CN1087749C - Polyacrylate type high water absorption resin - Google Patents
Polyacrylate type high water absorption resin Download PDFInfo
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- CN1087749C CN1087749C CN 97104129 CN97104129A CN1087749C CN 1087749 C CN1087749 C CN 1087749C CN 97104129 CN97104129 CN 97104129 CN 97104129 A CN97104129 A CN 97104129A CN 1087749 C CN1087749 C CN 1087749C
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Abstract
The present invention relates to high water absorption resin with the advantages of strong water absorbing capacity, high gel strength and high speed of water absorption. The application performance of the high water absorption resin is improved through the cross-linking copolymerization of acrylic acid, sodium acrylate and at least one another functional monomer and then chemical surface treatment.
Description
The invention relates to a kind of synthetic method of crosslinked salt polyacrylate class High hydrophilous resin, and improve its application performance by the chemical conversion treatment method.Specifically, be to be main raw material with vinylformic acid, sodium acrylate and other at least a functional monomer, through the crosslinking copolymerization reaction, carry out chemical conversion treatment with hydrophilic surface linking agent and the formulated mixing solutions of small molecules organic solvent then, finally obtain the High hydrophilous resin that water-retaining capacity is strong, gel-strength is high, absorption speed is fast.
Water-absorbing resin is succeeded in developing in 1969 by USDA north institute at first, and method is with W-Gum and acrylonitrile graft copolymer, uses sodium hydroxide hydrolysis again.Because this method adopts the very strong acrylonitrile monemer of toxicity, Japan replaced vinyl cyanide with vinylformic acid afterwards, again with the direct graft polymerization of starch.After this, various water-absorbing resins (for example United States Patent (USP) No. 3980663, No. 4093776, No. 4954562, No. 4880858 and european patent application disclose No. 467073, No. 478150, No. 454497 etc.) have been developed in the U.S., Japan, Europe in succession.Water-absorbing resin is at the physiological hygiene articles for use, medical material, and fields such as agricultural and gardening, agricultural chemicals, chemical fertilizer, petrochemical complex, daily-use chemical industry, fresh keeping product, foodstuffs industry, civil construction, textiles have obtained to use widely.
At present, the Application Areas of water-absorbing resin maximum is a personal hygiene article, such as: various suction articles for use such as Children's diaper, sanitary napkin.By adding a spot of water-absorbing resin, can improve its liquid retention characteristic, and reduce the fluid seepage amount, and can make sanitary towel or diaper become thinner, lighter, use more convenient comfortable.Secondly, water-absorbing resin can be used as water-loss reducer of soil on agricultural gardening, for example: add the water-absorbing resin of 0.1% (weight) in soil, can make soil have suff water required for plant in the long period, improve crop yield.In afforestation, deserted mountain transformation, desert afforestation, can utilize water-absorbing resin to keep soil moisture, improve plant germination and surviving rate.In addition, aspect building, water-absorbing resin can be used as impervious leakage-stopping agent, anti-caking distillate medicinal water; On petrochemical complex, be used as oil-water separating agent; Unemployed at textiles, be used to make anti-undershirt, Sweat-proof shoes pad etc.; In filed of daily-use chemical industry, can be used as and make slow releasing pharmaceutical, release controlled fertilizer, reodorant and change shape product etc.
After using common water-absorbing resin, it is found that the suction articles for use absorb such as behind the body fluid such as urine, blood, secretory product, formed gel is easily broken and make this articles for use distortion, thereby the liquid retention characteristic that causes these articles for use reduces and the fluid seepage amount increases, and makes the wearer feel uncomfortable.Therefore, need that development is a kind of to have water-absorbing resin than high gel stability to body fluid.In addition, normally used water-absorbing resin is prone to after its suction or moisture absorption " flake ", i.e. gel blockage effect, thereby hindered its further suction, thus reduced absorption speed.Therefore, be necessary to develop the fast water-absorbing resin of a kind of absorption speed.
In view of the foregoing, the present inventor in depth studies.Usually, pure polyacrylate type water-absorbing resin has higher suction multiple, but its gel-strength is not high.Discover that when adding another functional monomer, the water-absorbing resin as obtaining behind the maleic anhydride participation copolymerization not only has very high suction multiple, and suction back gel-strength improves.In addition, after the solution formulated with hydrophilic surface linking agent and hydrophilic small molecules organic solvent carried out chemical conversion treatment to water-absorbing resin, absorption speed obviously improved, thereby has improved its application performance.
That is to say that first purpose of the present invention provides the strong novel crosslinked salt polyacrylate type water-absorbing resin of a kind of water-retaining capacity.After tested, the ability that water-absorbing resin provided by the invention absorbs 0.9% physiological saline surpasses 70 times, and the ability of similar absorption of sample 0.9% physiological saline that Japanese catalyst chemical company provides only is 47 times.
Second purpose of the present invention provides a kind of to have the water-absorbing resin of high gel stability such as body fluid such as urine, blood, secretory product.
Another object of the present invention provides a kind of fast water-absorbing resin of absorption speed that has.
Describe these purposes of the present invention below in detail:
In first purpose of the present invention, provide a kind of synthetic method of novel polyacrylate type high water absorption resin.This novel polyacrylate type high water absorption resin carries out the crosslinking copolymerization reaction by vinylformic acid, sodium acrylate and other at least a functional monomer and obtains.Specific embodiment is: at first vinylformic acid is mixed with certain aqueous solution, neutralizes with alkali lye then.Neutralization finishes, and adds another functional monomer, adds linking agent again, is warming up to certain temperature of reaction, under nitrogen protection, adds initiator and carries out the crosslinking copolymerization reaction.Acrylic acid concentration is 15～40% (weight) in the above-mentioned reaction system, and the vinylformic acid degree of neutralization is 70～85%.Neutralizing agent is selected sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate or ammoniacal liquor for use.Another functional monomer is selected from methyl acrylate, ethyl propenoate, butyl acrylate, (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, (methyl) acrylamide, methylene-succinic acid, fumaric acid, methacrylic acid, toxilic acid (acid anhydride), vinyl sulfonic acid etc.The add-on of this functional monomer is 0.5～50% (weight) of vinylformic acid consumption.
In the above-mentioned crosslinking copolymerization reaction, used linking agent is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, a condensed ethandiol double methacrylate, tirethylene glycol double methacrylate, 1, ammediol double methacrylate, Viscoat 295, pentaerythritol triacrylate, glycidyl methacrylate, polyoxyethylene glycol double methacrylate.The consumption of linking agent has remarkable influence to the water-intake rate of final product.This is that polymkeric substance fails to form three-dimensional net structure because when dosage of crosslinking agent is very few, and macroscopical upper surface is water miscible, so water-intake rate is not high.But when dosage of crosslinking agent was too high, cross-linking set increased in the polymer ions network structure, and cross-linking density is excessive, caused that micropore diminishes in the network structure, so water-intake rate descends.The suitable consumption of linking agent is 0.05～2.0% (weight) of vinylformic acid consumption.
In the synthetic method of above-mentioned water-absorbing resin, used initiator comprises two kinds of Oxidizing and Reducing Agents.Oxygenant is selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate.Reductive agent is selected from S-WAT, sodium bisulfite, V-Brite B, Sulfothiorine, formaldehyde and closes Sodium Thiosulfate.The consumption of initiator also has than remarkable influence the water-intake rate of water-absorbing resin, because its consumption is directly connected to the molecular weight and the cross-linking density of polymkeric substance.Discover that the suitable consumption of oxygenant is 0.01～0.5% (weight) of vinylformic acid consumption, the suitable consumption of reductive agent is 0.02～0.75% (weight) of vinylformic acid consumption.
In above-mentioned crosslinking copolymerization reaction process, polymerization temperature is controlled at 35～65 ℃, and polymerization reaction time is 10～60 minutes, and be 1～4 hour time of drying, and drying temperature is 100～190 ℃.
In second purpose of the present invention, provide a kind of body fluid to have the water-absorbing resin of high gel stability to human body.In order to improve gel-strength, common way is to improve the crosslink density of water-absorbing resin.But when crosslink density increased, the suction multiple also can correspondingly reduce.Therefore, during actual the use, need to increase the consumption of water-absorbing resin, thereby be uneconomic.The High hydrophilous resin of the present invention's development participates in copolymerization by adding another functional monomer, the multiple height that not only absorbs water, and improved gel-strength, thereby to having high gel stability such as body fluid such as urine, blood, secretory product.
Another object of the present invention provides a kind of fast water-absorbing resin of absorption speed that has.Normally used water-absorbing resin after its suction or moisture absorption, easily produces " flake ", i.e. gel blockage effect, thus hindered its further suction, so absorption speed is slower.The present invention improves its absorption speed by water-absorbing resin is carried out chemical conversion treatment, and the reagent that wherein is used for chemical conversion treatment comprises: hydrophilic surface linking agent and hydrophilic small molecules organic solvent.The hydrophilic surface linking agent is selected from following at least a compound: poly-hydroxy alcohols, poly-hydroxy amine, poly epihydric alcohol ethers, polynary amine and polyvalent metal compounds class.The hydrophilic small molecules organic solvent is to be selected from one of following compound: methyl alcohol, ethanol, Virahol, propyl carbinol, acetone, positive butanone, 2-butanone.Water-absorbing resin is carried out the surface-treated detailed process is, at first a certain proportion of hydrophilic surface linking agent and small molecules organic solvent and an amount of water is mixed, and promptly obtains the surface crosslinking agent mixing solutions.Take by weighing the water-absorbent resin powder of quantitative aforementioned preparation then, and the surface crosslinking agent mixing solutions for preparing is under agitation slowly splashed in the water-absorbent resin powder.Make the resinous powder particles surface evenly cover the layer of surface linking agent, wherein the suitable consumption of hydrophilic surface linking agent and small molecules organic solvent is respectively 0.005～5% and 0.01～10% (by weight) of water-absorbing resin.Then, place 150～190 ℃ of baking ovens to carry out surface-crosslinked reaction the water-absorbing resin of so handling, the time was controlled at 20～45 minutes.Take out postcooling, and to be ground into granularity be 5～15 μ m water-absorbent resin powders.
By the water-absorbing resin that aforesaid method obtains, test its suction multiple and absorption speed with the tea bag method, the suction multiple calculates with following formula:
Used time representation when absorption speed then absorbs liquid and reaches capacity with resin.
Gel-strength is then represented with the peak pressure that resin suction back gel is born.
Describe the present invention in detail below in conjunction with embodiment:
Embodiment one:
Take by weighing 100g vinylformic acid, place three mouthfuls of reaction flasks that have thermometer, add the 180g deionized water then.Adding 100g concentration under stirring in 30 minutes is the sodium hydroxide solution of 30% (weight).Be warmed up to 60 ℃, add 6g acrylamide and 0.5g one condensed ethandiol double methacrylate, logical nitrogen 10 minutes is to evict dissolved oxygen from.Add the 0.1g ammonium persulphate then.After 2 minutes, add 0.15g Sulfothiorine again, continue stirring reaction after 30 minutes, reaction mixture is placed 130 ℃ of vacuum drying ovens, dry 3 hours.Cool off then, pulverize, obtain water-absorbent resin powder.
Get above-mentioned water-absorbent resin powder 50g, carry out chemical conversion treatment.At first 0.5g glycerol, 1.0g acetone and 5g deionized water are mixed, promptly obtain the surface crosslinking agent mixing solutions.This mixing solutions is under agitation slowly splashed in the above-mentioned 50g water-absorbent resin powder, make the resinous powder particles surface evenly cover the layer of surface linking agent.Be placed on then in 150 ℃ of vacuum drying ovens and carry out surface-crosslinked reaction, the time is 30 minutes.Cool off, be ground into the water-absorbing resin that granularity is 5～15 μ m.Test its ability that absorbs 0.9% normal saline solution, absorption speed and gel-strength respectively, the results are shown in subordinate list.
Embodiment two:
Take by weighing 100g vinylformic acid, place three mouthfuls of reaction flasks that have thermometer, add the 200g deionized water then.Adding 90g concentration under stirring in 30 minutes is the sodium hydroxide solution of 30% (weight).Be warming up to 55 ℃, add 4g maleic anhydride and 4g ethyl propenoate and 1.0g Viscoat 295.Logical nitrogen 10 minutes is to evict dissolved oxygen from.Add the 0.14g Potassium Persulphate then.After 3 minutes, add the 0.18g sodium bisulfite again.Behind the stirring reaction 45 minutes, reaction mixture is placed 150 ℃ of vacuum drying ovens, dry 2.5 hours.Cool off then, pulverize, obtain water-absorbent resin powder.
Get above-mentioned water-absorbent resin powder 50g, carry out chemical conversion treatment.At first 0.3g thanomin, the positive butanone of 1.5g and 4g deionized water are mixed, promptly obtain the surface crosslinking agent mixing solutions.This mixing solutions is under agitation slowly splashed in the above-mentioned 50g water-absorbent resin powder, make the resinous powder particles surface evenly cover the layer of surface linking agent.Be placed on then in 170 ℃ of vacuum drying ovens and carry out surface-crosslinked reaction, the time is 25 minutes.Cool off, be ground into the water-absorbing resin that granularity is 5～15 μ m.Test its ability that absorbs 0.9% normal saline solution, absorption speed and gel-strength respectively, the results are shown in subordinate list.Subordinate list: water-absorbing resin The performance test results
| The test event results sample | [annotating 1] suction multiple (g/g) | [annotating 2] absorption speed (second) | [annotating 3] gel-strength (kg/cm 2) |
| Embodiment one | 78 | 170 | 3.2 |
| Embodiment two | 72 | 150 | 2.8 |
[notes]:
1. the suction multiple is tested with the tea bag method.Absorbing medium is 0.9% normal saline solution.
2. used time representation when absorption speed absorbs liquid and reaches capacity with resin.
3. gel-strength is meant the peak pressure that gel bore after resin fully absorbs water.
Claims (9)
1, a kind of preparation method of polyacrylate type high water absorption resin is characterized in that at first vinylformic acid being mixed with the aqueous solution that weight concentration is 15-40%, neutralizes with alkali lye then; Neutralization finishes, and adds another functional monomer, heats up after adding linking agent again, under nitrogen protection, adds initiator and carries out the crosslinking copolymerization reaction;
Wherein, described another functional monomer is selected from methyl acrylate, ethyl propenoate, butyl acrylate, hydroxyethyl methylacrylate, Rocryl 410, Methacrylamide, methylene-succinic acid, fumaric acid, methacrylic acid, toxilic acid (acid anhydride), vinyl sulfonic acid;
Described linking agent is selected from N, N '-methylene-bisacrylamide, ethylene glycol diacrylate, a condensed ethandiol double methacrylate, tirethylene glycol double methacrylate, 1, ammediol double methacrylate, Viscoat 295, pentaerythritol triacrylate, glycidyl methacrylate, polyoxyethylene glycol double methacrylate;
Described initiator comprises two kinds of Oxidizing and Reducing Agents, and oxygenant is selected from ammonium persulphate, Potassium Persulphate, Sodium Persulfate; Reductive agent is selected from S-WAT, sodium bisulfite, V-Brite B, Sulfothiorine, formaldehyde and closes Sodium Thiosulfate.
2, preparation method as claimed in claim 1, the add-on that it is characterized in that described functional monomer is the 0.5-50% of the used weight of vinylformic acid.
3, preparation method as claimed in claim 1, the consumption that it is characterized in that described linking agent is the 0.05-2.0% of the used weight of vinylformic acid.
4, preparation method as claimed in claim 1, the consumption that it is characterized in that oxygenant is the 0.01-0.5% of the used weight of vinylformic acid, the consumption of reductive agent is the 0.02-0.75% of the used weight of vinylformic acid.
5, preparation method as claimed in claim 1 is characterized in that the vinylformic acid degree of neutralization is 70-85%.
6, preparation method as claimed in claim 1 is characterized in that neutralizing agent selects sodium hydroxide, potassium hydroxide, yellow soda ash, sodium bicarbonate or ammoniacal liquor for use.
7, preparation method as claimed in claim 1 is characterized in that in the crosslinking copolymerization reaction process that polymerization temperature is controlled at 35-65 ℃, and polymerization reaction time is 10-60 minute.
8, preparation method as claimed in claim 1 is characterized in that also comprising the material after the polyreaction is carried out drying.
9, preparation method as claimed in claim 8 is characterized in that be 1-4 hour time of drying, and drying temperature is 100-190 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104129 CN1087749C (en) | 1997-04-22 | 1997-04-22 | Polyacrylate type high water absorption resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 97104129 CN1087749C (en) | 1997-04-22 | 1997-04-22 | Polyacrylate type high water absorption resin |
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| CN1165152A CN1165152A (en) | 1997-11-19 |
| CN1087749C true CN1087749C (en) | 2002-07-17 |
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| CN 97104129 Expired - Fee Related CN1087749C (en) | 1997-04-22 | 1997-04-22 | Polyacrylate type high water absorption resin |
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