CN1339513A - High water absorption resin and its producing method - Google Patents
High water absorption resin and its producing method Download PDFInfo
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- CN1339513A CN1339513A CN 00119689 CN00119689A CN1339513A CN 1339513 A CN1339513 A CN 1339513A CN 00119689 CN00119689 CN 00119689 CN 00119689 A CN00119689 A CN 00119689A CN 1339513 A CN1339513 A CN 1339513A
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- water
- vinylformic acid
- acrylamide
- absorbing resin
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Abstract
The high water absorption resin consists of mainly high water absorption component produced by grafting polymerization of amylopectin in 5-40 wt%, acrylic acid in 50-90 wt% and acrylamide in 1-40 wt%. The present invention also provides the preparation process of the resin. The high water absorption resin of the present invention has strong absorbing capacity, especially to ion containing water and may be used to absorb water repeatedly, so that it is suitable for being used for maintaining water in soil.
Description
The present invention relates to fine chemistry industry novel material and technology thereof.More specifically, the present invention relates to a kind of new High hydrophilous resin and production method thereof.
High hydrophilous resin has developed comparatively rapid since three more than ten years of coming out.Technology the earliest is to take conventional corn starch and acrylonitrile graft copolymer, and technology is loaded down with trivial details, and vinyl cyanide toxicity is very big.
Afterwards, generally taked conventional corn starch and acrylic graft copolymer, but generally still exist to the absorptive character of distilled water still can, and for containing ionic water (all can not be to absorb pure water in the practical application), water regain greatly reduces.
In recent years, owing to reasons such as climatic anomaly, be subjected to the local increasing of arid and lack of water puzzlement.Plant trees, prevent multiple purposes such as Desertification for kind of a grass, need keep moisture effectively, so that the growth of plant.For in being mainly used in soil to absorb and to keep for the water-absorbing resin of moisture, because the water ions content is higher, so certain requirement is all arranged for the stability and the final degradability anti-ionic, resin of water-absorbing resin.For this reason, this area presses for the water-absorbing resin of Application and Development in soil.Better is that this water-absorbing resin can repeatedly absorb water effectively.
Purpose of the present invention just provides a kind of water-absorbing resin, and this water-absorbing resin has strong receptivity to containing ionic water, and the repeatedly effectively suction repeatedly of this water-absorbing resin.
Another object of the present invention provides the technology of making this water-absorbing resin.
In a first aspect of the present invention, a kind of water-absorbing resin is provided, it mainly is made of the suction composition that high amylopectin starch, vinylformic acid, acrylamide graft are polymerized, gross weight by the three, the high amylopectin starch weight percent is 5-40%, the vinylformic acid weight percent is 50-90%, and the acrylamide weight percent is 1-40%.
In a second aspect of the present invention, a kind of production method of water-absorbing resin is provided, it comprises step:
(1) mix high amylopectin starch, vinylformic acid, acrylamide and add initiator and linking agent, make high amylopectin starch, vinylformic acid, acrylamide generation graft copolymerization,
(2) under protection of inert gas, the oven dry reaction mixture,
(3) pulverization process, thus make water-absorbing resin.
Preferably, in high amylopectin starch and vinylformic acid, acrylamide three, by three's gross weight, the high amylopectin starch weight percent is 5-40%, and the vinylformic acid weight percent is 50-90%, and the acrylamide weight percent is 1-40%.
In one embodiment of the invention, in step (1) before, vinylformic acid is carried out pre-treatment: the 70-85% that is about to the vinylformic acid total amount neutralizes with KOH and/or ammoniacal liquor.Like this, when moisture was provided, water-absorbing resin of the present invention also can provide some required nutrients of plant-growth.
In a third aspect of the present invention, the purposes of water-absorbing resin of the present invention is provided, the moisture that it is used to soil keeps.
Definition
As used herein, " mainly by ... (composition) constitutes " refer to, water-absorbing resin of the present invention be to constitute basically by the suction composition that high amylopectin starch, vinylformic acid, acrylamide graft are polymerized.Certainly, this does not get rid of water-absorbing resin of the present invention yet and can contain other submembers (as potassium ion, ammonium ion) and impurity.
Inventive point of the present invention is that the raw material that forms water-absorbing resin has adopted high amylopectin starch (claiming waxy corn starch again) and acrylamide.It is about 70% that common starch contains the amylopectin molecule, amylose molecule about 30%.The character of two kind of starch molecules is difference to some extent: wherein amylopectin is soluble in water, a little less than the retrogradation; Amylose starch is insoluble in water, and retrogradation is strong.Contain the amylopectin molecule in the high amylopectin starch more than 99%, have unique character, it is carried out grafting, the graft copolymer that obtains also has characteristics such as resistance to deterioration is good, suction back gel transparency height than the common starch graft copolymer.
The polymkeric substance of acrylamide contains non-ionic suction group, be subjected to the branch intermediate ion concentration affects that absorbs water less.And when having acrylamide to exist in the multipolymer, the gel-strength after the water-absorbing resin suction is used the meaning of outbalance also than the copolymerization object height that does not contain acrylamide repeatedly for it.
In view of end-use of the present invention mainly is on agricultural, so in a preferred embodiment, use in KOH and/or the ammoniacal liquor and vinylformic acid.Like this, potassium ion in water-absorbing resin and ammonium ion also can play the effect of slow release fertilizer.Degree of neutralization is generally 60-90%, preferably is 70-85%, more preferably is about 80% (promptly have 80% vinylformic acid be neutralized).According to the actual needs of the farm crop of being used, can distinguish and use KOH or ammoniacal liquor separately, but also both mix use.
In the production method of preparation water-absorbing resin of the present invention, mainly may further comprise the steps:
At first mix high amylopectin starch, vinylformic acid, acrylamide, and add initiator and linking agent, make high amylopectin starch, vinylformic acid, acrylamide generation graft copolymerization.After polyreaction has been carried out one section preset time, reaction mixture is transferred in the drying plant, under protection of inert gas, the heat that utilizes outside heat and/or reaction system self to produce removes moisture.At last, the desciccate after the oven dry processing is carried out pulverization process, thereby make the resin of high-hydroscopicity of the present invention.
In the methods of the invention, the temperature of polyreaction is controlled at 35-45 ℃ usually, preferably is 37-42 ℃, is about 40 ℃ best.Temperature is too low, and reaction is carried out too slow; Temperature is too high, and then reaction is carried out too soon, and polymericular weight is less than normal, influence water-absorbent and reaction and is difficult to control.Polymerization reaction time is generally 20-60 minute, preferably is 25-45 minute.
Be used for initiator of the present invention and comprise that this area is usually used in the various initiators of polymeric acrylic acid and/or acrylamide.A kind of preferable initiator is formed redox initiation system by ammonium persulfate-sodium bisulfite, and this initiator system can reduce temperature of reaction.Usually, the weight ratio of ammonium persulphate and sodium bisulfite is controlled at 1: 2-3: between 1.Initiator content is generally the 0.5-1% of vinylformic acid weight, preferably is 0.5-0.8%.
For gel-strength after the suction that improves graft copolymer, also need add linking agent in the reaction system.Can be used for the various linking agents that linking agent of the present invention comprises that this area is commonly used.A kind of particularly preferred linking agent is a N,N methylene bis acrylamide.Dosage of crosslinking agent very little, it is soluble in water still to have the minor amounts of copolymerized thing; Dosage of crosslinking agent is too many, then can reduce water regain greatly.Therefore, the consumption of linking agent is generally the 0.03-0.07% of vinylformic acid weight, preferably is 0.04-0.06%.
Polyreaction among the present invention belongs to the radical-type polymerization reaction, and airborne oxygen can play inhibition, so this reaction needs to carry out in inert atmosphere (as nitrogen, helium etc.).Product is a gel because reaction is final when finishing, from reaction vessel, be difficult to take out, so the present invention's design reaction system become sticky thick after, promptly under the condition that has rare gas element (preferably selecting nitrogen for use) to protect, put into dish and dry.In drying course, react and proceed, and produce a large amount of heats, help taking away moisture.
With the water-absorbing resin of the inventive method preparation, to deionized water with contain ionized water very strong absorptivity is all arranged.Usually, the water regain of distilled water greater than 300 gram water/gram resins, the water regain of tap water is restrained water/gram resins greater than 150, and the decline of the water regain after 5 suction-oven dry is less than 10%, more preferably less than 5%.
Further set forth the present invention particularly below in conjunction with preferred embodiment.Should be understood that following embodiment only to be used to the present invention is described and be not used in the restriction scope of the invention.
Embodiment 1
The preparation of water-absorbing resin 1 and water absorbing properties
1. take by weighing high amylopectin starch 100 grams, add distilled water 1000 grams, be heated to 90 ℃, and kept 20 minutes, make the whole gelatinizations of starch, and feed nitrogen.
2. take by weighing 400 gram vinylformic acid, KOH 248 grams (being made into 30% aqueous solution), both neutralizations also are cooled to 40 ℃.
3. starch paste liquid is cooled to 40 ℃, adds the vinylformic acid neutralizer, acrylamide 10 grams, and ammonium persulphate 2 grams, sodium bisulfite 1 gram, N,N methylene bis acrylamide 0.2 gram stirs.
Reaction system remain on 40 ℃ 25 minutes, reaction solution begins to become sticky thick, has under the condition of nitrogen protection, puts into dish, admission passage formula drying unit is dried, and pulverizes.
The every gram of product in the present embodiment (water-absorbing resin 1) is inhaled distilled water 360 grams, inhales tap water 155 grams, and color and luster is a white.
Embodiment 2
The preparation of water-absorbing resin 2 and water absorbing properties
1. take by weighing high amylopectin starch 100 grams, add distilled water 1000 grams, be heated to 90 ℃, and kept 20 minutes, make the whole gelatinizations of starch, and begin to feed nitrogen.
2. take by weighing 400 gram vinylformic acid, restrain neutralization and be cooled to 40 ℃ with 20% ammoniacal liquor 377.
3. starch paste liquid is cooled to 40 ℃, adds the vinylformic acid neutralizer, acrylamide 20 grams, and ammonium persulphate 2 grams, sodium bisulfite 1 gram, N,N methylene bis acrylamide 0.2 gram stirs.
Reaction system remain on 40 ℃ 35 minutes, reaction solution begins to become sticky thick, has under the condition of nitrogen protection, puts into dish, admission passage formula drying unit is dried, and pulverizes.
The every gram of product in the present embodiment (water-absorbing resin 2) is inhaled distilled water 340 grams, inhales tap water 160 grams, and color and luster is dark and have redness, but does not influence its application at agriculture field.
Embodiment 3
The preparation of water-absorbing resin 3 and water absorbing properties
1. take by weighing high amylopectin starch starch 50 grams, add distilled water 500 grams, be heated to 90 ℃, and kept 20 minutes, make the whole gelatinizations of starch, and begin to feed nitrogen.
2. take by weighing 400 gram vinylformic acid, with KOH124 gram (being made into 30% aqueous solution), 20% ammoniacal liquor, 189 grams neutralize and are cooled to 40 ℃.
3. starch paste liquid is cooled to 40 ℃, adds the vinylformic acid neutralizer, acrylamide 100 grams, and ammonium persulphate 2 grams, sodium bisulfite 1 gram, N,N methylene bis acrylamide 0.2 gram stirs.
4. reaction system remains on 40 ℃ of half an hour, and reaction solution begins to become sticky thick, has under the condition of nitrogen protection, puts into dish, and admission passage formula drying unit is dried, and pulverizes.
The every gram of product in the present embodiment (water-absorbing resin 3) is inhaled distilled water 380 grams, inhales tap water 190 grams, and suction back gel is comparatively tough and tensile.
Simultaneously, be contrast with commercially available " high energy anti-drought water-retaining agent " (it is a kind of of better performances in the market), its every gram is inhaled distilled water 250 grams, inhales tap water 120 grams.
Embodiment 4
Repeat absorptive test
In this embodiment, carry out the test of repetition water-absorbent.
To the water-absorbing resin of the present invention 3 of embodiment 3, after suctioning tap water, 105 ℃ of oven dry, repeat suction-baking procedure then 4 times (totally 5 times), measure its water-absorbent again, the result shows that its water regain fall is less than 5%.
Same is contrast with commercially available " high energy anti-drought water-retaining agent " (it is a kind of of better performances in the market), and test under the same conditions repeats water-absorbent, and the result shows that after 5 suction-oven dry, water regain has descended about 20%.
All quote in this application as a reference at all documents that the present invention mentions, just quoted as a reference separately as each piece document.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Claims (10)
1. the production method of a water-absorbing resin is characterized in that, it comprises step:
(1) mix high amylopectin starch, vinylformic acid, acrylamide and add initiator and linking agent, make high amylopectin starch, vinylformic acid, acrylamide generation graft copolymerization,
(2) under protection of inert gas, the oven dry reaction mixture,
(3) pulverization process, thus make water-absorbing resin.
2. the method for claim 1 is characterized in that, in high amylopectin starch and vinylformic acid, acrylamide three, gross weight by the three, the high amylopectin starch weight percent is 5-40%, and the vinylformic acid weight percent is 50-90%, and the acrylamide weight percent is 1-40%.
3. the method for claim 1 is characterized in that, in step (1) before, vinylformic acid is carried out pre-treatment, and the 70-85% that is about to the vinylformic acid total amount neutralizes with KOH and/or ammoniacal liquor.
4. the method for claim 1 is characterized in that, described initiator is the redox initiation system that ammonium persulfate-sodium bisulfite is formed.
5. method as claimed in claim 4 is characterized in that, the weight ratio of ammonium persulphate and sodium bisulfite is 1: 2-3: 1.
6. the method for claim 1 is characterized in that, initiator content is the 0.5-1% of vinylformic acid weight.
