限公司 | Preparation method of starch-grafted polyacrylic acid super absorbent resin |
-
2014
- 2014-04-02 CN CN201410129141.3A patent/CN103923261B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1157295A (en) * | 1996-12-26 | 1997-08-20 | 国内贸易部谷物油脂化学研究所 | Method for preparation of starch graft copolymer acrylic acid (acrylate) super water-absorbing agent |
| CN1339513A (en) * | 2000-08-22 | 2002-03-13 | 上海众伟生化有限公司 | High water absorption resin and its producing method |
| CN102153703A (en) * | 2011-03-23 | 2011-08-17 | 浙江理工大学 | Preparation method of cellulose-based high-water-absorption high-water-retention resin |
| CN102344532A (en) * | 2011-07-21 | 2012-02-08 | 东华大学 | Method for synthesizing super absorbent resin by using invasive plant |
| CN103159895A (en) * | 2011-12-16 | 2013-06-19 | 四川师范大学 | Preparation method of biodegradable and farm-oriented water-absorbing adhesive resin |
| CN103554371A (en) * | 2013-11-19 | 2014-02-05 | 宜兴丹森科技有限公司 | Preparation method of starch-grafted polyacrylic acid super absorbent resin |
Non-Patent Citations (4)
| Title |
|---|
| CRISTIANE SPAGNOL等: "Superabsorbent hydrogel composite made of cellulose nanofibrils and chitosan-graft-poly(acrylic acid)", 《CARBOHYDRATE POLYMERS》 * |
| 张俐娜等: "《基于生物质的环境友好材料》", 30 June 2011, 化学工业出版社 * |
| 杨丽敏等: "《有机化学》", 31 March 2012, 人民卫生出版社 * |
| 黄洋等: "细菌纤维素晶须/聚（丙烯酸-丙烯酰胺）复合高吸水性树脂", 《高分子学报》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109942740A (en) * | 2019-03-25 | 2019-06-28 | 四川轻化工大学 | A kind of preparation method of the Sodium Polyacrylate composite material of wastewaters with modified calcium sulfate whiskers doping |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103923261B (en) | 2019-03-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102250276B (en) | Clay-based amphoteric hydrophobic salt-resistant and high water absorbent resin and its preparation method | |
| Ma et al. | Synthesis and characterization of a novel super-absorbent based on wheat straw | |
| CN103214616B (en) | A kind of preparation method of porous-super-absorberesin resin | |
| CN102844340A (en) | Absorbent resin, the surface of which is modified with a cationic polymer compound | |
| CN104961863A (en) | Method for preparing polysaccharide biogum polymer gel profile control agent | |
| CN103570859A (en) | Inorganic montmorillonoid composited cross-linked polymer microsphere as well as preparation method and application thereof | |
| CN102633944B (en) | Preparation method of salt-tolerance controlled-release high-water-absorption resin with hydrophobic chain segments | |
| CN102766232A (en) | Preparation method of epoxysuccinate /acrylic acid/2-acrylamido-2-methyl propane sulfonic acid copolymer | |
| CN102504292A (en) | Organic cross linking system for polymer flooding and preparation method of cross linking agent | |
| CN102617781A (en) | Synthesis method for resin with high water absorbability | |
| CN103965491A (en) | Preparation method for silk fibroin composite gel | |
| CN103130965B (en) | A kind of Humic acid type superabsorbent resin and preparation method thereof | |
| MX354487B (en) | Highly swellable polymers. | |
| CN110577619A (en) | Preparation method of super absorbent resin | |
| CN101412793A (en) | Method for modifying acroleic acid super absorbent polymers by using silk | |
| CN103923261A (en) | Preparation method of composite high-performance water-absorbing resin | |
| CN101440144A (en) | Zwitterion association type high wate-absorption resin and preparing method thereof | |
| CN104479074A (en) | High water-absorbing resin for diaper and preparation method thereof | |
| CN104629504A (en) | High-corrosion-resistance polyethylene powder paint containing graphene oxide grafted activated diatomite and preparation method thereof | |
| CN105330783A (en) | Preparation method of silane modified concrete internal curing agent | |
| CN103937139A (en) | Preparation method of poly (acrylic acid-vinyl acetate)-polyvinyl alcohol interpenetrating network super absorbent resin | |
| CN103641952A (en) | Production method of polyacrylamide modified water absorbent resin concrete internal curing agent | |
| CN109354700B (en) | Temperature-sensitive hydrogel and preparation method thereof | |
| CN109851965B (en) | Nano composite high water absorption material and preparation method thereof | |
| CN100404612C (en) | Preparation method of swelled vermiculite/ polyacrylic acid potassium- acrylamide high water absorption composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |