CN100415786C - Super electrolyte resistant high water absorption resin and its prepn - Google Patents
Super electrolyte resistant high water absorption resin and its prepn Download PDFInfo
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- CN100415786C CN100415786C CNB2005100950908A CN200510095090A CN100415786C CN 100415786 C CN100415786 C CN 100415786C CN B2005100950908 A CNB2005100950908 A CN B2005100950908A CN 200510095090 A CN200510095090 A CN 200510095090A CN 100415786 C CN100415786 C CN 100415786C
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Abstract
The present invention discloses a super electrolyte resistance high water absorption resin. The water absorption of the resin to distilled water is greater than 600g water/g resin, the water absorption of the resin to tap water is greater than 250g water/g resin, and the water absorption of the resin to tap water with 0.9% of sodium chloride is greater than 100g water/g resin. The preparation method of the resin comprises: water soluble cellulose, acrylamide and cationoid ethene polymerization monomers are mixed in water to form a mixing reaction system; the pH value of the reaction system is adjusted, and a radical polymerization initiating agent and a non-ionic crosslinking agent are added; after a graft copolymerization reaction, the electrolyte resistance high water absorption resin is obtained through dewatering, drying and pulverizing processing. The present invention has the advantages of low cost, environmental protection, strong electrolyte resistance capability, strong absorbing capacity, high gel strength, few soluble ingredient and strong enzymolysis resistance.
Description
Technical field
The present invention relates to a kind of High hydrophilous resin and preparation method thereof, relate in particular to a kind of super electrolyte resistant high water absorption resin and preparation method thereof.
Background technology
High hydrophilous resin is called super strength water absorbent (super absorbent polymer, be called for short SAP) again, is the field of polymer technology class type material that obtains developing rapidly in recent years.It is a kind ofly contain the strongly hydrophilic group, and through appropriately crosslinked functional high molecule material, can absorb the water of himself quality hundred times even thousands of times at short notice, and have good water retention property.At first succeed in developing the sixties from the U.S., carry out corn the seventies, the soybean seeds coating test is achieved success and in agricultural after the application, multiple super absorbent resin (disclosing 467073,478150,454497 etc. as United States Patent (USP) 3980663,4093776,4954562,4880858 and european patent application) is competitively developed in countries in the world, and has obtained to use widely at aspects such as physiological hygiene, agriculture and garden, civil construction.
Press the difference of raw material sources, SAP generally is divided into three major types such as synthetic resins system, starch-grafted system and cellulose graft system.Because the reaction of synthetic resins system is easy to realize and water-intake rate is higher, suitability for industrialized production is many based on synthesizing series, but the resin residue vinylformic acid that makes thus is unfavorable for HUMAN HEALTH, and is difficult for being belonged to the non-ambient friendly materials by biological degradation; Super absorbent resin suction and water retention height that starch graft copolymer is produced also have been used for suitability for industrialized production, but there is low, the easy mould shortcoming such as separate of gel-strength in starch system; Cellulose-based then because of the gel-strength height, solvable composition is few, and anti-mildew is separated the attention that ability has caused people by force, adds the Mierocrystalline cellulose wide material sources, have reduce cost, changing waste into resources and become the potentiality of environment-friendly material, be expected to become the new focus of super absorbent resin research and development.
Because the shortcoming of present High hydrophilous resin ubiquity electrolyte-resistant poor performance, the SAP contact nearly all is solion in actual applications, and therefore, improving SAP electrolyte-resistant ability is urgent problem.
Chinese patent 00119689.8 discloses and has been entitled as " High hydrophilous resin and production method thereof "; this method is to be raw material with high amylopectin starch, vinylformic acid and acrylamide; after starch pasting; under nitrogen protection; copolyreaction takes place in vinylformic acid, acrylamide, initiator and the linking agent etc. that add certain degree of neutralization.After reaction proceeds to certain hour, under nitrogen protection, reaction mixture is transferred to removes moisture in the drying plant, carry out aftertreatment again, obtain High hydrophilous resin.Although claiming this water-absorbing resin, this patent strong water-retaining capacity is arranged to containing ionic water, but only provide water regain to distilled water and tap water, do not provide water regain to 0.9% sodium chloride aqueous solution, and index is not high, being 340～380 gram water/gram resins to the water regain of distilled water in the example, is 155～190 to restrain water/gram resins to the water regain of tap water.