7. the method for claim 1 is characterized in that, described initiator be N,N methylene bis acrylamide as linking agent, consumption is the 0.03-0.07% of vinylformic acid weight.
8. the method for claim 1 is characterized in that, the temperature of polyreaction is 35-45 ℃, and the time is 20-60 minute.
9. water-absorbing resin, it is characterized in that, it mainly is made of the suction composition that high amylopectin starch, vinylformic acid, acrylamide graft are polymerized, gross weight by the three, the high amylopectin starch weight percent is 5-40%, the vinylformic acid weight percent is 50-90%, and the acrylamide weight percent is 1-40%.
10. water-absorbing resin as claimed in claim 9 is characterized in that, this resin greater than 300 gram water/gram resins, the water regain of tap water is restrained water/gram resins greater than 150, and the decline of the water regain after 5 suction-oven dry is less than 10% to the water regain of distilled water.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB001196898A CN1137913C (en) | 2000-08-22 | 2000-08-22 | High water absorption resin and its producing method |
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| CNB001196898A CN1137913C (en) | 2000-08-22 | 2000-08-22 | High water absorption resin and its producing method |
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| CN1339513A true CN1339513A (en) | 2002-03-13 |
| CN1137913C CN1137913C (en) | 2004-02-11 |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875742A (en) * | 2012-09-05 | 2013-01-16 | 喻小琦 | Manufacturing method of high branching degree acrylamide graft copolymer taking amylopectin as framework |
| CN103012683A (en) * | 2013-01-17 | 2013-04-03 | 海南大学 | Method for preparing manioc waste super absorbent resin |
| CN103145931A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Biodegradable agricultural water retaining material and preparation method thereof |
| CN103911161A (en) * | 2014-03-31 | 2014-07-09 | 北京安平联合环保科技有限公司 | Soil surface modifier and preparation method thereof |
| CN103923261A (en) * | 2014-04-02 | 2014-07-16 | 合肥杰事杰新材料股份有限公司 | Preparation method of composite high-performance water-absorbing resin |
| CN107189294A (en) * | 2017-06-21 | 2017-09-22 | 华中师范大学 | A kind of organic polymer modification of polysaccharides hydrogel diaphragm and preparation method thereof, application |
| CN108623397A (en) * | 2018-07-19 | 2018-10-09 | 安徽袁粮水稻产业有限公司 | A kind of rice fertilizer inhibiting ineffective tillering |
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| CN1926945B (en) * | 2006-09-29 | 2010-04-07 | 东北师范大学 | Method for saline-alkali land vegetation recovery by using apocynum root segment for breeding |
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2000
- 2000-08-22 CN CNB001196898A patent/CN1137913C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102875742A (en) * | 2012-09-05 | 2013-01-16 | 喻小琦 | Manufacturing method of high branching degree acrylamide graft copolymer taking amylopectin as framework |
| CN103012683A (en) * | 2013-01-17 | 2013-04-03 | 海南大学 | Method for preparing manioc waste super absorbent resin |
| CN103145931A (en) * | 2013-03-25 | 2013-06-12 | 山东汇盈新材料科技有限公司 | Biodegradable agricultural water retaining material and preparation method thereof |
| CN103911161A (en) * | 2014-03-31 | 2014-07-09 | 北京安平联合环保科技有限公司 | Soil surface modifier and preparation method thereof |
| CN103911161B (en) * | 2014-03-31 | 2015-06-10 | 北京安平联合环保科技有限公司 | Soil surface modifier and preparation method thereof |
| CN103923261A (en) * | 2014-04-02 | 2014-07-16 | 合肥杰事杰新材料股份有限公司 | Preparation method of composite high-performance water-absorbing resin |
| CN107189294A (en) * | 2017-06-21 | 2017-09-22 | 华中师范大学 | A kind of organic polymer modification of polysaccharides hydrogel diaphragm and preparation method thereof, application |
| CN107189294B (en) * | 2017-06-21 | 2020-08-18 | 华中师范大学 | Organic polymer modified polysaccharide hydrogel protective film and preparation method and application thereof |
| CN108623397A (en) * | 2018-07-19 | 2018-10-09 | 安徽袁粮水稻产业有限公司 | A kind of rice fertilizer inhibiting ineffective tillering |
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|---|---|
| CN1137913C (en) | 2004-02-11 |
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Application publication date: 20020313 Assignee: Jiangsu Wei Wei Biomass Technology Co., Ltd. Assignor: Zhongwei Bio-Chemical Co., Ltd., Shanghai Contract record no.: 2016990000191 Denomination of invention: High water absorption resin and its producing method Granted publication date: 20040211 License type: Exclusive License Record date: 20160509 |
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