CN103059224A - Starch/acrylic acid composite super-absorbent resin - Google Patents
Starch/acrylic acid composite super-absorbent resin Download PDFInfo
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- CN103059224A CN103059224A CN2012104800543A CN201210480054A CN103059224A CN 103059224 A CN103059224 A CN 103059224A CN 2012104800543 A CN2012104800543 A CN 2012104800543A CN 201210480054 A CN201210480054 A CN 201210480054A CN 103059224 A CN103059224 A CN 103059224A
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Abstract
The invention discloses a starch/acrylic acid composite super-absorbent resin. The super-absorbent resin is prepared by adding starch in a polymerization system of sodium alginate and acrylic acid. By using the starch as a cross-linking agent of sodium alginate and acrylic acid, the prepared super-absorbent resin is excellent in salt resistance property; and the water absorption rate is 890-960g/g, and the rate of absorbing normal saline is 98-110g/g, so that the water absorption property is excellent.
Description
Technical field
The present invention relates to a kind of High hydrophilous resin, particularly the compound High hydrophilous resin that makes of a kind of starch and vinylformic acid.
Background technology
High hydrophilous resin (Super absorbent polymer, SAP) is a kind of new functional macromolecule material.Because having a series of characteristics such as high-hydroscopicity energy, high-water performance, Reusability, security, over nearly 30 years, all be widely used at aspects such as agricultural, gardening, desert, medicine, industry, material of construction.Over past ten years, the research of High hydrophilous resin, production, application development have all been obtained many new achievements, and Application Areas also constantly enlarges.The super absorbent resin lipid species is day by day various, from the source of raw material, the different angles such as structure properties characteristics, production technique have multiple sorting technique.With regard to the development of present both at home and abroad High hydrophilous resin, be fairly perfect a kind of with the raw material sources classification, SAP mainly is divided into following 4 classes: (1) starch-series, (2) are cellulose-based, (3) synthetic resins system, (4) organic and inorganic composite high-water uptake system.
The High hydrophilous resin research origin is in starch, and development rapidly since occurring.Starch is a kind of poly-hydroxy natural compounds of originating abundant, inexpensive, but owing to poor, perishable rotten, the poorly water-soluble of its resistance toheat, be difficult to the shortcoming such as prolonged preservation it is limited by very large in Application and Development, therefore generally must carry out to it modifications such as physics, chemical aspect.Wherein graft copolymerization is one of main method, and what be commonly used to grafting has monomers such as propenyl, vinylformic acid, various acrylate.Yang Qingrong, Huang Tinggang be by orthogonal experiment, grafted propylene nitrile and the impact of proportioning and reaction conditions has been discussed on W-Gum, and having obtained absorbency is the resin of 800g/g.Ray etc. utilize starch-grafted vinyl cyanide cross-linked epoxy chloropropane, have prepared water-fast cross-linking products, and it not only can make water-retaining agent, and can Adsorption of Heavy Metal Ions, have widened its application aspect sewage disposal.The starch graft acrylic acid High hydrophilous resin greatly simplified technical process, and toxicity is lower than vinyl cyanide owing to not needing saponification, wash easyly, consume solvent few, water absorbing properties is good, therefore its research and production development are rapid, become the main products of starch based High hydrophilous resin.Water solution polymerization process graft acrylic acid on W-Gum is adopted in Ulan, Liu Mingzhu, and prepared High hydrophilous resin at room temperature 30min can suck the resin that ionized water and tap water are respectively 1000g/g and 200g/g.But on production technique, connect with chemical method that (the branch copolymerization process is still very complicated, and the three wastes that produce when producing are more, and is unfavorable to environment.The researchs such as domestic Pan Songhan a kind of take carboxymethyl starch as raw material can omit the grafting method of gelatinization and basic hydrolysis technique, the High hydrophilous resin that obtains, and the suction multiple is high, stable performance, and without waste water, be the important development direction of starch based High hydrophilous resin.The clear grade of Liu Xiu then adopted radiation graft polymerization, have need not add initiator, simple to operate, percentage of grafting is high, extent of polymerization is high, pollution-free discharge, low cost and other advantages, prepared starch-series resin can suck distilled water and tap water is respectively 766g/g and 278g/g.Xiang Aimin etc. adopt microwave initiated polymerization method, and the synthetic resins water-intake rate reaches 558g/g.Along with the deepening continuously and its performance requriements is improved constantly of SAP applied research, functionalization becomes the research direction of starch-series, wherein adopt on starch a plurality of monomers of graft copolymerization become of research main aspect.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of, production technique simple, salt resistant character good High hydrophilous resin good to environment is provided.
In order to realize above goal of the invention, the present invention by the following technical solutions: a kind of starch/vinylformic acid composite highly-absorbent resin is comprised of according to following quality proportioning following raw materials according: 100 parts in vinylformic acid; 20～25 parts of Zulkovsky starches; 10～15 parts of sodium alginates; 30～40 parts of acrylamides; 0.1～0.5 part of Potassium Persulphate; 5～10 parts of kaolin; 10～15 parts of alkaline solutions.
Described Zulkovsky starch adopts W-Gum, wheat starch, Starch rice, sweet potato starch or yam starch.
Described initiator is Potassium Persulphate.
Described alkaline solution is potassium hydroxide, sodium hydroxide or magnesium hydroxide solution.
Starch can adopt W-Gum, wheat starch, Starch rice, sweet potato starch or yam starch, wide material sources, and price is lower.
Marine alga is as the oceanic resources that output is large, value is low, regenerative power is strong, if be applied in the water-absorbing resin, being expected increases a kind of new natural function marine organisms degradable substance for Material Field.Sodium alginate and acrylic acid mixture are under the initiation of Potassium Persulphate, and the H in the acrylic molecules on the hydroxyl carbon atom is seized and produces free radical.Re-initiation sodium acrylate and kaolin generate sodium alginate-sodium acrylate/kaolin free radical, thereby carry out chain growth polymerization with sodium acrylate, last chain termination, and sodium acrylate also can produce free radical simultaneously, carries out the homopolymerization of sodium acrylate.
Starch is added sodium alginate and acrylic acid polymerization system, and as sodium alginate and acrylic acid linking agent, the Salt Tolerance for Super Absorbent Polymers that makes can be good with starch, and water absorbing properties is high.
Major advantage of the present invention and beneficial effect are:
(1) because native starch is cheap, wide material sources, the degradable plastics film of preparation has higher economic worth and social value;
(2) starch is added sodium alginate and acrylic acid polymerization system, as sodium alginate and acrylic acid linking agent, the Salt Tolerance for Super Absorbent Polymers that makes can be good with starch, and water absorbing properties is high;
(3) the degradable plastics membrane preparation method is simple, easy handling.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment one:
Prepare raw material by following quality proportioning: 100 parts in vinylformic acid; 20 parts of Zulkovsky starches; 15 parts of sodium alginates; 30 parts of acrylamides; 0.1 part of Potassium Persulphate; 5 parts of kaolin; 10 parts of potassium hydroxide solutions;
Vinylformic acid, Zulkovsky starch, potassium hydroxide solution and sodium alginate are at room temperature stirred, and reaction 30min gets polymeric solution;
Polymeric solution is added acrylamide, Potassium Persulphate, kaolin, put into 150 ℃ of baking oven reaction 5h after stirring, the block product that obtains is pulverized, sieving namely gets High hydrophilous resin.
Embodiment two:
Prepare raw material by following quality proportioning: 100 parts in vinylformic acid; 25 parts of Zulkovsky starches; 10 parts of sodium alginates; 40 parts of acrylamides; 0.2 part of Potassium Persulphate; 6 parts of kaolin; 12 parts of magnesium hydroxide solution;
Vinylformic acid, Zulkovsky starch, magnesium hydroxide solution and sodium alginate are at room temperature stirred, and reaction 30min gets polymeric solution;
Polymeric solution is added acrylamide, Potassium Persulphate, kaolin, put into 150 ℃ of baking oven reaction 5h after stirring, the block product that obtains is pulverized, sieving namely gets High hydrophilous resin.
Embodiment three:
Prepare raw material by following quality proportioning: 100 parts in vinylformic acid; 24 parts of Zulkovsky starches; 12 parts of sodium alginates; 35 parts of acrylamides; 0.5 part of Potassium Persulphate; 8 parts of kaolin; 15 parts of sodium hydroxide solutions;
Vinylformic acid, Zulkovsky starch, sodium hydroxide solution and sodium alginate are at room temperature stirred, and reaction 30min gets polymeric solution;
Polymeric solution is added acrylamide, Potassium Persulphate, kaolin, put into 150 ℃ of baking oven reaction 5h after stirring, the block product that obtains is pulverized, sieving namely gets High hydrophilous resin.
Embodiment four:
Prepare raw material by following quality proportioning: 100 parts in vinylformic acid; 24 parts of Zulkovsky starches; 14 parts of sodium alginates; 36 parts of acrylamides; 0.4 part of Potassium Persulphate; 7 parts of kaolin; 11 parts of magnesium hydroxide solution;
Vinylformic acid, Zulkovsky starch, alkaline solution and sodium alginate are at room temperature stirred, and reaction 30min gets polymeric solution;
Polymeric solution is added acrylamide, Potassium Persulphate, kaolin, put into 150 ℃ of baking oven reaction 5h after stirring, the block product that obtains is pulverized, sieving namely gets High hydrophilous resin.
Take by weighing dry High hydrophilous resin sample, place and fill the beaker that certain volume concentration is 0.9% physiological saline, inhale saturated after, after 20 order mesh screens sieves removes unnecessary water, claim whole gel quality affects, press Q=(m2-m1)/m1 calculates water absorbent rate or suction salt solution multiplying power.Wherein Q is suction (salt) the water multiplying power (g/g) of High hydrophilous resin; M1 is the quality (g) of compound salt tolerant SAR dry-eye disease; M2 is the quality (g) of gel behind compound salt tolerant High hydrophilous resin suction (salt) water.
Test result demonstration, the water absorbent rate of High hydrophilous resin of the present invention are inhaled the physiological saline multiplying power at 98～110g/g at 890～960g/g, and water absorbing properties is good.
In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop on the protection domain of requirement of the present invention.
Claims (4)
1. starch/vinylformic acid composite highly-absorbent resin is characterized in that being comprised of according to following quality proportioning following raw materials according: 100 parts in vinylformic acid; 20～25 parts of Zulkovsky starches; 10～15 parts of sodium alginates; 30～40 parts of acrylamides; 0.1～0.5 part of Potassium Persulphate; 5～10 parts of kaolin; 10～15 parts of alkaline solutions.
2. starch according to claim 1/vinylformic acid composite highly-absorbent resin is characterized in that: described Zulkovsky starch employing W-Gum, wheat starch, Starch rice, sweet potato starch or yam starch.
3. starch according to claim 1/vinylformic acid composite highly-absorbent resin, it is characterized in that: described initiator is Potassium Persulphate.
4. starch according to claim 1/vinylformic acid composite highly-absorbent resin, it is characterized in that: described alkaline solution is potassium hydroxide, sodium hydroxide or magnesium hydroxide solution.
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| CN2012104800543A CN103059224A (en) | 2012-11-23 | 2012-11-23 | Starch/acrylic acid composite super-absorbent resin |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153364A (en) * | 2015-08-25 | 2015-12-16 | 中国地质科学院郑州矿产综合利用研究所 | Brucite composite water absorbent and preparation method thereof |
| CN106916265A (en) * | 2017-04-27 | 2017-07-04 | 安庆师范大学 | One kind is based on modified broad bean powder, kaolin, the preparation method of the compound high absorbency material of acrylic acid |
| CN106947025A (en) * | 2017-04-27 | 2017-07-14 | 安庆师范大学 | A kind of preparation method based on starch graft acrylic acid and the compound water-keeping gel of sodium alginate, slag |
| CN110607177A (en) * | 2019-10-24 | 2019-12-24 | 成都新柯力化工科技有限公司 | Soil water-retaining agent for saline-alkali soil and preparation method thereof |
| CN112724443A (en) * | 2020-12-25 | 2021-04-30 | 宁波大榭开发区综研化学有限公司 | Hydrophilic membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266178C (en) * | 2004-04-21 | 2006-07-26 | 东华理工学院 | Method for preparing super high water uptake resin of copolymerization of acrylic ester grafted from sodium alginate |
| CN102372892A (en) * | 2010-08-17 | 2012-03-14 | 上海众伟生化有限公司 | Starch grafting acrylic acid compound water-retaining agent and production method thereof |
-
2012
- 2012-11-23 CN CN2012104800543A patent/CN103059224A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1266178C (en) * | 2004-04-21 | 2006-07-26 | 东华理工学院 | Method for preparing super high water uptake resin of copolymerization of acrylic ester grafted from sodium alginate |
| CN102372892A (en) * | 2010-08-17 | 2012-03-14 | 上海众伟生化有限公司 | Starch grafting acrylic acid compound water-retaining agent and production method thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105153364A (en) * | 2015-08-25 | 2015-12-16 | 中国地质科学院郑州矿产综合利用研究所 | Brucite composite water absorbent and preparation method thereof |
| CN106916265A (en) * | 2017-04-27 | 2017-07-04 | 安庆师范大学 | One kind is based on modified broad bean powder, kaolin, the preparation method of the compound high absorbency material of acrylic acid |
| CN106947025A (en) * | 2017-04-27 | 2017-07-14 | 安庆师范大学 | A kind of preparation method based on starch graft acrylic acid and the compound water-keeping gel of sodium alginate, slag |
| CN110607177A (en) * | 2019-10-24 | 2019-12-24 | 成都新柯力化工科技有限公司 | Soil water-retaining agent for saline-alkali soil and preparation method thereof |
| CN112724443A (en) * | 2020-12-25 | 2021-04-30 | 宁波大榭开发区综研化学有限公司 | Hydrophilic membrane and preparation method thereof |
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Application publication date: 20130424 |