Summary of the invention
The present invention proposes a kind of low cost, environmental protection, the electrolyte-resistant ability is strong, receptivity is strong super electrolyte resistant high water absorption resin and preparation method.
The present invention adopts following technical scheme:
A kind of super electrolyte resistant water-absorbing resin, it is characterized in that this resin restrains water/gram resins to the water regain of distilled water greater than 600, the water regain of tap water greater than 250 gram water/gram resins, is restrained water/gram resins to the water regain of 0.9% sodium-chlor polymer solution in water greater than 100.
A kind of preparation method of super electrolyte resistant water-absorbing resin may further comprise the steps:
The first step, mixing water cellulose of solubleness in water, acrylamide and cationic ethylenic polymer monomer, water soluble cellulose accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 5～30%, acrylamide accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 20～65%, cationic ethylenic polymer monomer accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 10～50%, form the hybrid reaction system after mixing, the material in the hybrid reaction system except water accounts for 20～50% of hybrid reaction system total mass;
Second step, after adjusting pH value to 3～6 of above-mentioned reaction system, add 0.5～3% the radical polymerization initiator account for acrylamide and cationic ethylenic polymer monomer total mass and account for 0.1～0.6% non-ionic type linking agent of acrylamide and cationic ethylenic polymer monomer total mass, make water soluble cellulose, acrylamide and cationic ethylenic polymer monomer generation graft copolymerization, the graft copolymerization temperature is 45～70 ℃, and the reaction times is 20～90 minutes.
In the 3rd step, after reaction finishes,, obtain electrolyte resistant high water absorption resin through dehydration, dry, pulverization process.
The present invention obtains following technique effect:
(1) the cellulose-based High hydrophilous resin of the present invention has the gel-strength height, and solvable composition is few, and anti-mildew is separated the strong advantage of ability.
(2) because of the Mierocrystalline cellulose wide material sources, the present invention can reduce cost, changing waste into resources and become environment-friendly material
(3) roll into a ball and the cellulosic structure unit owing in molecule, introducing positively charged ion and non-ionic hydrophilic simultaneously, thereby make institute of the present invention synthetic High hydrophilous resin have good electrolyte-resistant performance and biodegradability simultaneously.
(4) because Mierocrystalline cellulose is a natural reproducible resource with low cost, in petroleum resources exhausted day by day today, be applied to preparing super absorbent resin by graft copolymerization, can produce favorable economic benefit and social ecological benefits.
Cellulose-based High hydrophilous resin has the gel-strength height, solvable composition is few, anti-mildew is separated the strong advantage of ability, add the Mierocrystalline cellulose wide material sources, have reduce cost, changing waste into resources and become the potentiality of environment-friendly material, so cellulose-based High hydrophilous resin progressively becomes the new focus of super absorbent resin research and development.
Institute of the present invention synthetic High hydrophilous resin, owing in molecule, introduce positively charged ion and non-ionic hydrophilic group and cellulosic structure unit simultaneously, thus make the synthetic High hydrophilous resin have good electrolyte-resistant performance and biodegradability simultaneously.Adding Mierocrystalline cellulose is natural reproducible resource with low cost, in petroleum resources exhausted day by day today, is applied to preparing super absorbent resin by graft copolymerization, is expected to produce favorable economic benefit and social ecological benefits.
By the water-absorbing resin that aforesaid method makes, adopt the tea bag weighting method to measure its every gram resin water regain.Water regain to distilled water is calculated with following formula:
M in the formula
1Be the quality of dry resin before not absorbing water, g; m
2Be resin gel quality behind the suction distilled water, g;
Measuring method for the physiological saline water regain of tap water and 0.9% is the same.
Embodiment
Embodiment 1
A kind of super electrolyte resistant water-absorbing resin, this resin greater than 600 gram water/gram resins, greater than 250 gram water/gram resins, restrain water/gram resins to the water regain of 0.9% sodium-chlor polymer solution in water greater than 100 to the water regain of tap water to the water regain of distilled water.
Embodiment 2
A kind of preparation method of super electrolyte resistant water-absorbing resin may further comprise the steps:
The first step, mixing water cellulose of solubleness in water, acrylamide and cationic ethylenic polymer monomer, water soluble cellulose accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 5～30%, for example can for: 6%, 8%, 12%, 15%, 19%, 21%, 24%, 27.5%, acrylamide accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 20～65%, for example can for: 22%, 27%, 32%, 35%, 37%, 42%, 48%, 53%, 57%, 62%, cationic ethylenic polymer monomer accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 10～50%, for example can be 12%, 18%, 22%, 25%, 26%, 28%, 35%, 42%, 44%, 48%, form the hybrid reaction system after mixing, the material in the hybrid reaction system except water accounts for 20～50% of hybrid reaction system total mass;
Second step, adjust pH value to 3～6 of above-mentioned reaction system after, for example 4,5, add 0.5～3% the radical polymerization initiator account for acrylamide and cationic ethylenic polymer monomer total mass, per-cent can be 0.7%, 1.1%, 1.4%, 1.8%, 2.1%, 2.3%, 2.7%, 2.9%, add 0.1～0.6% the non-ionic type linking agent account for acrylamide and cationic ethylenic polymer monomer total mass, for example per-cent can be 0.22%, 0.3%, 0.45%, 0.52%, make water soluble cellulose, acrylamide and cationic ethylenic polymer monomer generation graft copolymerization, the graft copolymerization temperature is 45～70 ℃, for example can be 48 ℃, 53 ℃, 62 ℃, 68 ℃, reaction times is 20～90 minutes, for example can the position 25 minutes, 32 minutes, 44 minutes, 52 minutes, 65 minutes, 79 minutes, 83 minutes.
In the 3rd step, after reaction finishes,, obtain electrolyte resistant high water absorption resin through dehydration, dry, pulverization process.
In the present embodiment, used water soluble cellulose is water soluble celluloses such as carboxymethyl cellulose, Natvosol; Cationic ethylenic polymer monomer comprises dimethylaminoethyl acrylate methyl ammonia ethyl ester and quaternary ammonium salt derivative (as the methylacryoyloxyethyl trimethyl ammonium chloride) thereof; Described radical polymerization initiator is water-soluble radical polymerization initiator, as ceric ammonium nitrate, ammonium persulphate, Potassium Persulphate, hydrogen peroxide, wherein peroxidation class initiator is used separately or with S-WAT, ferrous sulfate, L-xitix, obtains redox initiator; Used non-ionic type linking agent is N, and N '-methylene-bisacrylamide, ethylene glycol bis glycidyl ether, or polyvalent alcohol are as ethylene glycol, glycerol, Sorbitol Powder, trolamine, polyoxyethylene glycol.
Embodiment 3
Take by weighing 10 gram carboxymethyl celluloses, 45 gram acrylamides, 55 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 0.4 gram N, N '-methylene-bisacrylamide, add 180ml distilled water, abundant stirring and dissolving, dilute hydrochloric acid solution with 3% is adjusted into 4 with its pH, adds 1.37 gram ammonium persulphates, 0.63 gram sodium bisulfite again.Under nitrogen protection, 60 ℃ were reacted 45 minutes, and after the product cooling, dry, pulverizing gets the powdery, water-absorbent resin.
Product in the present embodiment (water-absorbing resin 1) is a white powder, measures with the tea bag weighting method, and every gram resin is inhaled distilled water 602 grams, inhales tap water 257 grams, to water regain 112 grams of 0.9% sodium chloride aqueous solution.
Embodiment 4
Take by weighing 7.5 gram carboxymethyl celluloses, 50 gram acrylamides, 50 gram dimethylaminoethyl acrylate methyl ammonia ethyl esters and 0.35 gram ethylene glycol bis glycidyl ether, add 250ml distilled water, abundant stirring and dissolving, dilute hydrochloric acid solution with 3% is adjusted into 4 with its pH, adds 2.025 gram Potassium Persulphates, 1.337 gram L-xitix again.Under nitrogen protection, 55 ℃ were reacted 60 minutes, and after the product cooling, dry, pulverizing gets the powdery, water-absorbent resin.
Product in the present embodiment (water-absorbing resin 2) is a white powder, measures with the tea bag weighting method, and every gram resin is inhaled distilled water 625 grams, inhales tap water 261 grams, inhales 0.9% sodium chloride aqueous solution, 113 grams.
Embodiment 5
Take by weighing 6 gram Natvosols, 65 gram acrylamides, 35 gram methylacryoyloxyethyl trimethyl ammonium chlorides and 0.4 gram polyoxyethylene glycol, add 210ml distilled water, abundant stirring and dissolving, dilute hydrochloric acid solution with 3% is adjusted into 4 with its pH, adds 0.209 gram hydrogen peroxide, 0.877 gram ferrous sulfate again.Under nitrogen protection, 65 ℃ were reacted 90 minutes, and after the product cooling, dry, pulverizing gets the powdery, water-absorbent resin.
Product in the present embodiment (water-absorbing resin 3) is a white powder, measures with the tea bag weighting method, and every gram resin is inhaled distilled water 639 grams, inhales tap water 265 grams, to water regain 117 grams of 0.9% sodium chloride aqueous solution.
The water absorbing properties of resulting super absorbent resin fat prod among the above embodiment, the suction distilled water that obviously is better than High hydrophilous resin among Chinese patent 00119689.8 embodiment are that 340～380 gram water/gram resins, suction tap water are the water absorbing properties of 155～190 gram water/gram resins.
Claims (4)
1. the preparation method of a super electrolyte resistant water-absorbing resin is characterized in that may further comprise the steps:
The first step, mixing water cellulose of solubleness in water, acrylamide and cationic ethylenic polymer monomer, water soluble cellulose accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 5～30%, acrylamide accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 20～65%, cationic ethylenic polymer monomer accounts for water soluble cellulose, the per-cent of acrylamide and cationic ethylenic polymer monomer three total mass is 10～50%, form the hybrid reaction system after mixing, the material in the hybrid reaction system except water accounts for 20～50% of hybrid reaction system total mass;
Second step, after adjusting pH value to 3～6 of above-mentioned reaction system, add 0.5～3% the radical polymerization initiator account for acrylamide and cationic ethylenic polymer monomer total mass and account for 0.1～0.6% non-ionic type linking agent of acrylamide and cationic ethylenic polymer monomer total mass, make water soluble cellulose, acrylamide and cationic ethylenic polymer monomer generation graft copolymerization, the graft copolymerization temperature is 45～70 ℃, and the reaction times is 20～90 minutes;
In the 3rd step, after reaction finishes,, obtain electrolyte resistant high water absorption resin through dehydration, dry, pulverization process.
2. the preparation method of super electrolyte resistant water-absorbing resin according to claim 1 is characterized in that radical polymerization initiator is hydrogen peroxide and ferrous sulfate.
3. the preparation method of super electrolyte resistant water-absorbing resin according to claim 1 is characterized in that cationic ethylenic polymer monomer is a dimethylaminoethyl acrylate methyl ammonia ethyl ester.
4. according to the preparation method of claim 1 super electrolyte resistant water-absorbing resin, it is characterized in that the non-ionic type linking agent is the ethylene glycol bis glycidyl ether.
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| CNB2005100950908A CN100415786C (en) | 2005-10-28 | 2005-10-28 | Super electrolyte resistant high water absorption resin and its prepn |
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| CNB2005100950908A CN100415786C (en) | 2005-10-28 | 2005-10-28 | Super electrolyte resistant high water absorption resin and its prepn |
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| CN100415786C true CN100415786C (en) | 2008-09-03 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196334A (en) * | 1997-04-11 | 1998-10-21 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
| US6174978B1 (en) * | 1997-12-10 | 2001-01-16 | Nippon Shokubai Co., Ltd. | Production process of water-absorbent resin |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1196334A (en) * | 1997-04-11 | 1998-10-21 | 广州市环境保护科学研究所 | Method for preparing cation/amphoteric graft polyacrylamide flocculating agent |
| US6174978B1 (en) * | 1997-12-10 | 2001-01-16 | Nippon Shokubai Co., Ltd. | Production process of water-absorbent resin |
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Owner name: JIANGSU QIANGLIN BIOLOGY ENERGY CO., LTD. Free format text: FORMER OWNER: FOREST PRODUCTS CHEMICAL INDUSTRY INST., CHINA FORESTRY SCIENCE RESEARCH ACADEMY Effective date: 20121228 |
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Effective date of registration: 20121228 Address after: 213300 Liyang City, Jiangsu province Nandu town strong strong port town Road No. 88 Patentee after: Jiangsu Qianglin Biology Energy Co., Ltd. Address before: Five suojin village of Nanjing city in Jiangsu province 210042 No. 16 Patentee before: Institute of Chemical Industry of Forest Products, Chinese Academy of Forestry |
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